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Optics Communications 295 (2013) 45–52

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Optics Communications
journal homepage: www.elsevier.com/locate/optcom

First-principle study of optical properties of Cu-doped CdS


Ping Li a,b, Chang-wen Zhang b, Jie Lian a,n, Miao-juan Ren b, Pei-ji Wang b, Xiao-hong Yu a, Shang Gao a
a
School of Information Science and Engineering, Shandong University, Jinan, Shandong 250100, People’s Republic of China
b
School of Physics and Technology, University of Jinan, Jinan, Shandong 250022, People’s Republic of China

a r t i c l e i n f o abstract

Article history: Based on the full-potential linearized augmented plane wave (FLAPW) method, we study the electronic
Received 4 September 2012 structure and optical properties in the Cu-doped CdS semiconductor. We find that the d orbitals of Cu
Received in revised form are strongly hybridized with the p orbitals of S near the Fermi level, resulting in p and d charge transfer
8 December 2012
between Cu and S atoms. These lead to transit from a semi-metal to metal with increase of Cu dopant
Accepted 25 December 2012
concentrations, enhancing the conductivity of CdS significantly. As a consequence, the optical transition
Available online 24 January 2013
between valence band and unoccupied d states of Cu enhances greatly, and is stronger than the
Keywords: intrinsic optical transition of CdS semiconductor. Along with the increase of Cu concentrations, the
CdS absorption spectra gradually shift to higher energy (blue shifts), and optical absorption of Cd1  xCuxS
First-principles
increases in the visible range.
Optical properties
Crown Copyright & 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction been demonstrated including high quality field effect transistors,


optical switches, and light emitting diodes [15–20].
Over the last 30 years, the II–VI and III–V based semiconduc- In generally, electronic, magnetic, and optical properties of
tors have attracted a great deal interest due to their potential use semiconductor can be tuned efficiently by doping other elements,
as photoconductors and in fabricating optical detectors, light such as Mn, Fe, and Co-doped GaN [21–23], Cd and Nb-doped TiO2
sources and optoelectronic devices [1–3]. Their structural, elec- [24,25], Fe or Co-codoped In2O3 [26], Cu-doped ZnS [27] and ZnO
tronic and optical properties have been extensively studied in [28], et al. Recently, many progresses on Cu doped CdS have been
both theoretical and experimental works [4–6]. One of the reported, for example, quenching of photocurrent in Cu-doped
motives to investigate their properties is the desire to tune and CdS thin films prepared by Spray pyrolysis technique [34], Cu-
control the energy band gap of semiconductors, which provides doped CdS with the long-range ferromagnetism by First-
the base for achieving optimal range over which optical detectors principles calculations[35]. Following these conventions, based
and other optoelectronic devices operate [7,8]. More especially, on first-principles calculations, we study on the electronic struc-
the wide band gap II–VI semiconductors, such as ZnO, ZnS, et al., tures and optical properties of Cu-doped CdS semiconductor.
with the possibility of tailoring lattice parameters and band gap These results open a new route to CdS-based semiconductors in
through doping foreign atoms have recently drawn considerable optoelectronic applications.
attention because of their use in solar cells, electroluminescent
devices, light emitting and laser diodes[9,10]. Recently, to further
exploit their potential utilization in optical devices, a lot of 2. Models and calculation method
experimental and theoretical works have been done on ZnO-
based semiconductors [11–14]. The CdS semiconductor was generally adopted a hexagonal
Cadium sulfide (CdS) as an important II–VI group semicon- wurtzite structure with space group symmetry of P63mc. Each
ductor, is of considerable importance in optoelectronic applica- primitive cell contains two pairs of S and Cd atoms, in which Cd
tions because of its wide energy band gap (2.42 eV), which atom is located in the center of the tetrahedron composed of four
happens to be in the visible range. Also, CdS has been widely S atoms, i.e. CdS4 tetrahedron, and the arrangement of S atom is
used as an n-type window material in thin-film solar cell devices. similar to that of Cd atom. The primitive cell parameters adopted
In particular, several recent applications using CdS sheets have experiment number are a¼4.14 Å, c¼ 6.71 Å, a ¼ b ¼901, g ¼1201.
Based on the primitive cell, a 3  3  2 CdS supercell is con-
structed in Fig. 1(a). We also construct six configurations in which
a pair of Cu atom substitutes Cd in CdS supercell. After structural
n
Corresponding author. Tel.: þ86 0531 88361208. optimization, we find the ground-state configuration corresponds
E-mail address: lianjie_lip@163.com (J. Lian). to the shortest Cu–Cu distant. Based on these structural

0030-4018/$ - see front matter Crown Copyright & 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.optcom.2012.12.086
46 P. Li et al. / Optics Communications 295 (2013) 45–52

Fig. 1. Structure of CdS (3  3  2) supercell (a) pure CdS; (b) Cd1  xCuxS. Yellow, red and blue balls represent S, Cu and Cd, respectively. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

Cd_4d
tot DOS 6
200
DOS(states/eV)

0 0

-200
-6

Cd-5s S-3s
S-3p
0.1 0.1
DOS(states/eV)

0.0 0.0

-0.1 -0.1

-15 -10 -5 0 5 -15 -10 -5 0 5


Energy(eV) Energy(eV)

Fig. 2. DOS of pure CdS (a) TDOS, (b) LDOS of Cd 4d, (c) LDOS of Cd 5s, (d) LDOS of S 3s and 3p.

parameters, we calculate electronic and optical properties of Cu- c¼6.71 Å. Fig. 2 presents the total and partial DOS (PDOS) of the
doped CdS by replacing Cd up to 4 atoms in nearest-neighboring pure CdS semiconductor. It can be seen that the wurtzite CdS bulk
positions [Fig. 1(b)], corresponding to the Cu doping concentra- is direct band gap semiconductor with a band gap of 1.08 eV,
tions with x¼0, 0.0278, 0.0556, 0.0833 and 0.1111, respectively. which is consistent with the previous results [32]. The valence
All calculations have been performed with the full potential band can be divided into three different regions: the first part
linearized augmented plane wave (FLAPW) method, embedded in from 4.4 to 0 eV is mainly contributed by s states of Cd and S
wien2k code [29]. The generalized gradient approximation (GGA) (the lower part), as well as 4d states of Cd and 3p states of S ( near
[30] is used to treat the exchange correlation potential. The the Fermi level ), similar to the low valence band character
parameter RminKmax is chosen as 6.0. Following the Monkhorst– reported by Stoffel [33]; the second part from 7.8 to  6.4 eV
Pack scheme [31], a 3  3  2 k-point mesh is adopted. All comes mainly from 4d states of Cd; and the third part from  12.5
structures constructed are relaxed. The relaxations of lattices to  11.6 eV is mainly contributed by 3p states of S and s states of
are not stopped until the forces on each ion are converged to S and Cd. In addition, the lowest conduction band consist of 5s
less than 0.02 eV/Å. states of Cd and 3s states of S. These results are in qualitative
agreement with the experiment obtained by Stoffel [33], indicat-
ing the availability of our computational method.
3. Results and discussion To tune its electronic properties, we first dope a single Cu atom
into CdS. After structural optimization, we find that the relaxed
3.1. Electronic structure Cu–S bond length of CuS4 tetrahedron is 2.32 Å, which is shorter
than CdS (2.55 Å) in pure CdS semiconductor. These can be
We first relaxed the geometric structure of pure CdS, as shown attributed to the difference of atomic radius of Cu2 þ (0.73 Å)
in Fig. 1. After structural relaxation, the equilibrium lattice and Cd2 þ (0.95 Å), as well as the higher electronegativity of Cu
parameters are found to be a¼4.15 Å and c¼6.72 Å, which are (1.90) compared to Cd atom (1.69). The calculated DOS and
slightly larger than the experimental results of a ¼4.14 Å and corresponding band structure are shown in Fig. 3. Comparing to
P. Li et al. / Optics Communications 295 (2013) 45–52 47

0.2
Cu-4s
DOS(states/eV)

tot DOS
300
0.0
0

-300 -0.2

4
DOS(states/eV)

Cu-3d S-3p
0.6

0 0.0

-4 -0.6

S-3s 8
DOS(states/eV)

1.2 Cd-4d

0.6 0

0.0
-8
-0.6
-15 -10 -5 0 5 -15 -10 -5 0 5
Energy(eV) Energy(eV)

Fig. 3. Calculated band structure and DOS of one Cu-doped CdS supercell. The horizontal line indicates the EF position. (a) band structure, (b) DOS.

the undoped CdS, the remarkable feature in energy band for S atoms. We find that 1.77 electrons are transferred from Cu to
Cd1  xCuxS is that the spin-up channel preserves a semiconduct- the neighboring S atom. The valence band near the Fermi lever is
ing behavior with a band gap of 1.00 eV, smaller than that of pure mainly composed of Cu 3d electronic states strongly hybridized
CdS, while in spin-down channel, the impurity bands induced by with S 3p states, while from  12.5 to  11.6 eV in energy, the
Cu dopant appear crossing over the Fermi level, which indicates third part of the valence band is mainly contributed by 3s states
an intriguing half-metallic behavior. Obviously, the charges of S. The conduction band is mainly formed from Cu 3d and Cu 4s
within the impurity bands are sufficiently mobile and can be states hybridized with Cd 5s states.
excited easily from the valence band to the conduction band, To check the effects of the on-site Coulomb interactions
resulting in enhancement of the conductivity. Fig. 3(b) shows the associated with transition metal d electrons on the electronic
total DOS (TDOS) of the Cd1  xCuxS system and the PDOS of the Cu properties, we employ LDA þU calculations with parameter
dopant and the nearest-neighboring Cd and S atoms. The sub- values of U¼3.0 eV, J ¼0 eV, and U¼8.0 eV, J ¼0.9 eV to explore
stitution of Cd by Cu does not lead to the spin polarization of the the absolute position of the Cu 3d levels with respect to the Fermi
conduction band but results in a significant spin polarization of level of Cu-doped CdS (Fig. 4). Comparing to results from GGA
the valence band. Strong coupling between the d orbitals of Cu calculations, we can see that the partial occupied states of Cu d at
atoms and the p orbitals of S atoms near the Fermi level can be Fermi level have not obvious changes by applying LDA þU
seen from Fig. 3(b). The d orbitals of Cu are hybridized with the scheme. But the remarkable feature in energy band for Cd1  xCuxS
p orbitals of S, enhancing p and d charge transfer between Cu and is that the spin-up channel forms a band gap of 1.09 eV and
48 P. Li et al. / Optics Communications 295 (2013) 45–52

100 8
U=3.0eV,J=0eV Cu-3d(U=3eV)

DOS(states/eV)

DOS(states/eV)
50

0 0

-50 -4

-100 -8
-5 -4 -3 -2 -1 0 1 2 3 4 -5 -4 -3 -2 -1 0 1 2 3 4
Energy(eV) Energy(eV)

100 8
U=8.0eV,J=0.9eV Cu-3d(U=8eV)

50 4

DOS(states/eV)
DOS(states/eV)

0 0

-4
-50

-8
-100
-5 -4 -3 -2 -1 0 1 2 3 4 -5 -4 -3 -2 -1 0 1 2 3 4
Energy(eV) Energy(eV)

Fig. 4. DOS of one Cu-doped CdS supercell with LDA þU. The horizontal line indicates the EF position. (a) TDOS(U ¼ 3 eV,J¼ 0 eV), (b) LDOS of Cu 3d (U¼ 3 eV, J ¼0 eV),
(c) TDOS(U ¼8 eV,J¼0.9 eV), (d) LDOS of Cu 3d(U ¼8 eV,J¼ 0.9 eV).

1.16 eV for U¼3 eV and U¼8 eV, respectively, slightly larger than Table 1
the GGA results (1.00 eV). So the predicted optical properties are Relaxed Cu–S average bond length of the CuS4
tetrahedron after structural optimization. For com-
robust not depending on the selective U values.
parison, we also present the pure Cd–S bond
Next, we further increase the Cu doping concentrations in length.
Cd1  xCuxS with 2, 3, 4 Cu atoms, corresponding to x ¼0.0556,
0.0833, and 0.1111, respectively. To examine the doping possibi- x Cu–S average bond length (Å)
lity of Cu and identify the stable dopant position, we calculate the
formation energy of the Cu dopant in the CdS defined by 0 2.55
0.0278 2.32
Ef ¼ EðCdS:CuÞEðCdSÞ þ nCd mðCdÞ þ nS mðSÞnCu mðCuÞ ð1Þ 0.0556 2.30
0.0833 2.29
where E (CdS:Cu) is the total energy of the supercell with n Cd 0.1111 2.29
atoms replaced by Cu atoms and E(CdS) is the corresponding
energy in bulk structure. n is the number of ions (Cd, S, or Cu)
exchanged between a perfect cell and its corresponding reservoir
to form a defect, and m is the chemical potential of Cu, S, or Cd.
Two chemical extremes are considered. The upper limits for m(Cd) Table 2
(Cd-rich conditions) and m(S) (S-rich conditions) are determined Number of electrons transferred between Cu and S
as the total energies of metallic Cd and bulk S, respectively. The atoms with x¼ 0.0278, 0.0556, 0.0833, and 0.111.
chemical potentials of Cd under S-rich conditions and S under
x The transferred charges (per Cu)
Cd-rich conditions obtained from the thermodynamic equilibrium
m(Cd)þ m(S)¼ m (CdS). The calculated formation energies of one 0.0278 1.77
Cu-doped CdS are 1.98 eV and 0.74 eV in Cd-rich and S-rich 0.0556 2.01
conditions, respectively. It is noted that the Cu dopant prefers to 0.0833 2.03
0.1111 2.04
substitute for the Cd site under S-rich conditions. For two Cu,
three Cu and four Cu doped CdS, the formation energy is 1.16 eV,
1.19 eV, and 1.20 eV, respectively. The moderate formation energy increasing the doping Cu concentrations, Cu 3d states are hybri-
indicates that Cu doped CdS may be realized experimentally. dized strongly with S 3p, and thus the number of electrons to be
With increasing Cu doping concentrations, the relaxed Cu–S transferred out from Cu atom is increased correspondingly. Fig. 5
average bond length of CuS4 tetrahedron decreases (Table 1), gives the total DOS and band structure corresponding to several of
indicating stronger bond strength between Cu and S atoms. Based Cu concentrations. With the increase of Cu doping concentrations,
on Mulliken analysis, the numbers of charge transfer from Cu to S due to Cu 3d hybridizing gradually with S 3p, we find that the top
atom, with x¼0.0278, 0.0556, 0.0833, and 0.111, are found to be of valence band in spin-up channel gradually shifts to the high
1.77, 2.01, 2.03, and 2.04, respectively (Table 2). Obviously, with energy, and the corresponding shifts equal to 0.04 eV, 0.12 eV,
P. Li et al. / Optics Communications 295 (2013) 45–52 49

Fig. 5. TDOS and band structures of Cd1  xCuxS ( x ¼0.0278, 0.0556, 0.0833, and 0.1111 ): (a) TDOS, (b) x ¼ 0.0278, (c) x ¼0.0556, (d) x¼ 0.0833, and (e) x¼ 0.1111.

0.23 eV and 0.34 eV in energy. Meanwhile, with the increase of x, are as following,
the Cu-doped CdS transfer from a semi-metal to metal. So the Z
4p2 X 2  2  
3
electrons can easily hop from the valence band to the conduction e2 ðoÞ ¼ M C,V ðkÞ d EkC EkV _o d k
m2 o2 C,V BZ ð2pÞ3
band and the quantity of exciton would be greatly increased,
resulting in a better conductivity. We can conclude that the Z 1
2 o0 e2 ðoÞ
conductivity of the material would be improved by increasing e1 ðoÞ ¼ 1 þ r0 do
the number of impurity atoms.
p 0 o02 o2
where subscripts C and V represent conduction band and valence
band, respectively, BZ is the first Brillouin zone, k is reciprocal
lattice vector, o is angular frequency, EkC and Ekv is intrinsic energy
3.2. Optical properties lever of2conduction band and valence band, respectively, while
M C,v ðkÞ is momentum matrix element. Taking into account the
3.2.1. Dielectric function wurtzite structure, the optical property of CdS will be anisotropic
The calculated band gap value (1.08 eV) of pure CdS is smaller with one symmetric axis (c-axis is z-axis). Thus, the real and the
than the experimental data (2.42 eV) by DFT calculation. While imaginary parts of the dielectric function for Cd1  xCuxS both
the standard DFT calculation is known to underestimate band along the z and vertical z directions are shown in Figs. 6 and 7,
gaps due to the poor description of strong Coulomb correlation respectively.
and exchange interaction between electrons, it is possible to Fig. 6 shows the imaginary spectra of optical dielectric func-
make qualitative statements regarding the influence of dopants. tion e2 (o) at the concentrations of 0, 0.0278, 0.0556, 0.0833 and
As we know, Optical transitions between occupied and unoc- 0.1111, where three main dielectric peaks in energy region are
cupied states are caused by the electric field of the photon, thus found. The first peak ranges from1.1 to 3.8 eV, which has a wider
the optical properties of the medium can be derived from the distribution. It should be mainly caused by the transition between
complex dielectric function e(o)¼ e1(o)þie2(o). The imaginary S 3p orbital in higher valence band and Cd 5s in the lowest
part of the dielectric function (e2(o)) can be calculated from the conduction band. When Cu doped into CdS, the peak has the offset
full many-electron wavefunction directly, and the real part of the to the lower energy side (red shift) and is larger than that of pure
dielectric function (e1(o)) can be evaluated from the imaginary CdS. These phenomena can be explained by the density of states,
part via the Kramers–Kronig transform. The concerned formulas resulting in the impurity Cu atom provides a large number of
50 P. Li et al. / Optics Communications 295 (2013) 45–52

50
2.5 CdS_xx
CdS_zz 40
2.0 x=0.0278
x=0.0556
30

ε2(ω)_xx
1.5 x=0.0833
ε2(ω) x=0.1111
1.0 20

0.5 10

0.0 0

0 5 10 15 20 25 30 0.0 0.5 1.0 1.5 2.0 2.5 3.0


Energy(eV) Energy(eV)

24

20
x=0.0278
16 x=0.0556
ε2(ω)_zz

x=0.0833
12 x=0.1111
8

0.0 0.5 1.0 1.5 2.0 2.5 3.0


Energy(eV)

Fig. 6. Imaginary part of the dielectric function for Cd1  xCuxS, (a) x¼ 0, (b) along x direction, (c) along z direction.

3.5
3.0 ε1(ω)_xx
50
x=0.0278
ε1(ω)_zz x=0.0556
2.5 40 x=0.0833
x=0.1111
30
ε1(ω)_xx

2.0
ε1(ω)

1.5 20

1.0 10

0.5 0

0.0 -10
0 5 10 15 20 25 30 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Energy(eV) Energy(eV)

36
32 x=0.0278
x=0.0556
28 x=0.0833
24 x=0.1111

20
ε1(ω)_zz

16
12
8
4
0
-4
0 1 2 3 4 5
Energy(eV)

Fig. 7. Real part of the dielectric function for Cd1  xCuxS, (a) x ¼0, (b) along x direction, (c) along z direction.

conduction holes near the Fermi surface, changes the electronic material shows semi-metallic, the peak decreases and moves to
interband transitions, and has an impact on the dielectric function the high energy in low energy range. But for x¼0.0833 and
and optical properties. With x ¼0.0278 and x¼0.0556, the x¼0.1111, the material show metallic, the peak mainly caused
P. Li et al. / Optics Communications 295 (2013) 45–52 51

by the transition from S 3p to unoccupied Cd 4d. The second peak transitions between the top of the valence band and the bottom of
located at about 4.5–5.6 eV is mainly derived from the transition the conduction band. In the 0–1.1 eV energy range, absorption
between S 3s and Cd 5s orbital, and the third peak at 6.5–7.7 eV coefficients of pure CdS are zero, showing no absorption greater
can be attributed to the transition between the deep Cd 4d and S than 1129 nm for pure CdS. The absorption edge of polarization
3p. With the increase of x, the latter two peaks change little, along the z direction is located at relatively lower energy than
which is mainly affected by the deeper orbits. that of x direction. When the Cu atom is introduced into CdS,
It can be found from the real part of the dielectric function there are several absorption peaks in the lower energy comparing
(Fig. 7) along x direction that the static dielectric constant e1(0) of with pure CdS. This result has been predicted by the electronic
Cd1  xCuxS are 2.42 (the result being in consistent with the result structure calculations. The results show that the Cu-doped CdS
of the experimental value (2.43)), 42.97, 15.78, 49.70, 39.13 with material slowly transits from a semi-metal to metal with increase
x from 0 to 0.1111, respectively. The static dielectric constant of x from 0.0278 to 0.1111. So the electrons can easily excite from
e1(0) along z direction of Cd1  xCuxS are 2.52, 11.67, 11.58, 23.24, the valence band to the conduction band. With Cu concentrations
and 33.26, respectively. The static dielectric constant of pure CdS increasing, their absorption spectra slightly move to higher
along x direction is smaller than that along z direction. But the energy (blue shifts) and the intensity of peaks increase gradually.
static dielectric constants of Cd1  xCuxS (x 40 ) along x direction This will contribute to the absorptions in the visible range for Cu-
are larger than that along z direction. The dielectric constant of Cu doped CdS. Meanwhile, we noted that there are two optical
doped CdS changes obviously, becomes very large and decreases absorption peaks along the z direction for semi-metal material
rapidly with increasing photon energy. The change curves of e1(o) (x ¼0.0278 and x¼ 0.0556). One is peak E1 ( around 0.5 eV and
move to the high energy with the increase of dopants. But doping 0.6 eV ), another is peak E2 ( around 1.0 eV and 0.95 eV ). It is clear
concentration has no effect on the curves of e1(o) in high energy that E2 is the intrinsic transition between valence band and
region. conduction band, while E1 is due to transition between valence
band and unoccupied d states of Cu. E1 is stronger than intrinsic
optical transition in the configuration. In this low energy region
3.2.2. Absorption the absorption peaks of polarization along the x direction is much
The optical absorption spectrum is important to estimate the larger than that of z direction. In ultraviolet region, there is very
optical properties of materials which are used as optoelectronic large absorption coefficient.
devices. The absorption coefficient a (o) can be obtained from
e1 (o) and e2 (o), as expressed by
pffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
aðoÞ ¼ 2½ e21 ðoÞ þ e22 ðoÞe1 ðoÞ1=2 4. Conclusions

Fig. 8 shows the calculated absorption coefficients for We have studied on the electronic properties and optical
Cd1  xCuxS with x from 0 to 0.1111. There are three main peaks properties of Cu doped wurtzite CdS by using FP-LAPW approach
for the pure CdS corresponding to e2 (o). The absorption coeffi- in the framework of the DFT. The density of states analysis
cient a (o) is very large (about 104 cm–1) and decreases rapidly in indicate that the d orbitals of Cu are hybridized with the
the low energy region. For pure CdS, in the visible range, p orbitals of S near the Fermi level, enhancing p and d charge
absorption edge is around 1.1 eV, which comes from the direct transfer between Cu and S. The Cu-doped CdS slowly transits from

Fig. 8. Absorption spectrum of Cd1  xCuxS, (a) pure CdS, (b) along x direction, (c) along z direction, (d) along z direction in the 0–3.0 eV energy range.
52 P. Li et al. / Optics Communications 295 (2013) 45–52

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