Materials Letters 58 (2003) 5 – 9

www.elsevier.com/locate/matlet

Effects of complexing agent on CdS thin films prepared by

chemical bath deposition
Hui Zhang, Xiangyang Ma, Deren Yang *
State Key Lab of Silicon Materials, Zhejiang University, Hangzhou 310027, People’s Republic of China
Received 24 December 2002; accepted 9 May 2003

Abstract

CdS films have been prepared by chemical bath deposition (CBD) without stirring using weak and strong complexing agents, i.e.,
ammonia and ethylenediaminetetraacetic acid (EDTA). The optical, structural, and morphological properties of chemical bath deposited CdS
films have been investigated. When the complexing agent is ammonia, five peaks in the X-ray diffraction (XRD) patterns from the CdS film,
respectively, correspond to the interplanar spacing of 3.5498, 3.3429, 3.1449, 2.0574, and 1.7487 Å, which are definitely ascribed to
hexagonal structure; unfortunately, this hexagonal CdS film is with poor morphology and its optical property in the visible region is not
desirable for the solar cells. While, when the complexing agent is EDTA, three diffraction peaks in the XRD patterns from the CdS film,
respectively, correspond to the interplanar spacing of 3.1164, 2.6716, and 1.8507 Å, indicating that the film is of a cubic structure.
Furthermore, the CdS film has good morphology and its optical property in the visible region is compliant to the requirements of solar cells.
D 2003 Elsevier B.V. All rights reserved.

Keywords: Cadmium sulphide; Thin films; CBD

1. Introduction Herrero et al. [17], Castro-Rodriguez et al. [16], and

Vazquez-Luna et al. [18] also investigated the chemical
Over the years, CdS thin films have been intensively bath preparation and the properties of CdS thin films. In
investigated [1– 5]. For a wide and direct fundamental band the previous work, for the chemical bath deposition of CdS
gap (about 2.42 eV), they have been used in a lot of films, the ammonia was generally the complexing agent, in
applications including electronic and optoelectronic devices. this case, the stirring was always employed, and sometimes,
CdS thin films are also widely used as n-type window layers electric and magnetic field were applied. Obviously, these
in thin film solar cells. There are many methods to fabricate external means deserve additional setups for the CBD. In the
CdS thin films, such as electrodeposition [6], chemical bath present work, in order to remove the above-mentioned
deposition (CBD) [7], molecular beam epitaxy (MBE) [8], external means for the CBD, we use the EDTA which has
metal organic vapor phase epitaxy (MOVPE), metal organic much stronger complexing ability than ammonia as the
chemical vapor deposition (MOCVD) [9,10], close spaced complexing agent for the CBD. Therefore, the effects of
sublimation (CSS) [11], successive ionic layer adsorption ammonia and ethylenediaminetetraacetic acid (EDTA) on
and reaction (SILAR) [12], screen printing (SP) [13], and the morphology, crystal structure, and optical properties of
physical vapor deposition (PVD) [14]. Among them, the CdS films derived by CBD without stirring have been
chemical bath deposition (CBD) has been proven to be the investigated. As an outcome of this work, the EDTA is
most suitable method to produce CdS thin films for photo- proven to be very feasible for the preparation of CdS films
voltaic applications because it is an efficient, cost-effective, by CBD without stirring.
and large-scale method. In the 1960s, Soviet firstly used
CBD to prepare CdS thin films. Later, Sasikala et al. [15],
2. Experimental
* Corresponding author. Tel.: +86-571-87951667; fax: +86-571-
87952322. CdS thin films were deposited on 2  5 cm2 indium tin
E-mail address: mseyang@dial.zju.edu.cn (D. Yang). oxide (ITO) glass slides by CBD without stirring, respec-

0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0167-577X(03)00394-X
6 H. Zhang et al. / Materials Letters 58 (2003) 5–9

copy (SEM) and atomic force microscopy (AFM). Addi-

tionally, the optical property of the films was examined by a
Perkin-Elmer Lambda20 UV/VIS Spectrometer ranging
from 400 to 1000 nm.

3. Results and discussion

The effects of complexing agents on the phases of CdS

films were investigated by means of XRD. Fig. 1 shows the
XRD patterns of the chemical bath deposited films using
different complexing agents. When the comlexing agent was
ammonia, five peaks of X-ray diffraction (XRD) can be
found corresponding with 3.5498, 3.3429, 3.1449, 2.0574,
and 1.7487 Å interplanar spacings, which are definitely
attributed to the hexagonal structure. Generally, in the
previous studies, the chemical bath deposited CdS film of
hexagonal structure was reported to give rise to three
interplanar spacings of 3.34, 2.05, and 1.75 Å in the XRD
pattern, as a matter of fact, the attribution of these three
peaks is still controversial between the hexagonal and cubic
structure [15,21]. As will be illustrated later, the out layer of
the CdS film prepared using ammonia as complexing agent
is quite coarse and thus less oriented; accordingly, relatively
Fig. 1. XRD spectrum of CdS thin films under different complexing agent: more peaks are revealed in the XRD pattern shown in the
(a) complexing agent was ammonia; (b) complexing agent was EDTA.
present study, which is beneficial for us to determine the
phase of CdS film. While, when the complexing agent was
tively, using ammonia and EDTA as complexing agents. EDTA, three diffraction peaks of XRD correspond with
Firstly, the slides were cleaned using acetone and alcohol, 3.1164, 2.6716, and 1.8507 Å interplanar spacings, which
and then put into de-ionized water under ultrasonic stirring can be ascribed to a cubic structure. Judging from the
for 30 min. The chemical bath was an aqueous solution of intensities of the peaks, the CdS film can be regarded to
0.02 M CdCl2, 0.05 M CS(NH2)2, and different complexing be oriented with [111] direction. For reference, Table 1 lists
agents: ammonia with a buffer of 0.05 M NH4Cl or 0.01 M the experimental interplanar spacings obtained from XRD
EDTA. The temperature of the chemical bath was 80 jC and and the standard value. Sasikala et al. [15] have reported the
the pH was adjusted to 11 using ammonia. A deposition phase transformation of CdS film is due to the change of
time of 30 min was chosen for all experiments. After Cd2 + concentration that leads to different deposition rates.
deposition, the slides were removed from the chemical bath, In our experiment, there may be two reasons for the phase
and cleaned for several times with de-ionized water, then transformation. One is that the complexing constants of
dried in N2, finally annealed in 350 jC N2 for 60 min. ammonia and EDTA for Cd2 + are different, as shown in
The crystal phase of the films was determined by X-ray Table 2. Therefore, in two chemical baths with precursors of
diffraction (XRD), using CuKa radiation. The morphology the same concentration, when using ammonia and EDTA as
of the films was determined by scanning electron micros- complexing agent, respectively, the resulting concentrations

Table 1
Experimental interplanar spacings (dexp) obtain from XRD spectra of the CdS films prepared using ammonia and EDTA as complexing agent, respectively
CdS films prepared using ammonia as agent CdS films prepared using EDTA as agent
Experimental value Standard value Experimental value Standard value
dexp (Å) dhex (Å) Ihex (hkl)hex dexp (Å) dcub (Å) Icub (hkl)cub
3.55 3.59 62 (100) 3.12 3.16 100 (111)
3.34 3.36 91 (002) 2.67 2.73 70 (200)
3.14 3.16 100 (101) 1.85 1.93 60 (220)
2.45 29 (102) 1.64 20 (311)
2.06 2.07 48 (110) 1.57 20 (222)
1.90 50 (103) 1.36 10 (400)
1.79 8 (200)
1.75 1.76 31 (112)
 H. Zhang et al. / Materials Letters 58 (2003) 5–9 7

Table 2 the effective concentrations of Cd2 +, S2 , and CdS par-

Complexing constants with regard to Cd2 +
ticles. When the effective concentrations of Cd2 + and S2
Complexing agent Complexing constant are high and that of CdS particles is low, ions-by-ions
(pH = 10, T = 25 jC, concentration = 0.1 M)
deposition is dominant in CBD process; on the contrary,
Ammonia 3.0 the clusters-by-clusters deposition dictates the CBD process.
EDTA 14.7
Sasikala et al. [15] have proved that clusters-by-clusters
deposition is highly undesirable and it yields powdery and
of Cd2 + and S2 in solution will be different, thus leading non-adherent films; on the contrary, the ions-by-ions depo-
to different deposition rates. The other is supposed to be that sition is expectable and it leads to uniform films. From
the different metastable phases would form on the substrates Table 1, it is known that the effective concentration of Cd2 +
with different complexing agents and they are decomposed ions in the solution using EDTA as the complexing agent
in different modes, which results in different phases. was extremely low and the formation of CdS colloidal
From Fig. 2, we can learn the complexing agent effects particles in the solution was greatly suppressed, therefore,
on the morphology of as-deposited films. Fig. 2a reveals the ions-by-ions deposition dictated the film deposition,
that when ammonia was the complexing agent for CBD, the thus, resulting in smooth morphology. In contrast, the
film is rough and has quite a lot colloidal particles. Fig. 2b effective concentration of Cd2 + ions in the solution using
shows that the complexing agent of EDTA leads to very ammonia as the complexing agent was quite high and the
smooth film. During the CBD of CdS films, it is believed formation of CdS colloidal particles was appreciable, thus,
that there are two possible pathways, i.e., clusters-by-clus- the clusters-by-clusters deposition led to poor morphology.
ters deposition via CdS colloidal particles formed in the Fig. 3 shows the AFM images of the CdS films,
solution, and ions-by-ions deposition via metastable com- respectively, using ammonia and EDTA as complexing
plex comprising Cd and S agents [19 – 21]. These two agent in the CBD process. As mentioned above, when the
deposition pathways are competitive, which depends on complexing agent was ammonia, the clusters-by-clusters
deposition dictated the CBD process, thus, leading to
relatively rough morphology as shown in Fig. 3a, while,

Fig. 2. SEM images corresponding with CdS samples from different

complexing agent: (a) complexing agent is ammonia; (b) complexing agent Fig. 3. AFM analysis related to CdS samples from different complexing
is EDTA. agent: (a) complexing agent is ammonia; (b) complexing agent is EDTA.
8 H. Zhang et al. / Materials Letters 58 (2003) 5–9

to different deposition rates, and thus, the film thickness,

which also contributes to different transmission in the
visible region.

4. Conclusions

CdS thin films have been successfully prepared by the

simple and flexible CBD method without stirring. When
using ammonia as the complexing agent, the clusters-by-
clusters deposition is dominant, which leads to the forma-
tion of films with rough morphology; while, when using
EDTA as the complexing agent, the ions-by-ions deposition
favors the formation of films with smooth morphology.
Moreover, the effect of complexing agent on the crystal
phase of CdS films is found, that is, the films are of
hexagonal and cubic structure when using ammonia and
Fig. 4. Optical transmission of CdS films under different agent: Complex-
ing agent is ammonia; (a) complexing agent is ammonia; (b) complexing EDTA as complexing agent, respectively. As for the optical
agent is EDTA. properties of chemical bath deposited CdS films, the derived
film using EDTA as complexing agent has more significant
transmission in the visible region than that using ammonia
when the complexing agent was EDTA, which possesses as complexing agent, which is ascribed to different crystal
quite a lot stronger complexing ability than ammonia, the structures, morphologies, and thicknesses of two CdS films.
ions-by-ions deposition was overwhelming in the CBD
process, resulting in very smooth morphology, as shown
in Fig. 3b. Obviously, the results of AFM are consistent with Acknowledgements
those of SEM.
The optical properties of CdS thin films were measured The authors would like to appreciate the financial
by UV spectrometer. Fig. 4 shows the optical transmission supports of the Natural Science Foundation of China
spectra of two chemical bath deposited CdS films, respec- (60225010), 863 project (No. 2001AA513023).
tively, using ammonia and EDTA as complexing agent in
CBD process. As it can be seen, the transparencies of the
CdS films in the visible region strongly depend on the References
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