Chemical Physics Letters 481 (2009) 220–223

Contents lists available at ScienceDirect

Chemical Physics Letters

journal homepage: www.elsevier.com/locate/cplett

Raman spectroscopy of Co-doped wurtzite ZnS nanocrystals

Chong Bi a, Liqing Pan a,*, Mei Xu a, Jinhua Yin a, Zhengang Guo a, Liangqiang Qin a, Hao Zhu b, John Q. Xiao b
a
Department of Physics, University of Science and Technology Beijing, Beijing 100083, China
b
Department of Physics and Astronomy, University of Delaware, Newark, DE 19716, USA

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

Article history: Raman spectra of wurtzite CoxZn1 xS nanocrystals were investigated. Two main broad Raman peaks cen-
Received 9 July 2009 tered at 259 and 331 cm 1 were observed for low doping concentration, which are assigned to A1(TO) and
In final form 25 September 2009 E1(LO) phonon modes and had large redshift compared with that for bulk counterpart. It is suggested that
Available online 30 September 2009
such phenomena be attributed to phonon confinement effects, relaxation of the wave-vector selection
rule due to doping effects. Besides two broad peaks, Raman spectra of high doping concentration exhibit
five additional peaks at 229, 308, 340, 348, and 362 cm 1, whose relative intensities are enhanced while
frequencies keep constant with increasing Co concentration due to the small reduced mass difference.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction spectroscopy of ZnS doped by Mn, Fe, Ni, Co, Cu, Al, and Cr have been
studied [11–15], but most of them have the cubic zinc blende (sphal-
Semiconductor nanocrystals have attracted considerable atten- erite) structure which is a stable phase at low temperature for ZnS.
tion over the past decade because of their novel electric and optical Few works regarding the Raman spectroscopy of hexagonal (wutzite)
properties originating from Quantum confinement effects. More- ZnS doped with metal ions are reported, because hexagonal phase,
over, in the strong confinement regime, the grain size spatially the high-temperature (1020 °C) [16] polymorph of sphalerite, is very
confined effects are expected to influence both electronic and difficult to be formed at mild temperature [17,18]. Co-doped wurtzite
vibrational states and their coupling. The lattice dynamics modifi- ZnS nanocrystal, as an important member in the family of ZnS-based
cations in nanocrystals can be explained by considering that trans- DMSs, has been synthesized at low temperature (150 °C) and its
lational invariance is significantly broken when the crystal structural and luminescent properties also have been studied in our
extension is limited to 100 nm and a description of atomic vibra- previous work [19]. In this work, we report the detailed results of Ra-
tions in terms of phonons with a well-defined wave vector is no man spectra of Co-doped wurtzite ZnS nanocrystals (CoxZn1 xS,
longer valid in such a domain [1,2]. For a long time, nondestructive 0.0031 6 x 6 0.084).
and fast Raman scattering has been recognized as a powerful tool
to probe such nano-related effects in nanomaterials. One of the
main reasons why this approach is particularly valuable is the pos- 2. Experimental
sibility to analyze quantitatively some of the observed spectral fea-
tures in terms of conformational and structural organization [3,4]. The synthesis of CoxZn1 xS nanocrystals was carried out by a
In addition, the nature of substitution, the concomitant defects and solution-phase thermal decomposition route at 150 °C as described
the lattice disorder in diluted magnetic semiconductor (DMS) [5,6] in our previous work [19]. Briefly, nominal amounts of Co(N-
where the nonmagnetic host ions are partially substituted by the O3)2
6H2O and ZnCl2 at 15 mM and thiourea at 15 mM were
magnetic ions has always been the focus of scientific interest. Ra- weighed and dissolved into 200 mL of ethylene glycol for each
man spectroscopy can reveal the detailed modification of the lat- reaction. Under vigorous magnetic stirring, the pink reactant solu-
tice vibrational modes caused by the lattice distortion in such tion was heated to 150 °C and maintained for 2 h. The color of reac-
nanocrystals . tant solution turned milky white with yellow about 15 min from
As one of the important wide and direct band gap semiconductors, initial pink, and then gradually became yellow for low doping con-
ZnS has received a lot of attention due to its excellent properties and centrations or black for high doping concentrations. After the solu-
wide applications as phosphors, electroluminescent materials, solid tion was cooled to room temperature, the prepared CoxZn1 xS
state solar window layers, and photocatalysts [7–10]. Doping with samples were separated from the product by centrifugation, and
suitable elements in ZnS can significantly modify its structural, vibra- washed several times with deionized water and ethanol. Finally,
tional, and optical properties [11,12]. In the previous studies, Raman the CoxZn1 xS samples were dried in a desiccator for 10 h at
80 °C until complete evaporation of the solvent. As a comparison,
* Corresponding author. Fax: +86 10 62332587. a control sample was also prepared by using this method, but with-
E-mail address: lpan@sas.ustb.edu.cn (L. Pan). out ZnCl2 added.

0009-2614/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2009.09.089
 C. Bi et al. / Chemical Physics Letters 481 (2009) 220–223 221

The real doping concentrations of Co (x) in the as-prepared

CoxZn1 xS samples were determined by inductively coupled plas-
ma atomic emission spectrometry (ICP-AES, JY, ULTIMA, France).
The structure of samples was characterized by X-ray powder dif-
fraction (XRD) with Cu Ka radiation filtered by a crystal monochro-
mator (wavelength k = 0.15417 nm). The morphology and
electronic diffraction (ED) patterns of the nanocrystals were ob-
served by a JEM-2010 high-resolution transmission electron
microscope (HRTEM) operated at 200 kV. The TEM samples were
prepared by re-dispersing a drop of ethanol dissolved with the
CoxZn1 xS powder on the copper mesh. The Raman spectroscopy
of the samples was measured by a triple Horiba Jobin Yvon
T64000 spectrometer equipped with an optical microscope and li-
quid-nitrogen-cooled back-illuminated charge-coupled device
(CCD) detector. The CoxZn1 xS nanocrystals were pressed into thin
slices for the measurement. A 50 long-working-distance objec-
tive was employed to focus the laser beam, with a wavelength of
785 nm, into a spot of about 4 lm in diameter on the samples,
and to collect the scattered light. All measurements were carried
out at room temperature under ambient atmosphere and a base-
line has been subtracted from the measured Raman spectra to de-
duct the background and make the comparison of the Raman peaks
more definite.

3. Results and discussion

Table 1 shows the correspondence of the real x in CoxZn1 xS de-

tected by ICP to the nominal Co doping level in reactant solution.
Although a little difference between them, it is clear that both of
them have a consistent tendency. The representative HRTEM
images of CoxZn1 xS sample (x = 0.084) in Fig. 1a and b show the
lattice fringes of nanocrystals with a spacing of 0.225 nm, which
Fig. 1. (a, b) Typical HRTEM images of CoxZn1 xS sample (x = 0.084). The insert is
corresponds to an interplanar distance of the (102) plane of hexag- the corresponding ED pattern. (c) The corresponding XRD pattern.
onal ZnS (JCPDS No. 80-0007). The average size of these nanocrys-
tals estimated from HRTEM observation is about 5 nm. The
corresponding selected area ED pattern is presented in the inset
Zn ions, which also be confirmed by the Raman scattering depicted
of Fig. 1a. The ED pattern shows a set of concentric rings instead
in the following text.
of sharp spots as a diffraction from polycrystalline particles. The
As one knows, wurtzite ZnS belongs to C46v (C63mc) with a prim-
diffraction rings can be indexed to (0 0 2), (1 1 0), (1 1 2) planes
itive cell of two formula units where all the atoms occupy the C3v
of the hexagonal ZnS phase (JCPDS No. 80-0007). It has been fur-
sites. Group theory predicts the following q = 0 lattice phonons:
ther confirmed by the XRD measurement. The typical XRD pattern
one A1 and one E1 mode which are both IR and Raman active,
of Co0.084Zn0.916S is presented in Fig. 1c. It shows that even in high
two E2 modes which are Raman active, and two silent B1 modes
doping concentration (x = 0.084), the XRD pattern of the prepared
[20–22]. The A1 and E1 symmetry splits into two components:
sample is in good agreement with hexagonal ZnS (JCPDS No. 80-
transverse optic (TO) and longitudinal optic (LO), and both of them
0007, vertical bars), which is consistent with the results obtained
are highly isotropic, A1 (TO) = E1 (TO) and A1 (LO) = E1 (LO), which
from ED pattern. The significant broadening of the diffraction
is a characteristic feature of the wurtzite ZnS [22]. Fig. 2 displays
peaks is ascribed to the tiny grain size of the nanocrystals. Accord-
the Raman spectra (100–800 cm 1) of CoxZn1 xS nanocrystals
ing to Debye–Scherrer formula, the average size of the sample is
(x = 1 corresponding to the control sample). It is not surprised that
about 5 nm, which is consistent with the HRTEM results. No other
no Raman peak was observed for control sample, because crystal-
peak of impurity phase such as Co or CoS was detected for such
line CoS can be hardly formed in such experimental condition as
high doing concentration. It should be pointed that the XRD pat-
proved by XRD result. The overlapping bands were deconvoluted
tern of the control sample (not shown) did not show any peaks,
into separated peaks by Lorentzian fitting and typical fitting curves
which reveals here the crystalline CoS phase can be hardly formed.
for high doping (x = 0.018) and low doping (x = 0.0031) samples are
However, the clear boundary of each nanocrystal (as shown in
shown in Fig. 3a and b, correspondingly. The dashed lines denote
Fig. 1a and b, typically) and the ED patterns of randomly selected
the individual components by Lorentzian fitting, and the smooth
spots show that few amorphous phases exist even in so high dop-
solid lines denote the sum of individual fitting lines. For low dop-
ing samples. Therefore, it is reasonable to conclude the cobalt ion
ing concentration, there are two broad peaks centered at 259 and
incorporation within ZnS nanocrystals, probable substitution for
331 cm 1, respectively, which are different from the corresponding
A1(TO) and E1(LO) phonon modes of bulk wurtzite ZnS (273 and
351 cm 1, respectively) [22]. Such phonon softening and line
Table 1
broadening of the Raman peaks can be associated with phonon
Co doping concentration in reactant solution (nominal x) and x of CoxZn1 xS samples
(real x) analyzed by ICP-AES. confinement effects [2]. It is known that the optical properties of
crystals reveal itself different when their size becomes tiny. The
Nominal x 0.0030 0.0050 0.010 0.040 0.050
reduction of the repetition period in a system of small particles,
Real x 0.0031 0.0062 0.018 0.053 0.084
owing to the boundaries, will lead to breakdown of the law of con-
222 C. Bi et al. / Chemical Physics Letters 481 (2009) 220–223

observed through the redshifts and broadenings in the allowed Ra-

man peaks [26,27]. In addition, the local heating induced by laser
in the sample is also a possible reason for the observed redshift
[28,29].
In Fig. 3a , besides two main broad peaks for low doping sam-
ples, the Raman spectra also show five additional modes with fre-
quencies of 229, 308, 340, 348, and 362 cm 1 for high doping
concentration. As analyzed above, the five additional modes cannot
be from crystalline or amorphous CoS, because no crystalline CoS
phases were observed by XRD and HRTEM and no Raman peak
was observed for amorphous phase, so the only possible is they
originate from the incorporation of cobalt ion in ZnS nanocrystals,
which is also consistent with the above conjecture based on XRD
and HRTEM results. There are two reasons why the incorporation
can induce these additional modes: one is the relaxation of Raman
Fig. 2. Raman spectra of CoxZn1 xS samples at the range of 100–800 cm 1
(x = 1 selection rules which take place in Brilliouin central zone. As men-
corresponding to the control sample). tioned above, Co ions substitution, particularly in large concentra-
tions, induces not only topological disorder but often also
structural disorder in the host crystal. In this case, crystal momen-
servation of momentum which holds strictly only for large crystals. tum is no longer conserved, and q – 0 phonons can appear in the
Ultimately, the fundamental q = 0 Raman selection rule is relaxed Raman spectra [15,30]. Another reason is the introduction of host
for such finite-size domain, allowing the participation of phonons lattice defects. When Co ions were doped into ZnS lattice, host lat-
away from the Brillouin-zone center. In such case, the width of tice defects, such as sulfur and zinc vacancies, were created. Simi-
the Raman peaks in the fundamental region broadens, and the lar to the metal ions doped ZnO [6,31], they will induce new Raman
maxima of peaks should be red shifted as compared with the bulk modes and should lead to the relative intensities of these new
crystals [23]. Another possible reason for the redshift and broaden- peaks increasing with the increment of Co content, which has been
ing of the Raman peaks is doping effects. When Co ions substitute approved by the enhanced intensity of those five additional peaks
the Zn ions, the substitution affects the local crystal field due to al- as shown in Fig. 2. It is worth to mention that the frequency of the
loy potential fluctuations [24] resulting from the failing of transla- Raman active modes of the ZnS host remained basically to be unal-
tional invariance in the doped lattice, which also results in the tered even for large impurity concentrations (see Fig. 2), which is
breakdown of the q = 0 Raman selection rules [25] thus making different from most other doped crystals [32,33]. Moreover, the
scattering events from the extended Brillouin central zone can be frequencies of five additional features observed in high doping
samples are also independent of doping concentration. These
unconventional Raman behaviors can be attributed to remarkably
similar effective masses of the end members (lZnS = 21.48 amu,
lCoS = 20.74 amu, and Dl = |lZnS lCoS| = 0.74 6 2) for CoxZn1 xS
[13], and are different from other metal ions doped ZnS such as
Cd [34] whose effective mass difference Dl = 3.43 > 2.

4. Conclusions

Co-doped wurtzite ZnS nanocrystals synthesized by a solution-

phase thermal decomposition route at 150 °C were investigated by
ICP, XRD, HRTEM, and Raman scattering. The XRD and HRTEM re-
sults show that the as-prepared samples are hexagonal wurtzite
structures and the uniform diameter is about 5 nm. No secondary
phase was found. Room temperature Raman spectra for low doping
concentration exhibit two main broad peaks centered at 259 and
331 cm 1, which are assigned to the A1(TO) and E1(LO) phonon
modes, respectively, and indicate a redshift compared with the Ra-
man spectra of bulk wurtzite ZnS. Phonon confinement effects,
relaxation of the wave-vector selection rule, and local heating in-
duced by laser in the sample should be responsible for the redshift
and broadening of the two peaks. Besides the two peaks mentioned
above, five additional peaks at 229, 308, 340, 348, and 362 cm 1
are observed for high doping concentration, and their relative
intensities increase with the increase of Co doping concentration,
while their frequencies are independent of doping concentration.
In addition, the possible reasons for such unconventional Raman
behaviors are also discussed.

Acknowledgements

Fig. 3. Raman spectra of (a) Co0.018Zn0.982S and (b) Co0.0031Zn0.9969S nanocrystals. This work was supported by NSF of China (Grant Nos.
Dashed lines: the results of multipeak Lorentz fittings. 50472092, 50672008 and 50971023), NSF (Grant No: 3122133),
 C. Bi et al. / Chemical Physics Letters 481 (2009) 220–223 223

and U.S. Environmental Protection Agency STAR Program (Grant [15] M. Zigone, M. Vandevyver, D.N. Talwar, Phys. Rev. B 24 (1981) 5763.
[16] J.L. Birman, Phys. Rev. 115 (1959) 1493.
No. R833318).
[17] Z.X. Deng, C. Wang, X.M. Sun, Y.D. Li, Inorg. Chem. 41 (2002) 869.
[18] S.H. Yu, M. Yoshimura, Adv. Mater. 14 (2002) 296.
References [19] C. Bi et al., Mater. Chem. Phys. 116 (2009) 2009.
[20] C.A. Arguello, D.L. Rousseau, S.P.S. Porto, Phys. Rev. 181 (3) (1969) 1351.
[1] H. Richter, Z.P. Wang, L. Ley, Solid State Commun. 39 (1981) 625. [21] M. Abdulkhadar, B. Thomas, Nanostruct. Mater. 5 (1995) 289.
[2] I.H. Campbell, P.M. Fauchet, Solid State Commun. 58 (1986) 739. [22] O. Brafman, S.S. Mitra, Phys. Rev. 171 (1968) 931.
[3] J.R. Durig, Y.E. Nashed, Y. Jin, G.A. Guirgis, J. Mol. Struct. 449 (1980) 1. [23] T. Kanata, H. Murai, K. Kubota, J. Appl. Phys. 61 (1987) 969.
[4] D.A. Pink, T.J. Green, D. Chapman, Biochemistry 19 (1980) 349. [24] P. Parayanthal, F.H. Pollak, Phys. Rev. B 52 (1984) 1822.
[5] K. Samanta, P. Bhattacharya, R.S. Katiyar, W. Iwamoto, P.G. Pagliuso, C. Rettori, [25] B. Jusserand, J. Sapriel, Phys. Rev. B 24 (1981) 7194.
Phys. Rev. B 73 (2006) 245213. [26] B.A. Weinstein, Solid State Commun. 20 (1976) 999.
[6] J.B. Wang, G.J. Huang, X.L. Zhong, L.Z. Sun, Y.C. Zhou, E.H. Liu, Appl. Phys. Lett. [27] R. Shuker, R.W. Gammon, Phys. Rev. Lett. 25 (1970) 222.
88 (2006) 252502. [28] K.A. Alim, V.A. Fonoberov, A.A. Balandin, Appl. Phys. Lett. 86 (2005) 053103.
[7] K. Manzoor, S.R. Vadera, N. Kumar, T.R.N. Kutty, Appl. Phys. Lett. 84 (2004) 284. [29] L. Bergman, X.B. Chen, J.L. Morrison, J. Huso, A.P. Purdy, J. Appl. Phys. 96 (2004)
[8] N. Karar, F. Singh, B.R. Mehta, J. Appl. Phys. 95 (2004) 656. 675.
[9] A.B. Cruz, Q. Shen, T. Toyoda, Mater. Sci. Eng. C 25 (2005) 761. [30] J.G. Naeini, B.M. Way, J. Dahn, J.C. Irwin, Phys. Rev. B 54 (1996) 144.
[10] D.X. Jiang, L.X. Cao, G. Su, H. Qu, D.K. Sun, Appl. Surf. Sci. 253 (2007) 9330. [31] B.C. Cheng, Y.H. Xiao, G.S. Wu, L.D. Zhang, Appl. Phys. Lett. 84 (2004) 416.
[11] Y.T. Nien, I.G. Chen, Appl. Phys. Lett. 89 (2006) 261906. [32] R.G. Alonso, E.K. Suh, A.K. Ramdas, N. Samarth, H. Luo, J.K. Furdyna, Phys. Rev. B
[12] M. Zigone, M. Vandevyver, D.N. Talwar, Phys. Rev. B 24 (1981) 763. 40 (1989) 3720.
[13] S.J. Sandoval, A.L. Rivera, J.C. Irwin, Phys. Rev. B 68 (2003) 054303. [33] D.N. Talwar, Z.C. Feng, P. Becla, Phys. Rev. B 48 (1993) 17064.
[14] A. Krol, A. Hoffmann, J. Gutowski, Phys. Rev. B 38 (1988) 10946. [34] Y.T. Nien, P.W. Chen, I.G. Chen, J. Alloys Compd. 462 (2008) 398.