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��ࡱ�>��	���������{�}�����������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������	����bjbjBrBr	4�  �4
���������������������8<O|�)(��____����&�&�&�&�&�&�&$?+��-J'�������'��__4�'I!I!I!�*�_�_�&I!��&I!I!�#�#_����0�ڥ������#�&�'0)(�#+.W�+.�#+.��#���I!�����''I!���)(������������������������������������������������������������������������+.����������	�:	@Synthesis, Dielectric and Solid State Parameters of CdS nanoparticles by Wet chemical Method
Sagadevan Suresh*
Crystal Growth Centre, Anna University, Chennai-600 025, India
Corresponding Author email-sureshsagadevan@yahoo.co.in

Abstract 
	CdS is one of the most important II�VI semiconductors with applications in solar cells, optoelectronics and electronic devices. CdS nanoparticles were synthesized by wet chemical technique. The crystal structure and grain size of the particles were determined using X-ray diffraction (XRD). The optical properties were studied by Ultraviolet-Visible (UV-Vis) absorption and Photoluminescence (PL) spectrum. The dielectric properties of CdS nanoparticles were carried out in the frequency range of 50Hz-5MHz at room temperature. Some characteristic data such as valance electron plasma energy, Penn gap, Fermi energy and electronic polarizability of the CdS nanoparticles were calculated.
Key words: Nanoparticles, CdS, XRD, UV analysis, PL, Dielectric constant and Dielectric loss
Introduction 
	Nanomaterials have attracted interest and attention due to their special characteristics that differ from that of the bulk solids and molecules. Since novel properties of nanomaterials depend on their size, structure and shape, understanding of their mechanism as well as a new direction for synthesis methods are significant issues in nanoscience and nanotechnology [1]. As a result of the high surface-to-volume ratio of the nanoparticles, the surface properties have significant effects on their structure and in turn have influence on the nanoscale devices in electronics to target in drug delivery [2].In recent years, semiconductor nanoparticles exhibit specific properties due to the quantum confinement effects. As a consequence of their size in nanometric range and the special luminescent properties, caused by widening the band gap when the spatial dimension is reduced [3�5]. In semiconductors, quantum confinement modulates the band structure of nanoparticles and hence, many properties can be tuned by changing the nanoparticles size. Due to the quantum size effect of semiconductor nanoparticles, especially the II�VI semiconductor nanoparticles exhibit size-dependent optical properties [6], which are of great importance for potential applications such as light emitting diodes [7], biological labels [8,9], optoelectronic devices [10] and solar cells [11]. Semiconducting nanoparticles research is one of the most investigated subjects due to their wide field of applications. Recently, the surface modification of fluorescent semiconductor nanoparticles by biomolecules and nucleic acids has added a new dimension to nanoparticle research with respect to their biological applications [12]. This article deals with the preparation of CdS nanoparticles using wet chemical method. The prepared nanoparticles were characterized structurally and optically using powder XRD, UV-Vis absorption and photoluminescence spectra. The dielectric measurements were carried out in the frequency range 50Hz -5MHz at room temperature.  Fundamental parameters like plasma energy, Penn gap, Fermi energy and electronic polarizability of the CdS nanoparticles were determined.
2. Experimental Procedure 
	Nanoparticles of CdS were synthesized in wet chemical technique starting from cadmium nitrate and sodium sulfide precursors. Glucose was used as capping agent. After 12 hours of constant stirring, a pale yellow colored solution was obtained. The precipitates were washed several times with ethonal and centrifuged and dried at 50�C for 3 hours in vacuum. The structure and phase of the sample were determined by XRD with CuK� radiation (�=1.5481nm), the 2� range used was from 10 to 70� at a scanning rate of 0.02 deg/sec.         UV visible spectrum of synthesised CdS nanoparticles had been recorded using Varian Cary Model 5000 spectrophotometer in the wavelength range of 400-700 nm. The photoluminescence study was done for the CdS nanoparticles using JOBIN YVON FLUROLOG-3-11 SPECTRO FLUROMETER. The dielectric constant and the dielectric loss of the pallets of CdS nanoparticles in disk form were studied at room temperature using a HIOKI 3532 LCR HITESTER in the frequency region from 50 Hz to 5 MHz. 
3. Results and discussion 
3.1. XRD 
	XRD pattern of CdS nanoparticles is shown in Fig.1. The XRD peaks are found to be broad which indicate the fine sized grain. The synthesized nanoparticles have good crystallinity and the average particle size obtained using the diffraction pattern resulted to be 3.85 nm. The XRD pattern exhibits the prominent broad peaks at 2� values of 26.80, 43.90 and 52.20�. 

Fig. 1 XRD pattern of Cadmium sulphide nanoparticles

3.2. UV-Absorption 
The UV-visible absorption spectroscopy has been used to focus the optical properties of quantum-sized particles. The absorption spectrum of the nanoparticles of CdS is shown in Fig. 3. The systematic shift in the absorption edge with changing particle size is obviously due to the quantum size effect of CdS nanoparticles. It is interesting to note a strong absorption band at 480 nm is observed in Fig. 2, which indicates the narrow distribution of CdS nanoparticles. It is well known that the diameter of the particles is related to the absorption edge [13, 14]. Generally, wavelength of the maximum exciton absorption decreases as the particle size decreases as a result of quantum confinement of the photo generated electron-hole pairs. The energy bandgap of these synthesized nanoparticles was estimated using the relation, 
                                                       EMBED Equation.3                                                                            (1)
where Eg, the bandgap, h, Planck�s constant, c, the velocity of light, �max, the maximum absorption of CdS nanoparticles.  The value of the bandgap is found to be 2.58 eV. The absorption band edge was shifted to 480 nm and the corresponding bandgap is 2.58 eV which is higher compared to bulk CdS bandgap (2.4 eV). 


Fig.2 Absorbance spectrum of Cadmium sulphide nanoparticles

3.3 Photoluminescence
	The photoluminescence spectrum of the as-prepared CdS nanoparticles is given  in Fig. 3. Fig. 3 shows the emission spectrum of the nanoparticles obtained and it has a broad band with a maximum around 650 nm. This is due to the surface states arising from the deep trap formed due to sulphur vacancy [15, 16] whereas the band edge emission is nearly 500 nm. This notably affects the particle formation. The cadmium ions (Cd2+) and sulphur ions (S) are unstable in reaction medium and nucleate to form CdS nanoparticles due to the large Coulomb force between them. 




Fig.3. Photoluminescence spectrum of CdS nanoparticles

3.4 Dielectric properties

	The Fig. 4 shows the plot of dielectric constant (�r) versus applied frequency. It is observed (Fig.4) that the dielectric constant decreases exponentially with increasing frequency and then attains almost a constant value in the high frequency region. The dielectric loss studied as a function of frequency at room temperature is shown in Fig.5. These curves suggest that the dielectric loss is strongly dependent on the frequency of the applied field, similar to that of dielectric constant. In the low frequency region, high energy loss is observed, which may be due to the dielectric polarization, space-charge and rotation-direction polarization occurring in the low frequency range. The value of dielectric loss is found to be higher than that the value for the bulk CdS in the low frequency region.  The high value of dielectric constant at low frequencies may be due to the presence of all the four polarizations, namely, space charge, orientation, electronic and ionic polarization and its low value at higher frequencies may be due to the loss of significance of these polarizations gradually [17].  This may lead to large values of dielectric constant at low frequencies. The CdS pellets exposed to an external electric field, positive and negative charges on interfaces moves towards the negative and positive poles of electric field, respectively. Meanwhile, a great number of dipole moments are unavoidably formed after they have been trapped by defects. Consequently, space-charge polarization occurs in the interfaces of CdS nanoparticles, which results in the much larger dielectric constant of CdS nanoparticles. For conventional CdS powders, it is impossible to observe space-charge polarization due to the smaller specific surface. The dielectric constant value of CdS nanoparticles is found to be very high as compared to bulk CdS, which is in good agreement with earlier reports [18]. 

Fig.4. Dielectric constant of CdS nano particles, as a function of frequency


Fig.5. Dielectric loss of CdS nano particles, as a function of frequency

3.5 Solid State Parameters of the CdS nanoparticles

	The total number of valence electrons of cadmium sulfide Z = 11, density � = 2.692 g.cm-3 and molecular mass M =254.47, the valence electron plasma energy, [�p, is calculated using the relation,

                                   EMBED Equation.3                                                                      (2)


                                    EMBED Equation.3                  				             (3)


Plasma energy are the Penn gap and the Fermi energy [19] given by

                            	   EMBED Equation.3              				             (4)

Then we obtained electronic polarizability � using a relation [20, 21],

                   		      EMBED Equation.3                                 (5)

where S0 is a constant given by

                         	   EMBED Equation.3                                                                  (6)

The value of � obtained from equation (5) closely matches with that obtained using Clausius-Mossotti relation,

                                             EMBED Equation.3                                                                    (7)

Considering that the polarizability is highly sensitive to bandgap [22], the following empirical relationship is also used to calculate �,

                                       EMBED Equation.3     			             (8)

where Eg is the bandgap determined through UV studies. All the above parameters as estimated are shown in Table 1.  

Table.1 Solid state parameters of CdS nanoparticles 

ParametersValue
Plasma energy (h�p)9.824 eVPenn gap (Ep)0.908 eVFerm%&*JNV\]o��վ���y�bN7")h�h�B*CJOJPJQJaJph,h�h�5�B*CJOJPJQJaJph&h�5�B*CJOJPJQJaJph,hRc�h��5�B*CJOJPJQJaJph,hRc�h
�5�B*CJOJPJQJaJph,hRc�h+
�5�B*CJOJPJQJaJph,h�C�h�C�5�B*CJOJPJQJaJph,hRc�h6
5�B*CJOJPJQJaJph,hRc�h�C�5�B*CJOJPJQJaJph&h�C�5�B*CJOJPJQJaJph]o�����������^���������������
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la��yt�;i Energy (EF)6.156 eVElectronic polarizability (Penn analysis)3.64 x 10-23 cm-3Electronic polarizability (using CM relation)3.65 x 10-23 cm-3Electronic polarizability (using band gap)2.62 x 10-23 cm-3

4. Conclusion 
	Nanoparticles of CdS are synthesized using wet chemical method. The crystal structure and grain size of the particles are determined using XRD studies and the particle size of the CdS nanoparticle is found to be 3.85 nm. From the optical absorption spectrum, the blue shift of 480 nm with respect to bulk counterpart is contributed from the quantum confinement effect. The value of bandgap is found to be 2.58 eV. The broad emission band observed in the PL spectrum for CdS nanoparticles is assigned to the surface trap induced fluorescence which involved the recombination of electrons trapped inside a sulphur vacancy with the hole in the valence band of CdS nanoparticle. The dielectric constant and dielectric loss of synthesized CdS nanoparticles are measured in the frequency range of 50Hz-5MHz at room temperature. The dielectric constant of CdS nanoparticles is found to be much larger than that of the bulk CdS. Fundamental parameters like plasma energy, Penn gap, Fermi energy and electronic polarizability of the CdS nanoparticles have been calculated.





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