Journal of Alloys and Compounds 659 (2016) 74e81

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Controllable synthesis of CdS nanowire by a facile solvothermal

method and its temperature dependent photoluminescent property
Bing Ren a, 1, Meng Cao a, 1, Qing Zhang a, Jian Huang a, Zhi Zhao b, Xiang Jin c, Chao Li a,
Yue Shen a, Linjun Wang a, *
a

School of Materials Science and Engineering, Shanghai University, Shanghai 200444, PR China
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, PR China
Key Laboratory for Magnetism and Magnetic Materials at Universities of Inner Mongolia Autonomous Region, Baotou Teachers' College, Baotou, 014030,
PR China
b
c

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 17 August 2015
Received in revised form
10 October 2015
Accepted 4 November 2015
Available online 10 November 2015

CdS nanowires with controllable size, orientation, and morphology were synthesized on a large scale by a
solvothermal method. The mechanism for the formation of CdS nanowires evolved from CdS spherical
particles can be divided into a short-period solidesolid transformation process and a long-period
ripening process. Near-band-emission without distinct split phenomenon was observed in the PL
spectrum of CdS nanowires at 10 K. The best t results based on Varshni empirical equation support our
assignment of FX. Temperature dependent integrated peak intensity and linewidth of FX were analyzed
by means of a two-step quenching process model and well tted by Toyozawa's theory. All tted results
including thermal activation energy, LO-phonon energy were close to that observed in bulk CdS, indicating high quality of nanomaterial but also revealing its promising applications in photonics.
2015 Elsevier B.V. All rights reserved.

Keywords:
CdS nanowires
Solvothermal method
Low temperature photoluminescence
Free exciton

1. Introduction
The manipulation of one-dimensional (1D) nanostructures
growth over CdS has attracted considerable attention due to its
intriguing physical properties and potential optoelectronic application [1e3]. Up to now, numerous methods have been employed
to synthesize CdS nanocrystals with controllable morphology and
crystallization, such as, chemical vapor deposition [4,5], hot
colloidal method [6], solvothermal method [7e11], and hydrothermal method [12]. It is well-known that the solvothermal
method is one of the most ideal routes to synthesize wellcrystallized CdS nanowires (NWs) for its low temperature reaction, facile procedure and maneuverability. What's more, it would
be effective and simple to tune its morphology and size by
employing various reactants, temperature, solvents, surfactants,
and coordination agents [8,11,13,14]. Dalvand et al. investigated the
structure and morphology of CdS nanowires synthesized by

* Corresponding author.
E-mail address: ljwang@shu.edu.cn (L. Wang).
1
These authors contributed equally to this work.
http://dx.doi.org/10.1016/j.jallcom.2015.11.030
0925-8388/ 2015 Elsevier B.V. All rights reserved.

solvothermal processing with various solvents [11]. An novel solvothermal method assisted by L-cysteine was reported to control
the nano-structures of CdS from 3D to 1D [14]. However, structure
and morphology controlled synthesis of CdS nanowires inuenced
by solvothermal temperature, reaction time and the amount of Cd
and S source are not studied in detail, especially their effects on the
photoluminescent property of CdS nanowires.
Notably, temperature dependent PL emission spectrum, is a
sensitive but non-destructive tool to measure activation energies of
defects and understand different recombination processes [15e17].
It is widely accepted that optoelectronic devices based on CdS NWs
are usually required to work on a large range of temperature
variation, especially at low temperature; Thus, it is of great
importance to investigate its structure and properties in a broad
temperature variation.
In this study, CdS nanowires with controlled size, orientation,
and morphology were synthesized by a simple solvothermal
method. The mechanism for the formation of CdS nanowires was
investigated in detail. Our systematic study of the temperaturedependent PL spectra illustrated us distinct pictures about FX behaviors from low temperature to room temperature, which would
be essential for the material selection and device fabrication.

B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

2. Experimental
2.1. Materials
All chemical regents (cadmium acetate dihydrate (Cd(CH3COO)

98.5%), L-cysteine (C3H7NO2S,
98.5%) and ethylenediamine (NH2(CH2)2NH2) used in the experiment were of A. R. grade
and supported by J&K chemical Ltd (Shanghai).
2$2H2O,

2.2. Synthesis of CdS nanowires

Typically, x mmol Cd(OAc)2 (Cd(CH3COO)2$2H2O), y mmol Lcysteine, 18 ml ethylenediamine (En) and 2 ml distilled water were
put into a 50 ml Teon vessel (x 0.5, y 1; x 1, y 2; x 1.5,
y 3). Then the autoclave was sealed and heated in an electric oven
at 140  C, 160  C, 180  C and 200  C, respectively. In order to observe
the evolution of CdS nanowires, the processing was maintained for
0.5 h, 1 h, 3 h, 8 h, 12 h and 24 h, respectively. After reaction, the
precipitates were ltered off and washed with ethyl alcohol and
chloroform several times to remove by-products. Finally, the
products were dried at 80  C for 6 h.
2.3. Characterization methods
The X-ray diffraction (XRD) operated on D/MAX 2500 diffractometer with Cu Ka radiation (l 1.54 ) were used to determine
crystalline phase, microstructure. The morphologies of CdS nanocrystals were examined by scanning electronic microscope (FESEM,
JSM-6701F). The nanostructures and growth direction were further
investigated by transmission electron microscopy (TEM), highresolution transmission electron microscopy (HRTEM) and
selected area electron diffraction (SAED) on the JEOL TEM-2010F. PL
spectrum at room temperature was measured by a Raman spectrometer (JY, H800UV) excited by 325 nm wavelength laser. The low
temperature PL measurement was performed on a Jobin Yvon
uorescence spectrometer (Fluorolog-3-TAU) in the temperature
range from 10 to 300 K using 420 nm as an excitation source produced by a Xe lamp.
3. Results and discussion
3.1. Effect of the solvothermal temperature
It is well-known that the solvothermal temperature plays a
crucial role in the formation of CdS nanowires with various crystal
structures, shapes, and sizes. Temperature dependent morphologies are shown in Fig. 1(a)e(d). When the reaction temperature
was kept at 140  C, small randomly oriented nanowires of
diameter~40 nm and length 200e300 nm were formed, revealing
that CdS nanowires proceeded at a very slow rate. As a result, it is
predicted that it takes a relatively longer period to obtain long
nanowires during the ripening process. With the elevating of reaction temperature, the nanowires grew in both length and diameter, besides, with increasingly preferred orientation. At a relatively
high temperature (200  C), however, as-synthesized nanowires
developed into thicker and shorter nanowires, which may be
attributed to the much weakened adsorption of the capping ligands
(En molecules) on the lateral surfaces of the growing 1D nanocrystals at such a high temperature [9].
Generally speaking, the anisotropic growth of CdS is supported
by a certain driving force, which seemed to originate from the En
solvent [18,19]. During the reaction, En is preferred to bind with Cd
ion to form unstable CdeEn complexes. Then, S2 released from Lcysteine would combine with the inorganic-organic hybrid ions
and CdS lamellar products are formed. The volatile interlayered En

75

molecules are gradually decomposed at high temperature

(>150  C); Therefore, pure CdS nanowires are left behind. This can
also be veried by the corresponding XRD measurements
(Fig. 1(e)). All the diffraction peaks can be indexed to hexagonal
phase of CdS wurtzite structure, matched well with those of the
JCPDS standard card (No. 41-1049). However, the XRD peaks of
cubic and hexagonal phases of CdS lie very close to each other. We
could not exclude cubic CdS not existing in our samples. Many researchers always infer the phase composition of CdS nanocrystals
by the intensity ratios of the peaks corresponding to the (103) and
(110) planes of the wurtzite structure [11]. Because the (103) peak
at 48.1 is only assigned to the wurtzite phase CdS, while the (110)
peak at 43.9 may be contributed to both zinc blende and wurtzite
crystal structure CdS. After calculating, the (103)/(110) value from
standard XRD patterns of wurtzite CdS (JCPDS card No. 41-1049) is
1.04. However, the ratio value in nanocrystals at different solvothermal temperature is much lower than 1.04. In this regard, we
can infer that these CdS nanocrystals are mixture of cubic and
hexagonal phases. The samples obtained at lower temperature
(140  C) are in poor crystallinity with several diffraction peaks. As
the increasing of solvothermal temperature, the peak ratio I(110)/
I(100) continuously increases, indicating preferential (110) orientation growth.
Photoluminescent spectroscopy is an effective and powerful
technique to understand the nature of defects and band-to-band
transition in semiconductor materials. Parameters including full
width at half maximum (FWHM) of near band edge (NBE) emission
and the intensity ratio between NBE and defects, are always
calculated to evaluate it quantitatively. PL spectra of the samples
prepared at different temperature are depicted in Fig. 2. It can be
observed that PL spectra are dominated by a sharp near band edge
(NBE) emission located at about 507 nm, accompanied with a broad
defects emission (~700 nm), which are close to those in previous
reports for CdS nanocrystals [9,14,20]. As shown in Fig. 2(b), it is
clear to see that the FWHM of NBE emission decreases with the
increasing of reaction temperature, indicating the total quality
promotion of nanowires. Furthermore, the intensity ratio between
NBE emission and defects emission increases to 14.18 at solvothermal temperature of 180  C before dropping to 12.19 at
200  C. It is widely believed that defects peak at 700 nm is derived
from surface defects, such as the excess of sulfur on the nanowire
surfaces [9]. Notably, L-cysteine as sulfur source is excessive than Cd
source in our processing (L-cysteine: Cd(OAc)2 2:1). Take all the
measurements into consideration, we can conclude that nanowires
synthesized at 180  C are of high crystallinity with less defects.
3.2. Role of amounts of Cd(OAc)2 and L-cysteine
During the experiment, we found that various amounts of
Cd(OAc)2 and L-cysteine but with the same ratio have great inuence on CdS nanocrystals. Fig. 3 (a)e(c) show SEM images of asprepared products at various amounts of Cd(OAc)2 and L-cysteine
with the same volume of solvents (18 ml En and 2 ml water), while
the molar ratio Cd(OAc)2/L-cysteine was kept at the same level. It
can be observed that some urchin-like spheres are obtained when
the least volume of Cd and S source (0.5 mmol Cd(OAc)2 and
1 mmol L-cysteine) were participated in reaction. With the
increasing amounts of Cd and S source, CdS NWs formed and
became wider in diameter but shorter in length. These phenomena
may be associated with the growth mechanism of CdS nanostructures, where L-cysteine dominates the nucleation-growth
process and En dominates oriented assembly process [14]. In
other words, Cd ions prefer to bind with En to form unstable CdeEn
complexes (equilibrium (1)), while other uncoupled Cd2 can coordinate with L-cysteine to form an L-cysteine-Cd2 complex that

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B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

Fig. 1. FESEM images of samples prepared at different temperature: (a) 140  C, (b) 160  C, (c) 180  C, (d) 200  C, (e) XRD patterns for (a), (b), (c) and (d). In all cases, the volume of
Cd(OAc)2 and L-cysteine was kept at 1 and 2 mmol, with reaction time of 24 h.

then decompose into initial amorphous CdS subsequently served as

nuclei for the growth of CdS NWs in solution (equilibrium (2), (3))
[14,19]. Then, S2 released from L-cysteine would combine with the
inorganic-organic hybrid ions to form CdS lamellar products.

Fig. 2. (a) PL spectra of the samples prepared at different temperature. The inset
displays normalized PL spectra of previous samples. (b) FWHM of NBE emission and
intensity ratio between NBE and defects as a function of solvothermal temperature.

However, the volatile interlayered En molecules are decomposed at

high temperature (>150  C). Finally, pure CdS nanowires are left
behind (equilibrium (4)). Too much reagent En would make much
En-chelating atoms be contained in each CdS nuclei and adsorb
onto the incipient CdS nuclei, resulting in a rapid reaction process.
Thus, it would hinder the anisotropic growth of the precursor
originating from the match between the special CdS atomic surface
structures and the linear molecular structure of En. Finally, 3D
urchin-like spheres obtained. This can also be veried by XRD
patterns with multi-peak, indicating polycrystalline nature (see
Fig. 1(d)). When 1 mmol Cd(OAc)2 and 2 mmol L-cysteine were put
into the same solvents, the volume of En relatively decreased. Thus,
the reaction was proceeding at a low pace, providing enough time
for the anisotropic growth of the precursor, with a result of
preferred growth of CdS NWs. Therefore, as-products exhibit
preferred (100) and (110) orientation. However, too much Cd and S
source (1.5 mmol Cd(OAc)2 and 3 mmol L-cysteine) would result in
thicker but shorter nanowires. All diffraction peaks of samples with
various amount of Cd(OAc)2 and L-cysteine can be assigned to
hexagonal phase of CdS wurtzite structure, according to the JCPDS
standard card (No. 41-1049). But the ratios of (103)/(110) are all
lower than 1.04, especially for more amount of Cd(OAc)2 and Lcysteine involved in the chemical reactions (x 1, y 2; x 1.5,
y 3), indicating the mixture nature of cubic and hexagonal phases
in products and the increasing of cubic phase fraction in the
mixture with the increasing amount of Cd(OAc)2 and L-cysteine.

2
coordination
Cd2 2En





! CdEn2

(1)

2
coordination
Cd2 nL  cysteine





! CdL  cysteine2

(2)

2 decomposition

CdL  cysteine2








! CdS nuclei

(3)

2

S2 /CdS
CdEn2

(4)

Fig. 4(a) shows the laser-induced PL spectra of CdS nanowires

synthesized with different amounts of Cd(OAc)2 and L-cysteine. It is
clear to see that PL spectra are dominated by a sharp near band

B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

77

Fig. 3. FESEM images of the samples prepared under different mole of Cd(OAc)2 and L-cysteine: (a) x 0.5, y 1, (b) x 1, y 2, x 1.5, y 3. (d) XRD patterns for (a), (b) and (c).
In all cases, the molar ratio of Cd(Ac)2/L-cysteine 1:2, with reaction for 24 h at 180  C.

edge (NBE) emission located at about 507 nm, accompanied with a

broad defects emission (~700 nm). No obvious shift occurs to the
peaks. When 1 mmol Cd(OAc)2 and 2 mmol L-cysteine are participation in reaction, products exhibit narrowest FWHM while
greatest intensity ratio between NBE emission and defects emission. Hence, prescription (1 mmol Cd(OAc)2 and 2 mmol L-cysteine)
would be benet to form CdS nanowires with less defects
comparing with others.
The morphology and structure of the typical CdS nanowires
synthesized at solvothermal 180  C (x 1, y 2) for 24 h were
further analyzed by TEM and SAED. The panoramic view with low
magnication (Fig. 5(a)) clearly displays a large amount of regularshaped nanowires emerging with a typical diameter of ~48 nm.
Fig. 5(b) records the typical high revolution TEM (HRTEM) image of
nanowire and its corresponding SAED pattern. The crystal lattice
fringes are clearly observed and the spacing of the crystallographic
planes is measured to be about 0.355 nm, matched well with the
(100) plane lattice distance of hexagonal CdS. The SAED pattern
recorded from the single CdS nanowire is indexed to the (110),
(002) and (112) planes of wurtzite phase. HRTEM-EDS element
mapping were performed to clarify the compositional and
elemental distributions in the nanowires, as shown in Fig. 5(c)e(e).
The existence of the two elements of CdS can be conrmed by EDS
data collected from all the points in the selected area. The 2Dprojected elemental maps indicate that Cd and S element distribute
homogeneously throughout the nanowire. All the phenomena
mentioned above reveal that as-prepared CdS nanowire are of
single-crystalline in nature and grow preferentially along the [001]
direction (c axis).

3.3. Evolution of CdS nanowires

In order to explore the evolution of CdS nanowires, holding time
dependent experiments were carried out by varying the reaction
time from 0.5 h to 24 h Fig. 6(a)e(f) exhibit SEM images of CdS
nanostructures synthesized for different time with solvothermal
method at 180  C (x 1, y 2). It can be seen that CdS sub-micro
spheres are formed at the earlier stage (0.5 h), however, with poor
crystallinity, veried by XRD measurements (Fig. 6(g)). When the
holding time was kept at 1 h, a whole lot of nanowhiskers are
formed on the surface of the spherical particles (Fig. 6(b)). With the
increasing of reaction time, spheres constructed from nanorods can
be observed, deduced from nanowhiskers, as depicted in Fig. 6(c).
After growing for more than 8 h, nanowires begin developing,
which maybe ruptured from clew-like particles (Fig. 6(d)e(f)).
Fig. 6(g) shows the XRD patterns of CdS nanostructures synthesized
for different time. For samples synthesized for 0.5 h, the XRD
pattern shows that the majority of the products were poorly crystallized, nearly amorphous property. When the reaction time was
prolonged, the crystallinity of sample was obviously improved.
According to previous discussions, prepared CdS are the mixture of
cubic and hexagonal phases. Compared to other literatures, CdS
nanowires exhibit relatively stronger (100) and (110) diffraction
peaks, while weaker (002) peaks, with the increase of reaction
time. When the time of the reaction reached 24 h, (100), (110) peaks
are dominated with less presence of multiple peaks.
On the basis of the above experimental investigation and
structural determination, the formation of CdS nanowires can be
proposed to undergo following various stages: (1) the formation of

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B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

sub-micro spheres with amorphous property at the earlier stage

(Fig. 6(a)), (2) formation and growth of nanowhiskers on the surface of the spherical particles (Fig. 6(b)), (3) nanorods originated
from nanowhiskers on the surface of the spherical particles
(Fig. 6(c)), (4) rupture of clew-like particles into dispersive nanorods (Fig. 6(d)), (5) ripening growth of nanorods into nanowires
Fig. 6(d)e(f). Evolutionary phenomena of CdS nanostructures
observed are similar to the report of Xu [9], who suggested that a
solidesolid transformation process was involved in the rst three
stages and the last two stage is a Ostwald ripening process [21].
3.4. Temperature dependent photoluminescent properties

Fig. 4. (a) PL spectra of CdS prepared under different amounts of Cd(OAc)2 and Lcysteine. (b) FWHM of NBE emission and intensity ratio between NBE and defects as a
function of mole of Cd(OAc)2.

Low temperature PL spectrum is a kind of useful and sensitive

tool to investigate the electronic structure of CdS nanowires, but
also provides ready insight into their structural quality. As discussed before, ultra-long CdS nanowires with high quality were
synthesized at solvothermal temperature of 180  C (x 1, y 2) for
24 h. It is meaningful to investigate such typical samples by low
temperature PL technique. Fig. 7(a) exhibits temperature dependent PL spectra of CdS nanowires measured from 10 K to 300 K. It
can be observed that a single asymmetric peak at an energy of
2.53 eV in high revolution PL spectra measured at 10 K (the inset of
Fig. 7(a)), which is comparable to the energy for excitonic emission
from bulk CdS, deriving from band-edge recombination assigned as
free exciton (FX). Furthermore, no split peak is observed, differing
from low temperature PL spectrum of CdS nano-belts or
irregularly-shaped nanowires reported in other literatures [5,16].
Compared to low-temperature PL spectrum, PL spectrum at roomtemperature of CdS nanowires is not sensitive to the structure of
defects. Moreover, a broad but strong defects-related emission peak
is more distinct than NBE at low temperature. The energy band
diagram of CdS nanowires at 10 K is exhibited in the inset of Fig
7(b). The possible reason is that there exist more excitons at low
temperature, resulting in the increasing rate of e-h recombination
between exciton band and the vacancy of Cd (VCd). As a result, a
distinct defects-related emission peak was obtained. But the
mechanism of this phenomenon still needs further studies. The FX

Fig. 5. (a) TEM and (b) high-resolution TEM for CdS nanowires synthesized at 180  C for 24 h, while the volume of Cd(OAc)2 and L-cysteine was kept at 1 and 2 mmol, respectively.
STEM-EDS elemental mapping for (c) as-synthesized CdS nanowires, (d) Cd element, (e) S element, respectively. The inset of (b) displays SAED for CdS nanowires.

B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

79

Fig. 6. HRSEM images of six samples, showing different growth stages of CdS nanocrystals. These samples were taken after different aging times: (a) 30 min, (b) 1 h, (c) 3 h, (d) 8 h,
(e) 12 h and (f) 24 h, respectively. (f) XRD curves for six samples mentioned before.

emission peak tends to shift to the shorter wavelength with

decreasing temperature, while quenching of the emission can be
observed at elevated temperatures.
The temperature dependent red-shift of FX emission is illustrated in Fig. 7(b). More intensely drastic electron phonon interaction and lattice expansion at elevated temperature should be
responsible for the red-shift of FX emission line without considering the changing of the exciton binding energy [5,22,23]. The
fundamental energy gap as a function of temperature can be well
tted numerically with empirical equation, known as Varshni
equation [23].

.
ET E0  aT 2 T b

(5)

where E(0) is the band gap assumed at 0 K; a and b are constants

related to materials, which are deemed as Varshni's coefcients.
Notably a represents the linear shift of E(T) at high temperature
resulting from thermal expansion, while b stands for the quadratic
variation of E(T) at low temperature deriving from electron phonon
interaction effect. A good agreement between the experimental
data and the best-t curve is observed for E(0) 2.533 eV,
a 0.3558 meV K1, and b 74.28 K, which is close to others'
reports [5,24].

Fig. 7. (a) Temperature dependent PL spectra of CdS nanowires. The inset reveals high resolution PL spectrum of CdS nanowires at 10 K. (b) A plot of FX peak energy position versus
the temperature for CdS nanowires and the blue dash curve is the corresponding tting result based on Varshni equation. The inset displays the energy band diagram of CdS
nanowires at 10 K. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

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B. Ren et al. / Journal of Alloys and Compounds 659 (2016) 74e81

Differentiating the Varshni equation with respect to temperature, we obtain

h
.
i
dET=dT a 2T=T b  T 2 T b2

(6)

The temperature coefcients dE(T)/dT for CdS nanowires at

300 K can be determined to be about 3.42  104 eV/K, which is in
consistent with the literature value (2.5 to 4.5  104 eV/K),
supporting our assuming [24].
The exciton linewidth (FWHM) can be determined from the
measurements of the lifetime broadening. The lifetime of the
exciton always increases with the decreasing of temperature for a
reduction in the impurity scattering in the crystal, resulting in a
more narrow FX emission. Fig. 8(a) shows the measured linewidth
in the temperature range between 10 K and 300 K. The obtained
value can be well reproduced by Toyozawa's equation [25].

Y A

.

eZu=kT  1 C

(7)

where C is a constant linewidth at low temperature and Zu represents the average energy of the phonon participating in the
quenching process. The t yields C 66 meV, the measured value of

the exciton linewidth at 25 K, and Zu 37.8 meV, which are found

to be in fair agreement with the LO phonon energy of CdS (38 meV)
[26].
The logarithms of the integrated luminescence intensity for free
exciton are plotted versus reciprocal temperature in Fig. 8(b). The
best t for the temperature dependence of the FX luminescence
intensity exhibits a two-step-quenching process as described by
the following expression [27].

IT I0=1 C1 exp  E1 =kT C2 exp  E2 =kT

(8)

where I(T) represents the integral intensity of the FX at different

temperatures; I(0) indicates the theoretical integral intensity at 0 K;
C1 and C2 are tting parameters and E1 and E2 are the thermal
activation energies in the low- and high-temperature quenching
processes, respectively. From the tting we can get two activation
energies for thermal activation process are 29.3 meV and 4.3 meV.
Noticeably, the activation energy of 29.3 meV corresponds to
thermal dissociation of the free exciton at the ground state and is
comparable with the exciton binding energy of (28e30) meV
[24,28].
From the systemically experimental and theoretical analysis, the
observation of FX and tted optical constants indicate high quality
of CdS nanowires, because the emission peak of the exciton can
only be observed under the condition of long-range Coulomb
coupling between the electron and the hole. It can be proposed that
CdS nanowires reported in this paper exhibit excellent property
nearly closed to that of bulk CdS materials.
4. Conclusions
In summary, uniform and ultra-long CdS nanowires with high
quality were synthesized on a large scale by a solvothermal method
and characterized by XRD, SEM and TEM. The mechanism for the
formation of CdS nanowires evolved from CdS spherical particles
can be divided into a short-period solidesolid transformation
process and a long-period ripening process. The PL spectrum of CdS
nanowires at 10 K did not show split phenomenon. The best t
results based on Varshni empirical equations support our assignment of FX. Temperature dependent integrated peak intensity of FX
was analyzed by means of a two-step quenching process model,
where the thermal activation energy of FX is estimated to be
29.3 meV. Besides, the temperature dependence of the linewidth
for FX can be well tted by Toyozawa's theory. The average energy
value of Zu used for Toyozawa's theory was 37.4 meV, and this value
was found to be in good agreement with the LO-phonon energy of
CdS (38 meV). All these phenomena indicate high quality of
nanomaterial, but also reveal its promising applications in
photonics.
Acknowledgments
We gratefully thank the Instrumental Analysis & Research
Center, Shanghai University for XRD and HR-TEM analysis. The
temperature dependent PL spectroscopy was measured in Hefei
National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China. This work was nancially supported by the National Natural Science Foundation of
China (Grants No. 61176072, 61006089, 11404320), and Shanghai
City Board of Education Innovation Fund (13YZ003).

Fig. 8. (a) Exciton linewidth as a function of temperature in the range between 10 and
300 K. (b) Natural logarithm of the integrated P L intensity of FX as a function of 1/T,
and the blue dash curve is the corresponding t based on a two-step-quenching
process. (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.)

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