Materials Letters 59 (2005) 1 – 5

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Influence of growth process on the structural, optical and electrical

properties of CBD-CdS films
Li Wenyi a,*, Cai Xun a, Chen Qiulong a, Zhou Zhibin b
a
Key Laboratory of the Ministry of Education for High Temperature Materials and Testing, Shanghai JiaoTong University, Shanghai 200030, China
b
Department of Physics, Solar Energy Institute, Shanghai JiaoTong University, China
Received 17 February 2003; received in revised form 5 April 2004; accepted 10 April 2004
Available online 9 June 2004

Abstract

The hexagonal cadmium sulphide (CdS) thin films with strong (002) orientation are successfully prepared by chemical bath deposition
(CBD) technique using the reaction between CdCl2 and CS(NH2)2. Especially, polyglycol is used to modify the CBD system without magnetic
agitation. The influence of bath temperature on the properties of the CdS films such as optical transmission, surface morphology and the
structure is researched. The results show that polyglycol can flatten the films and diminish the pinhole. X-ray diffraction (XRD) and
transmission electron microscopy (TEM) tests verify that the deposited CdS films presented a hexagonal structure and no secondary or mixed
phases are found. A preferential columnar growth parallel to the substrate edge is also observed. It is found that the bath temperature plays a vital
role on the quality of the CdS films. The increase of bath temperature improves the surface morphology of the CdS films and also diminishes
pinholes on the films. The optimum bath temperature is 85 jC. The band gap calculated from transmission spectra is about 2.56 – 2.336 eV.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Photovoltaic material; Cadmium sulfide; Chemical bath deposition

1. Introduction CdS films can be grown with a and h phases depend-

ing on the deposition condition [10]. It is well known that
Extensive research has been done on the deposition and a-CdS invariably grows with columnar structure along the
characterization of cadmium sulphide (CdS) semiconduct- c-axis perpendicular to the substrate. This means that there
ing thin films due to their potential application in the area of are less grain boundaries parallel to the junction which
electronic and optoelectronic device [1,2]. Polycrystalline would impede the flow of photogenerated excess carries to
CdS thin films are generally used in CuInSe2 (CIS) and the grid [11]. In this paper, for the first time, the wetting
CdTe solar cells, as a window material for transmitting the agent (polyglycol) is successfully used in the process of
light absorbed by CIS or CdTe and also as the n-type CBD to obtain good quality CdS films. The hexagonal a-
material for p –n junction of the solar cells [3]. This material CdS thin films with excellent (002) orientation are suc-
has been prepared by several methods including evaporation cessfully prepared. The role of bath temperature on the
[4], sputtering [5], electrodeposition [6] and spray [7]. structural, optical and electrical properties of deposited
Chemical bath deposition (CBD) emerged as an alternative layer has been investigated.
for deposition of CdS. Compared with other methods, CBD
is convenient, cheap and has been successfully applied in
the fabrication of large-area high efficiency conversion solar 2. Experimental
cells [8]. Conversion efficiencies of 15.8% have been
achieved for CBD-CdS films on CIS-based solar cell by The CdS films were deposited at different temperature on
National Renewable Energy Laboratory (NREL) [9]. glass and silicon substrates from aqueous solutions of CdCl2,
KOH, NH4NO3, CS(NH2)2 and some polyglycol. Before
deposition, the substrates were ultrasonically cleaned with
* Corresponding author. Tel.: +86-21-629-32087. acetone and rinsed with deionized water. The glass substrates
E-mail address: wenyill@sohu.com (L. Wenyi). were vertically immersed into the chemical bath solution

0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2004.04.008
2 L. Wenyi et al. / Materials Letters 59 (2005) 1–5

Fig. 1. Morphology of CdS thin films at different deposition temperatures.

with the temperatures of 65, 75, 85 and 95 jC, respectively, ogy and their relations with other properties, as is shown in
and no agitation was needed during film deposition. After Fig. 1. In this case, a preferential columnar growth parallel
growing for 1 h, the film was ultrasonically cleaned in to the substrate edge is observed on CdS films deposited at
deionized water to remove any loosely adhered particles. 65, 75, 85 and 95 jC. The microstructures of the CdS films
The overall reaction is given below [12]: changed depending on the bath temperature. It can be
founded that there are many pinholes on the CdS film
CdðNH3 Þ2þ 
4 þ ðNH2 ÞCS þ 2OH ZCdS þ CH2 N2 þ 4NH3
deposited at 65 jC. In heterojunction application, any
þ 2H2 O pinhole of the films may affect the electronic characteristic
of apparatus by short circuit [13]. The increase of the bath
The surface morphology of the CdS films was examined temperature is an effective method to diminish the pinhole
by Nanoscope IIIa Atomic Force Microscopy. The structural on the CdS films. As the bath temperature increases, the
data were obtained by using RigkuD-MAXIII X-ray diffrac- surface morphology of the CdS becomes more homoge-
tion (XRD) and PH-800 transmission electron microscopy neous. It has been reported that the uniformity of the films
(TEM). The optical absorption studies were carried out with mainly depends on the rotate speed of stirrer during the
a UV-VIS-NIR spectrophotometer. entire period of deposition without polyglycol. Variation in
the rotate speed affects the uniformity of the CdS films and

3. Results and discussions Table 1

Values of the roughness and grain size of CdS film deposited at different
temperature
3.1. Morphological analysis
Temperature (jC) 65 75 85 95
AFM images were taken on CdS films deposited at RMS (nm) 35.025 26.303 14.045 9.625
different temperature in order to study the surface morphol- Grain size (nm) 180.5 164.2 145.5 105.0
 L. Wenyi et al. / Materials Letters 59 (2005) 1–5 3

3.2. Structural analysis

The crystallographic properties have been investigated

by X-ray diffraction technique using CuKa radiation. As is
well known, CdS can exist in two crystalline modifications:
the hexagonal (wurtzite) phase and the cubic (zincblende)
phase. For solar cell application, hexagonal CdS films are
preferable due to its excellent stability [17]. Fig. 2 shows X-
ray Diffraction curves of CBD-CdS films deposited at
different temperature. CdS films deposited by CBD show
a predominant single peak at 2h = 26.7j which can be
assigned to the (002) plane of hexagonal or the (111) plane
of cubic CdS. This preferred orientation of CdS films is due
to the controlled nucleation process associated with the low
Fig. 2. XRD patterns of CdS films deposited at different temperatures. deposition rate. With the increase of bath temperature, there
is an increase in intensity and sharpening of this peak, which
may result in island growth on the film surface [14]. is caused by improving crystallinity of the films.
According to the mechanism described by Kostoglou et CBD-CdS films show four diffraction peaks at 26.7, 44.3
al. [15], CdS films may grow by the decomposition of a and 52.3 which are associated with the (002), (103) and
metastable complex, Cd(OH)2(NH2)2SC(NH2)2, going with (112) reflections of the hexagonal modification or (111),
a release of NH3. The absorbed NH3 on the substrate would (220) and (331) reflections of the cubic CdS structure as
hinder the growth of CdS and cause the island growth or the shown in Fig. 2. In order to confirm the exact structure of
hole on the films. And it could concluded that desorption of the film, the structural analysis is detected with TEM, and a
NH3 is the main factor which affect the uniformity of CdS typical selected area diffraction pattern is shown in Fig. 3.
films. Both agitation and polyglycol are beneficial for the All the obtained (hkl) indices of the diffracted rings matched
desorption process of NH3 and the uniformity of the CdS well with those of the JCPDS 41-1049 data for hexagonal a-
films. Comparing with those CdS films deposited with CdS. Therefore, the existing experimental results indicate
magnetic agitation, the films deposited with polyglycol that the structure of deposited CdS films is hexagonal phase.
own larger grain size [16]. No cubic phase, complex of cubic and hexagonal or
Table 1 shows the roughness and grain size of CdS film secondary phases is observed. Diffracted rings of (100),
deposited at different temperatures. The root mean square (002), (110), (112), (211), (300) and (205) were observed in
(RMS) value is used to evaluate the surface roughness. With SAD pattern. This anomaly could be due to the difference in
the increase of bath temperature, both the RMS and grain sample thickness that is 30 nm for SAD and 120 nm for
size of the deposited CdS films decrease, which means that XRD. In thinner samples, the orientation of the planes was
the uniformity of the CdS films become better. For films random compared with the results of thicker films [18]. At
deposited at 95 jC, there are several hills on the film which the beginning of deposition, the glasses are isotropic body
may be caused by the clinging of CdS particles formed in and random nucleation occurs. With the growth of the films,
the solution, the optimum bath temperature is 85 jC. CdS is inclined to orientational deposition along the former

Fig. 3. TEM image and SAD pattern of CdS thin film for 20 min.
4 L. Wenyi et al. / Materials Letters 59 (2005) 1–5

Fig. 4. XRD patterns of CdS films: (a) deposited at 65 jC and (b) 85 jC.

grain for the slow growth rate. This columnar structure lattice parameter are due to enlargement of the CdS grain
along the c-axis perpendicular to the substrate means that size. The lattice constants for CdS films deposited at 85 jC
there are few grain boundaries parallel to the junction that were calculated from the XRD data to be a = 4.086 nm and
would impede the flow of photogenerated excess carries to c = 6.676 nm.
the grid.
Fig. 4 shows the XRD patterns of CdS films annealed at 3.3. Optical analysis
400 jC for 15 min. Peaks corresponding to reflections from
(002), (103) and (112) of hexagonal CdS are present in Optical properties of CdS films were measured with UV-
annealed samples and the intensities of all these peaks VIS-NIR spectrophotometer. Fig. 5 presents the transmis-
slightly increase after heat treatment. In addition, a few sion curves of CdS films deposited at different temperatures.
extra slight peaks appear after heat treatment and which are It can be found that the CBD-CdS films present high
due to the reflection from (201) of hexagonal CdS and transmission (70 – 95%) in the visible range. The absorption
(111), (200) of CdO. After annealing, the intensity of the edge of the films becomes steeper with increase of bath
2h = 26.7 peak increases and a slight shift towards lower temperature and get to the maximum for CdS films depos-
scattering angles is observed, no subpeaks are found. The ited at 85 jC. This indicates that bath temperature affect the
appearance of CdO phase might be due to oxidation of band gap value of CdS films. Using the standard expression
hexagonal CdS. Increase in the peak intensity indicates for direct transition materials (ahm)2 = A(hm-Eg), the band
improved crystallinity due to annealing. The shift towards gap of CdS films deposited at different temperature are
a lower scattering angle and the consequent increase in the found to be 2.56 – 2.336 eV (as shown in Fig. 6). An Eg shift
toward the blue wavelength region as temperature decreases
is noticed [19]. It can be proposed that at low temperature

Fig. 5. Transmittance of CdS thin films as a function of bath temperature. Fig. 6. Variation of the square of the ahm with light wavelengh.
 L. Wenyi et al. / Materials Letters 59 (2005) 1–5 5

columnar structure along with the c-axis perpendicular to

the substrate means that there are few grain boundaries
parallel to the junction that would impede the flow of
photogenerated excess carried to the grid. And it is also
found that bath temperature had obvious affection for the
morphology and optical properties. The increase of bath
temperature improves the surface morphology of the CdS
and also diminishes pinholes on the films. When bath
temperature is decreased, a shift of Eg toward the blue
wavelength region attributing to the improvement of crys-
tallinity is noticed. The optimum bath temperature is 85 jC.
The band gap calculated from transmission spectra are about
2.56 – 2.336 eV.
Fig. 7. Conductivity test of CdS film illuminated by light.

the dispersion of ion in solution due to thermal movement is References

reduced, and a preferential columnar growth parallel to the
[1] K. Senthil, D. Mangalaraj, S.K. Narayandass, Appl. Surf. Sci. 169 – 170
substrate edge appears. The decrease in band gap can be
(2001) 476.
attributed to the improvement of crystallinity. Although the [2] G. Sasikala, P. Thilakan, C. Subramanian, Sol. Energy Mater. Sol.
low bath temperature is beneficial for the crystallinity of Cells 62 (2000) 275.
CdS films, the rough surface contributed to big crystalline [3] A. Romeo, D.L. Bätzer, H. Zogg, C. Vignali, A.N. Tiwari, Sol. En-
size bring the flat absorption edge, and may destroy the ergy Mater. Sol. Cells 67 (2001) 311.
[4] R. Inov, D. Desheva, Thin Solid Films 213 (1992) 230.
electric property for short current. The proper bath temper-
[5] J. Pouzet, J.C. Bernede, A. Khellil, H. Essaidi, S. Benhida, Thin Solid
ature is 85 jC. The CdS film deposited at 85 jC owns Films 208 (1992) 252.
excellent optical property. [6] R.P. Raffaelle, H. Forsell, T. Potdevin, R. Fridefeld, J.G. Mantovani,
S.G. Bailey, S.M. Hubbard, E.M. Gordon, A.F. Hepp, Sol. Energy
3.4. Electrical analysis Mater. Sol. Cells 57 (1999) 167.
[7] K. Subba Ramaiah, V. Sundara Raja, Sol. Energy Mater. Sol. Cells 32
(1994) 1.
All films obtained during the present investigations result [8] M.T.S. Nair, P.K. Nair, R.A. Zingaro, E.A. Meyers, J. Appl. Phys. 75
in n-type conductivity, similar with other reports [20,21]. (1994) 1557.
Under illumination (100 mW cm2), the CdS films are [9] M.A. Contreras, M.J. Romero, B. To, F. Hasoon, R. Noufi, S. Ward,
highly photoactive and their conductivity increases approx- K. Ramanathan, Thin Solid Films 403 – 404 (2002) 204.
[10] E.P. Warekois, M.C. Layine, A.N. Mariano, H.C. Gatos, J. Appl. Phys.
imately one order of magnitude (Fig. 7). It can be found that
33 (1962) 690.
the ascending edge is flatter than the descending edge [11] G. Sasikala, P. Thilakan, C. Subramanian, Sol. Energy Mater. Sol.
caused by the reaction of crystal lattice phonon with Cells 62 (2000) 275.
photons. The time of descending period is about 0.5 –1 s. [12] O. Vigil, A. Arias-Carbajal, F. Cruz, Mater. Res. Bull. 36 (2001) 521.
During such short time, phonons excitated by heat has not [13] J.E. Granata, J.R. Sites, Pro. 25th Photovoltaic Specialists Confer-
ence, Washington, D.C., May 13 – 17, IEEE, USA, 1996, p. 853.
attenuated for inertia of heat transfer. And the interval of
[14] M. Rami, E. Benamar, M. Fahoume, F. Chraibi, A. Ennaoui, Solid
light response can be seemed as the life of light carrier. State Sciences t1 (1999) 179.
[15] M. Kostoglou, N. Andritsos, A.J. Karabelad, Thin Solid Films 387
(2001) 115.
4. Conclusion [16] S.A.Al. Kuhaimi, Vacuum 51 (1998) 349.
[17] C.Y. Yeh, Z.W. Lu, S. Froyen, A. Zunger, Phys. Rev., B 46 (1992)
10086.
For the first time, with wetting agent (polyglycol), CdS [18] K.S. Ramaiah, R.D. Pilkington, A.E. Hill, R.D. Tomlinson, A.K.
thin films are deposited on glass substrate by chemical bath Bhatnagar, Mater. Chem. Phys. 68 (2001) 22.
deposition. The films present uniformity, strongly adher- [19] O. Vogil, Y. Rodrı̀guez, O. Zelaya-Angel, C. Vàzquez-Lòpez, A.
ence, excellent transmission in visible light range. XRD and Morales-Acevedo, J.G. Vàzquez-Luna, Thin Solid Films 322 (1998)
329.
TEM tests verify that the deposited CdS films exhibit
[20] O.A. Ileperuma, C. Vithana, K. Premaratne, S.N. Akuranthilaka,
hexagonal structure with strong orientation and no second- S.M. Mcgregor, I.M. Dharmadasa, J. Mater. Sci. 9 (1998) 367.
ary or mixed phases are investigated. A preferential colum- [21] M. Rami, E. Benamar, M. Ranoume, F. Chraibi, A. Ennaoui, Solid
nar growth parallel to the substrate edge is observed. This State Sciences t1 (1999) 179.