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Procedia Engineering 53 (2013) 217 224

Malaysian Technical Universities Conference on Engineering & Technology 2012, MUCET 2012 Part 1 Electronic and Electrical Engineering

Structural, Analysis and Optical Studies of Cadmium Sulfide Nanostructured

Abdulwahab S. Z. Lahewil* , Y. Al-Douri, U. Hashima, N. M. Ahmedb
Institute of Nano Electronic Engineering, University Malaysia Perlis Kangar, Perlis, Malaysia b School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
a

Abstract Cadmium sulfide (CdS) thin films of nanostructure were prepared and deposited on glass substrates with Cd:S (1.2 to 0.05 mol/L) annealed at 400 C and different spin coating speed (1000 and 5000 rpm) using sol-gel spin coating technique. Structural, morphological and analytical studies were investigated by x-ray diffraction XRD, scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-VIS Spectrophotometer. It is found that the average grain size of CdS thin films is 1.35 to 2.66 nm for the thin films prepared at 1000 and 5000 rpm respectively. The band gap was also calculated from the equation relating absorption coefficient to wavelength. The band gap indicates the film is transmitting within the visible range and the band gap changes because of the grain size of the CdS in the films. The effect of grain size on the semiconductor properties is under consideration. And the calculated results by specific models of refractive index are in agreement with experimental and theoretical data. The physical conditions were kept growing and identically.

2013The The Authors. Published by Elsevier 2013 Authors. Published by Elsevier Ltd. Ltd. Selection and peer-review under responsibility of the Research Management Innovation Centre, Universiti Malaysia Selection and/or peer-review under responsibility of the Research& Management & Innovation Centre, Universiti Malaysia Perlis Perlis.
Keywords: CdS; Sol-gel spin coating speed; Grain size and band gap.

1. Introduction Nanostructures have attracted great interest in recent years because of their unique chemical, physical, optical, electrical and transport properties which are different from those of either the bulk materials or single atoms [1,2]. Due to the vast surface area, all nanostructured materials posses a high surface energy and thus, are thermodynamically unstable or metastable. One of the great challenges in fabrication and processing of nanomaterials is to overcome the surface energy and to prevent the nanomaterials from growth in size driven by the reduction of overall surface energy. Due to high surface energy of the nanoparticles, they are extremely reactive and most systems without protection or passivation of their surfaces

* Corresponding author. E-mail address: alkmatys@yahoo.com

1877-7058 2013 The Authors. Published by Elsevier Ltd. Selection and peer-review under responsibility of the Research Management & Innovation Centre, Universiti Malaysia Perlis doi:10.1016/j.proeng.2013.02.029

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undergo aggregation [3]. Organic stabilizers are usually used to prevent nanoparticles from aggregation by capping their surfaces [4]. CdS is an II-VI semiconductor. Bulk CdS has hexagonal wurtzite-type structure [5], melting point 1600 0C [6] and band gap Eg = 2.42 eV [7] at room temperature. As the semiconductor nanoparticles exhibit size dependent properties, the melting point of 2.5 nm CdS crystallites is as low as ~ 400 0C, the band gap of 0.7 nm CdS crystallites is 3.85 eV [8] and at very high pressure phase changes from hexagonal wurtzite type to rock salt cubic phase [9]. Since CdS has 2.42 eV (515 nm) band gap, so it is most promising candidate among II-VI compounds for detecting visible radiation. As CdS has wide band gap, it is used as window material for hetero junction solar cells to avoid the recombination of photogenerated carriers which improves the solar cells efficiency. It has also application in light emitting diodes, photo detectors, Sensors, address decoders and electrically driven lasers [10]. In this paper we report a simple chemical precipitation synthesis route at room temperature without using any capping agent. CdS nanoparticles were synthesized by several other methods given as controlled precipitation reaction method, rapid hot-injection based synthesis method, photochemical method and physical methods. 2. Experimental All chemicals were of analytical grade and used as received from Malaysia Sigma-Aldrich company. CdS nanostructures were grown by sol-gel spin coating method at room temperature. Polyethylene glycol 200 (PEG) sol was prepared by mixing 0.6 ml of PEG, 8.5 ml of ethanol and 0.5 ml of acetic acid under stirring for one hour. 0.05 mol/L thiourea and 1.2 mol/L cadmium nitrate as a source of S and Cd, and 15 ml ethanol accompanying 60 C. Prepared solution was slowly added to the PEG sol with vigorous stirring for 6 hours. As the reaction was started the reaction system gradually changed from transparent to light yellow. The precipitate collected from centrifugation was dried at 120 C for one hour. This dried CdS is used to characterize by x-ray diffraction XRD pattern (Philips PW 1710 X-ray diffractometer), atomic force microscopy (AFM) SII Sciko Instrument INC SPI 3800N Probe station, scanning electronic microscopy (SEM) JEOL-JSM-6460 LA analytical and UV-Visible spectrophotometer, Perkin Elmer Lambda 950.

3. Result and Discussion

3.1 X-ray diffraction XRD

The nanostructural properties of the spin coated CdS thin films have been investigated by X-ray diffraction (XRD) technique as the shown in Fig.1. a and b prepared by different spin coating speed at 1000 and 5000 rpm, annealed for one hour at 400 C and 0.05 thiourea concentration. XRD pattern provided information about crystalline phase of the nanoparticles as well as the crystallite size. Figure 1. a shows the X-ray diffraction pattern of the as synthesized CdS nanoparticles. Peaks are observed at 24.97, 27.81, 29.98 and 43.55 corresponding to the (111), (200), (002), and (210) planes of the cubic and hexagonal phases of CdS thin film prepared at 1000 rpm, while Fig. 1. b shows the thin film prepared at 5000 rpm appeared one peak at 29.98 corresponding to the (002) plane of the hexagonal phase. The intensity of the peak is observed at thin film deposited at 5000 rpm is higher than the film deposited at 1000 rpm. The observed sharp peak compared to bulk CdS sample indicates the presence of good crystalline nature, which is good for photocatalytic reaction.

(1) Where D is the crystallite size, XRD patterns of the as synthesized sample was recorded on X-ray diffractmeter using rotating anode with Cuis the full width at half maxima (FWHM) of the diffraction peak in radian. Operating at 35.0 (kV), current = 25.0 (mA), scan range =10.000 to 80.000, scan speed = 5.000 (deg/min), present time = 0.24 (sec). The particle size is increase with increase the spin coating speed due to the calculation of grain size by Scherrer, s formula and it also can be seen that in SEM images the particle CdS size is increasing clearly. In addition, the dislocation density ( ) and strain of the films ( ) were determined using these XRD data and following relations: D2hkl (2)

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219

120

100

Intensity (a. u.)

80

60

40

20 10 20 30 40 50 60 70 80

2 theta

800 700 600

Intensity (a. u.)

500 400 300 200 100 0 10 20 30 40 50 60 70 80

2 theta

Fig. 1. X-ray diffraction (XRD) for CdS thin film deposited on glass substrates, concentration of thiourea 0.05 mol/L, and a) 1000 and b) 5000 rpm spin coating speed.

/4

(3)

The defects like dislocation density and strain in the films are determined the highest dislocation density (0.37041014 lines/m2) decrease regularly with increasing the spin coating speed and the highest strain 0.8117 x 10-3 increase regularly at 1000 rpm but decrease with increasing spin coating speed at 5000 rpm [13,14]. The interplanar distance (d) is calculated for all set of films using Brogg,s formula; /2sin (4)

and the lattice parameters a and c were calculated by the equations 5 and 6, the average lattice constant a is 1.021 and c 3.026 when CdS thin film deposited on glass substrate annealed at 400 C and spin coating speed 1000 rpm. The lattice constant a =1.026 and c = 3.086 when CdS thin film deposited on glass substrate annealed also at 400 C spin coating speed 5000 rpm. (5) (6)

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Table. 1 Shows the results and determinations using xrd data of cds thin films deposited on glass substrates, annealed at 400 c for one hour and 1000, 5000 rpm spin coating speed

Spin coating Speed (rpm)/(sec) 1000/30

Peak 24.97

Particle Size (nm) 1.35

Dislocaction density (1014 lines/m2) 0.3704

Strain (103 ) 0.2538

interplanar distance (d) () 1.82

Miller indices (khl) 111

Lattice parametes a and c () a=1.214* a=4.086a a=4.1b c=3.480* c=6.667a c=6.7b a=1.100* c=3.304* a=1.026* c=3.086* a=0.745* c=2.235* a=1.026* c=3.086*

27.81 29.98 43.55 4. 5000/30

*

1.38 1.40 1.61 6. 2.31

0.2415 0.2381 0.2070 7. 0.2162

0.2476 0.2425 0.8117 8. 0.1472

1.65 1.54 2.71 9. 1.54

200 002 210 10. 002

5. 29. 98

Measured value.; aRef. [10] Theo.; bRef. [14] Exp.

3.2 Scanning Electron Microscopy (SEM) The surface morphology of CdS thin films is very helpful to study the surface morphology of the CdS thin films. Sol-gel

(a) (b)

Fig. 2(a)(b): Scanning Electron Microscopy (SEM) for CdS thin films on glass substrates at 1000 and b) 5000 rpm spin coating speed.

The CdS thin films annealed at 400 C, in spin coating speed 1000 and 5000 rpm cases are presented in Fig. 5, a and b respectively, each at magnification of 30,000x. In the former case some cabbage like structure is seen, which improves in the later one. Earlier workers [15] found well developed cabbage structure, which they interpreted in terms of overlapping of different layers formed under continuous growth.

3.3 Atomic Force Microscopy (AFM)

Figure 3 shows typical 2D and 3D dimension images using atomic force microscope (AFM), scan area 2000 nm (2um2um) and scan speed 2 HZ. The CdS nanostructured deposited on glass substrates at different spin coating speed 1000and 5000 rpm and annealed at 400 oC. The thickness of CdS nanostructures show in Fig. 3 found to 20 and 10 nm

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respectively, for these results the crystallization shows nanostructures and morphology of CdS with uniform grain size and shape.

Fig. 3 shows two and three dimensions using atomic force microscopy (AFM) of CdS nanostructured deposited on glass substrates a) and b) at 1000 and 5000 rpm respectively.

3.4 Transmittance spectra studies

The study of optical properties transmission is important in understanding the behavior of semiconductor nanocrystals. A fundamental property of semiconductors is band-gap energy separation between filled valence band and the empty conduction band. Optical excitations of electrons across the band-gap are strongly allowed, producing an abrupt increase in absorption at the wavelength corresponding to the band-gap energy. The Fig. 3. a, b shows the transmittance spectrum in the wavelength range 400-2000 nm of the nanostructured CdS thin films. The films show more than 40-50 % transmission film prepared at 1000 rpm however the film prepared at 5000 rpm appears more than 80% transmission for wavelengths longer than 450 nm. It can seen that the film prepared at 5000 rpm present higher transmission than the film prepared at 1000 rpm that is due to the spin coating speed and annealing temperature [16].

60

50

Transimssion (%)

40

30

20

10

400

600

800

1000

1200

1400

1600

1800

2000

wavelength (nm)

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90

88

Transmission (%)

86

84

82

80 400 600 800 1000 1200 1400 1600 1800 2000

Wavelength (nm)

Fig. 3, a, b. shows the transmission experimental result from spectrophotometer for CdS thin films deposited on glass substrates at a) 1000, b) 5000 rpm spin coating speed respectively.

The optical band gap (Eg) of the films is determined by applying the Tauc model [17], which allows one to directly estimate the Eg fr -Eg 2 Fig. 4 The Eg can be obtained by extrapolating the linear portion to the photon energy axis as shown in the Fig. 4.

versus hv showing the estimation of the optical band gap of CdS thin film deposited on glass substrates, annealed at 400 oC for one hour and spin coating speed 1000, 5000 rpm.

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The refractive index n is an important physical parameter related to microscopic atomic interactions. Theoretically, the two different approaches in viewing this subject are the refractive index related to density, and the local polarizability of n related to the energy band structure of the material, complicated quantum mechanical analysis requirements and the obtained results. Many attempts have been made to relate the refractive index and the energy gap E g through simple and Eg will be reviewed. Ravindra et al. [21] suggested as a function of Eg: n
g

(7)

-1 . To be inspired by simple physics of light refraction and dispersion, Herve and Vandamme [22] proposed an empirical relation as:
2

A Eg B

(8)

where A = 13.6 eV and B = 3.4 eV. Ghosh et al. [23] took a different approach to the problem by considering the band structural and quantum-dielectric formulations of Penn [24] and Van Vechten [25]. Introducing A as the contribution from the valence electrons and B as a constant additive to the lowest band gap Eg, the expression for the high-frequency refractive index are written as: n2-1=A/(Eg+B)2 (9)

where A = 25Eg + 212, B = 0.21Eg + 4.25 and (Eg + B) refers to an appropriate average energy gap of the material. Thus, these three models of variation n with energy gap have been calculated. Also, the calculated values of the optical dielectric cons = n2 [26]. Our calculated refractive index values are in good agreement with experimental value as given in Table 2. This is giving an appropriate model of Herve and Vandamme for optoelectronic applications.
Table 2, The transmission, thickness, energy gap (eg), refractive index (n ) of cds nanostructures using ravindra et al. [21], herve and vandamme [22] and ghosh et al. [23] models on glass substrate at different spin coating speed. Spin coating speed (rpm/sec) 1000/30 Annealed (C/h) Thickness (d) (nm) Energy Band Gap (Eg) Optical Refractive index dielectric (n)

5000/30

5.4616 b 29.8290b 2.28* 2.3943c 400/1 20* 5.7326c a d 2.50 5.4760 29.9865d e 2.529 b 5.6352 31.7554b 2.56* 2.4913c 400/1 10* 6.2065c 2.50a 5.1123d 26.1356d 2.529e * a,e b c d Measured value; Ref. [20].; Ref. [21] cal.; Ref. [22] cal.; Ref. [23] cal.

4. Conclusion sol-gel spin coating method has been successfully developed to synthesize CdS nanostructures without using any capping agent at room temperature. XRD pattern shows diffraction lines due to CdS X-ray diffraction patterns revealed that the synthesized CdS nanostructures have hexagonal structure we found that the grain size increase with increasing the spin coating speed from 1000 to 5000 rpm to be 1.35 to 2.66 nm respectively. Ultra violet visible (UV-VIS) spectroscopy shows the transmission in Fig. 4. at 5000 rpm better than the transmission at 1000 rpm. The change in optical band gap associated

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with spin coating speed and annealing effects is deduced from optical measurements. The band gap of CdS films varied between 2.28 and 2.39 eV, depending on the spin coating speed and annealing process. SEM studies shows layered growth cluster of nanocrystals. The refractive index is proven that Herve and Vandamme model is the appropriate for optoelectronic devices. In addition, the characterizations, analysis and simulation studies recommended CdS nanostructures for photovoltaic and optoelectronic application. of films. The SEM image shows the thin film layers are improved better at 5000 rpm than the image at 1000 rpm due at the growing and the cluster of nanocrystals. The refractive index is proven that Herve and Vandamme model is the appropriate for optoelectronic devices. In addition, the characterizations, analysis and simulation studies recommended CdS nanostructures for photovoltaic and optoelectronic application. Acknowledgement This work has been achieved using FRGS grants numbered: 9003-00249 & 9003-00255. One of us; (Y. A.) would like to acknowledge TWAS-Italy, for full support of his visit to JUST-Jordan under TWAS-UNESCO Associateship. References
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