Journal of Non-Crystalline Solids 353 (2007) 29342937 www.elsevier.

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Electrical conductivity and single oscillator model properties of amorphous CuSe semiconductor thin lm
F. Yakuphanoglu
a

a,*

, C. Viswanathan

Faculty of Arts and Sciences, Department of Physics, Firat University, 23169 Elazig, Turkey b Department of Physics, Bharathiar University, Coimbatore 641 046, India Received 27 August 2006; received in revised form 24 June 2007 Available online 8 August 2007

Abstract The structural, optical dispersion and electrical conductivity properties of the CuSe thin lm have been investigated using X-ray diffraction, electrical and optical characterization methods. X-ray diraction results indicate that CuSe thin lm has an amorphous structure. The electrical conductivity of the CuSe lm increases with increasing temperature. The activation energy and room temperature conductivity values of the lm were found to be 1.32 meV and 3.89 103 S/cm, respectively. The refractive index dispersion of the thin lm obeys the single oscillator model and single oscillator parameters were determined. The Eo, n1, and So values of the CuSe thin lm were found to be 5.08 eV, 3.55 and 1.92 1014 m2, respectively. The obtained results suggest that CuSe lm is an amorphous semiconductor. 2007 Elsevier B.V. All rights reserved.
PACS: 71.23.Cq; 73.61.r; 78.20.Ci Keywords: Amorphous semiconductor; Conductivity; Absorption; X-ray diraction

1. Introduction Metal chalcogenide compounds having semiconductor structure are important materials for electronics and electro-optical devices. They show continuous change of physical properties with change in chemical composition. Chalcogenide glasses have been intensively investigated because of their technological properties [1]. A lot of work has been done on impurity eect on conductivity and optical properties [2,3]. Copper selenide is a metal chalcogenide semiconductor with a wide range of stoichiometric compositions and also with various crystallographic forms for each of these compositions [4]. Copper(I) selenide is a ptype semiconductor material which has suitable electrical

Corresponding author. Tel.: +90 4242370000; fax: +90 4242330062. E-mail address: fyhan@hotmail.com (F. Yakuphanoglu).

and optical properties for photovoltaic applications and also as a super ionic conductor. Copper(I) selenide exists in widely dierent crystallographic modications even at room temperature. This includes orthorhombic, monoclinic and cubic forms, depending on the method of preparation [48]. Chalcogenide glasses containing metal atoms form an interesting class of amorphous semiconductors. Amorphous semiconductor materials have been emerged as promising materials due to their potential technological importance. They can be used in the fabrication of electrophotographic devices and, switching and memory devices. The electrical and optical properties of chalcogenide glassy semiconductors in a desired direction can be changed by doping. We attempt to produce a amorphous semiconductor based on CuSe thin lm. The electric-optical characterization of thin lm prepared has been performed via X-ray diraction, conductivity and optical methods.

0022-3093/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2007.06.055

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2. Experimental CuSe lm was prepared by the thermal evaporation technique using a Hind Hivac Coating unit (12A4) with conventional rotary and diusion pumps maintaining a residual pressure better than 2 105 Torr. The CuSe alloy was prepared from its own constituent elements. Appropriate weights of Copper and Selenium (of purity 99.99% Nuclear Fuel Complex, Hyderabad) were mixed together and placed in a silica glass, which is sealed under a vacuum of 105 Torr. The sealed silica glass with the charge was placed in a rotating furnace at a temperature 1373 K for 24 h and then the compound was slowly cooled down to room temperature. The CuSe ingot was taken out and made into ne powder. Copper selenide thin lm is deposited on highly cleaned glass substrate in vacuum better than 105 Torr by using thermal evaporation method. The thickness of CuSe thin lm is measured by using multiple beam interference (MBI) technique and was found to be 217 nm. The temperature dependence of direct current (dc) conductivity of the lm was measured using a Keithley 6517A electrometer at a heating rate of 4 C/min. Absorption spectrum of the lm was recorded by Shimadzu 3600 UVVISNIR spectrophotometer. 3. Results and discussion 3.1. Crystal structure, electrical conductivity and absorption edge of CuSe thin lm X-ray diraction spectra of the CuSe thin lm is shown in Fig. 1. The spectrum indicates a wide and shallow peak, suggesting an amorphous structure. The temperature dependence of conductivity of the lm is shown in Fig. 2. The electrical conductivity of the CuSe lm increases with increasing temperature. The conductivity plot indicates that the electrical conductivity mechanism of the CuSe lm takes place through thermally activated process. The CuSe thin lm exhibits a semiconductor behavior. The electrical

Fig. 2. Electrical conductivity dependence on temperature of the CuSe thin lm.

conductivity of the lm is analyzed by the well-known equation, r ro expE=kT ; 1 where ro is the pre-exponential factor corresponding to 1/ T = 0, E is the activation for electrical conductivity, k is the Boltzmann constant and T is the temperature. The activation energy E and ro values were determined from the slope and intercept of Fig. 2 and were found to be 1.32 meV and 4.10 103 S/cm, respectively. The pre-exponential factor is associated with the density of localized states. The obtained E and ro values suggest that the conduction is due to thermally assisted tunneling of charge carriers in the localized states in band tails [9]. The interband transition in amorphous solid is characterized by a slow rise in the absorption coecient with photon energy. The optical band gap and the nature of optical transitions can be obtained dependence of absorption coecient on photon energy. It is evaluated that the band structure of the lm obeys the rule of direct transition and in a direct band gap material, the absorption

Fig. 1. X-ray diraction pattern of the CuSe thin lm.

Fig. 3. Plot of (ahm)2 vs hm of the CuSe thin lm.

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F. Yakuphanoglu, C. Viswanathan / Journal of Non-Crystalline Solids 353 (2007) 29342937

coecient dependence on photon energy is expressed by the well-known relation ahm Ahm Eg
1=2

where A is a constant, hm is the photon energy and Eg is the optical band. The plot of (ahm)2 vs hm is shown in Fig. 3. The optical band gap of the CuSe thin lm was determined from the intercept of extrapolated linear portion of (ahm)2 vs hm plot, as shown in Fig. 3, indicating a direct transition. The optical band gap of the lm was found to be 3.55 eV. Electrical conductivity and optical results of the lm suggest that the CuSe thin lm is an amorphous semiconductor of direct band gap. 3.2. Refractive index dispersion properties of CuSe thin lm The spectrum of reectance R of the thin lm is shown in Fig. 4. The refractive index is obtained by the following relation [1012], ; 3 2 n 1 k 2 where n is the refractive index and k is extinction coecient given by k ak : 4p 4 R n 1 k 2
2

Fig. 5. Refractive index dispersion curve of the CuSe thin lm.

The values of refractive index of the lm were determined from reectance spectrum. The spectral dependence of the refractive index is shown in Fig. 5. At lower wavelengths, the refractive index decreases with wavelength, i.e. refractive index shows normal dispersion. But, at higher wavelengths, the refractive index tends to a constant, i.e. the lm becomes non-dispersive. The refractive index dispersion in semiconductors can be analyzed using single oscillator model. The dispersion of the refractive index is expressed as [13], n2 1 Ed E o E2 o hm
2

Fig. 6. Plot of 1/n2 1E2 of the CuSe thin lm.

where h is Plancks constant, m is the frequency, hm is the photon energy, Eo is the average excitation energy for elec-

tronic transitions and Ed is the dispersion energy, which is a measure of the strength of interband optical transitions. The Eo and Ed values for the CuSe lm were determined from the slope and intercept of 1/n2 1hm2 plot, as shown in Fig. 6 and were found to be 5.08 and 64.09 eV, respectively. The oscillator model can be also written as [14], n2 1 S o k2 o 1 ko =k
2

where k is the wavelength of incident light. So is the average oscillator strength and ko is an average oscillator wavelength. Eq. (6) also can be transformed as [15],  2 n2 1 ko 1 1 ; 7 n2 1 k where n1 is the refractive index at innite wavelength. The n1, and So values of the CuSe thin lm were determined from the slope and intercept of (n2 1)1 vs k2 curves plotted and were found to be 3.55 and 1.92 1014 m2, respectively. The complex dielectric constant for CuSe lm can be expressed by the following relation [16],
Fig. 4. Reectance spectrum of the CuSe thin lm.

e e1 ie2 ;

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where c is the velocity of light, N/m* is the carrier concentration to the eective mass ratio, eL is the lattice dielectric constant. The eL value was calculated from the slope of n2 vs k2 curve plotted and was found to be 19.86. A dierence between e1 and eL values was observed. This is due to the free-carrier contribution. 4. Conclusions The structural, optical dispersion and electrical conductivity properties of the CuSe thin lm have been investigated. X-ray diraction results indicate that CuSe thin lm has amorphous structure. The activation energy and room temperature conductivity values of the lm were found to be 1.32 meV and 3.89 103 S/cm, respectively. The refractive index dispersion obeys the single oscillator model and single oscillator parameters were determined. It is evaluated that CuSe thin lm is an amorphous semiconductor with calculated electronic parameters. References
[1] M. Zope, B.D. Muragi, J.K. Zope, J. Non-Cryst. Solids 103 (1988) 195. [2] R.M. Mehra, R. Sham, P.C. Mathur, Phys. Rev. B 19 (1979) 6525. [3] K. Arai, T. Kuhat, H. Namikawa, S. Saito, Jpn. J. Appl. Phys. 11 (1972) 1080. [4] S.K. Haram, K.S.V. Santhanam, M. Neumann-Spallart, C. LevyClement, MRS Bull. 27 (1992) 1185. [5] S.K. Haram, K.S.V. Santhanam, Thin Solid Films 238 (1994) 21. [6] R.M. Murray, R.D. Heyding, Can. J. Chem. 53 (1975) 878. [7] Z. Vucic, O. Milat, V. Horvatic, Z. Ogorelec, Phys. Rev. B 24 (1981) 5398. [8] H. Okimura, T. Matsumae, R. Makabe, Thin Solid Films 71 (1980) 53. [9] N.F. Mott, Philos. Mag. 22 (1970) 7. [10] D.J. Gravesteijin, Appl. Opt. 27 (1988) 736. [11] K. Oe, Y. Toyoshima, H. Nagai, J. Non-Cryst. Solids 20 (1976) 405. [12] Y. Caglar, S. Ilican, M. Caglar, F. Yakuphanoglu, Spectrochim. Acta Part A 67 (2007) 1113. [13] M. DiDomenico, S.H. Wemple, J. Appl. Phys. 40 (1969) 720. [14] Fahrettin Yakuphanoglu, Opt. Mater. 29 (2006) 253. [15] A.K. Wolaton, T.S. Moss, Proc. Roy. Soc. 81 (1963) 5091. [16] M.M. Wakkad, E.Kh. Shokr, D.H. Mohamed, J. Non-Cryst. Solids 265 (2000) 157. [17] S.H. Wimple, M. DiDomenico, Phys. Rev. Lett. 23 (1969) 1156. [18] M.B. El-Den, M.M. El-Nahass, J. Opt. Laser Technol. 35 (2003) 335.

Fig. 7. Real and imaginary parts of the dielectric constant dependence on wavelength.

where e1 and e2 are real and imaginary parts of the dielectric constant, respectively. The single oscillator parameters Eo and Ed can be related to the imaginary of e2 of the complex dielectric constant. The M1 and M3 moments of the ei spectrum for the lm is described as [17], E2 o M 1 M 3 M3 E2 1 d M 3 Ed : Eo 9 10

and the dielectric constant for long wavelength is dened e1 1 11

The e1, M1 and M3 values for the lm were found to be 13.60, 12.61 and 0.48 eV2, respectively. The real and imaginary parts of the dielectric constant are related to the n and k values and these values are dened as [16], e 1 n2 k 2 ; e2 2nk: 12

The real and imaginary parts of the dielectric constant dependence on wavelength are shown in Fig. 7. The real part of dielectric constant of the thin lm is higher than the imaginary part. The relation between the lattice dielectric constant and refractive index is given by the following relation [18], n2 e L e2 N 2 k; c2 p m 13