Photoluminescence Study of Copper Selenide Thin Films

K.S Urmila, Namitha Asokan T and B.Pradeep

Solid State Physics Laboratory, Cochin University of Science and Technology, Kochi 682 022, Kerala, India
E-mail: urmilaks7@gmail.com

Abstract. Thin films of Copper Selenide of composition of composition Cu 7Se4 with thickness 350nm are deposited on
glass substrate at a temperature of 498K±5K and pressure of 10-5 mbar using reactive evaporation, a variant of Gunther’s
three temperature method with high purity Copper (99.999%) and Selenium (99.99%) as the elemental starting material.
The deposited film is characterized structurally using X-ray Diffraction. The structural parameters such as lattice
constant, particle size, dislocation density; number of crystallites per unit area and strain in the film are evaluated.
Photoluminescence of the film is analyzed at room temperature using Fluoro Max-3 Spectrofluorometer.

Keywords: Copper Selenide; Thin films; Reactive evaporation; XRD; Photoluminescence.

PACS: 81.15.-z; 61.05.cp.

INTRODUCTION has been found that the deposition of stoichiometric

compound layers by simultaneous evaporation of
Copper Selenide is a technologically well- individual components is possible only by selecting a
recognized metal chalcogenide belonging to I-VI suitable substrate temperature and adequate incident
family of semiconductors with p-type conductivity, a rates for the components [14].
property useful for soar cell fabrication. Thin films of In the present work, a conventional vacuum system
copper selenide are important materials for operated in the range of 10-5 mbar is used for the
applications in Solar Cells [1], Superionic Conductors preparation of Cu7Se4 thin film. Ultrasonically cleaned
[2], Solar Control Coatings [3], Thermoelectric optically flat glass slides are used as the substrates and
Converters [4] and Microwave Shielding Coatings [5]. are mounted on a substrate holder with a heating
The attraction of this material lies in its feasibility of arrangement. The temperature of the substrate is
producing CuInSe2 that can be used as an efficient measured using a fine wire chromel-alumel
absorber layer in solar cell fabrication [6]. It exists in a thermocouple. When the required substrate
wide range of stoichiometric (CuSe, Cu2Se, CuSe2, temperature 498K±5K is attained, high purity
Cu3Se2, Cu5Se4, Cu7Se4) and non-stoichiometric Selenium (99.99%) from a glass crucible kept in a
(Cu2-xSe) compositions [7]. Several methods such as molybdenum basket is evaporated. When sufficient
Chemical Bath Deposition [8], Electrodeposition [9], flux of Selenium is obtained high purity Copper
Thermal Evaporation [10], Electroless Deposition [11] (99.999%) from a molybdenum boat is evaporated in
and Pulsed Laser Deposition [12] are reported for the the atmosphere of selenium. Rate of evaporation of
preparation of copper selenide thin films of different copper and selenium is controlled by the amount of
crystalline modifications and varying stoichiometries. current that passes through the sources. When
This paper deals with the structural and sufficient fluxes of copper and selenium are attained
photoluminescence properties of copper selenide thin the shutter kept above the sources is removed so that
films of composition Cu7Se4 preapared by reactive the vapours of individual elements reach the substrate
evaporation. and react to form the compound film on the substrate
surface. Unreacted elemental atoms or molecules will
re-evaporate from the substrate surface due to its
EXPERIMENTAL DETAILS
elevated temperature. Source and substrate
temperatures are properly controlled throughout the
Thin films of Cu7Se4 are prepared by reactive
film deposition so as to obtain good quality Cu7Se4
evaporation, which is a variant of Gunther’s three
thin films.
temperature method [13]. For many binary systems it

Optics: Phenomena, Materials, Devices, and Characterization

AIP Conf. Proc. 1391, 770-772 (2011); doi: 10.1063/1.3643675
© 2011 American Institute of Physics 978-0-7354-0960-6/$30.00

770
 X-Ray Diffraction (XRD) analysis is used to 1
identify the phase and structure of the film and is ρ=
D2
carried out using Rigaku D MaxC X-Ray The number of crystallites N per unit area is
Diffractometer for 2 varying from 100 to 900 with estimated as 16.204 1014 m-2 using the relation [15]
CuK (1.5404 Ǻ) as the radiation source. The t
accelerating voltage is 30 KV and tube current is N= 3
20mA. Photoluminescence spectrum of the film is D
recorded at room temperature using Fluoro Max-3 where t is the thickness of the film.
Spectrofluorometer that functions under the control of The strain is calculated as 9.899 10-1 using the
DataMax Spectroscopy software. The excitation expression [15]
source used is a 150W Xenon flash lamp.  1  λ 
S=    βcos θ 
 sinθ   D 
RESULTS AND DISCUSSION
Photoluminescence Properties
Structural Properties
PL spectrum of a typical Cu7Se4 thin film of
The XRD pattern of the as prepared Cu7Se4 thin thickness 350nm is shown in figure 2.
film of thickness 350nm is shown in figure 1.
5500
60000
(222) 5000

50000 4500

4000
Intensity(arbitrary units)

PL Intensity (arbitrary units)

40000
3500

3000
30000

2500
20000
2000

1500
10000

1000

0 500
0 20 40 60 80 100
0
2(Degree)
600 650 700 750 800 850 900
Wavelength (nm)

FIGURE 1. The XRD pattern of the as prepared Cu7Se4

thin film. FIGURE 2. The PL spectrum of the as prepared Cu7Se4 thin
film.
The calculated d value well matched with that of
PL spectrum of the Cu7Se4 thin film is recorded at
Cu7Se4 in the standard JCPDS (File No.26-557). XRD
room temperature. The excitation wavelength given is
pattern shows a well-defined peak with very high
550nm, which is the wavelength, corresponding to the
intensity at 2
which suggests that the prepared
optical band gap (2.25eV) of the prepared Cu7Se4 thin
film is polycrystalline in nature. All the other peaks are
film [16]. PL emission is observed at energies 2.1eV,
suppressed due to preferential orientation of the
1.9eV and 1.5eV.The difference in energies can be
crystallite along the (222) plane. The structure of
considered to have its origin from a radiative donor-
Cu7Se4 is simple cubic with a lattice constant
acceptor pair recombination at defect levels with
calculated as 11.33 Ǻ.
energies 2.1eV, 1.9eV and 1.5eV within the band gap
Particle size is calculated as 60nm using Debye
of the film [17]. It can be concluded that there is a
Schrrer formula [15]
non radiative transition from conduction band to defect
0.9λ levels with energies 2.1eV, 1.9eV and 1.5eV and from
D=
βcos θ these defect levels radiative transitions occurred with
where  is the wavelength of the X-Ray used,  is the energies 2.1eV, 1.9eV and 1.5eV to valence band. PL
fill width at half maximum in radians and 
is the emission of the film is due to these radiative
Bragg’s angle. transitions from defect levels to valence band. PL
Dislocation density is estimated as 2.778 1014 studies can be used as one sensitive method to detect
lines/m2 using the relation [15] the defect states present in the film.

771
 CONCLUSION 5. Ivan Grozdanov, Synthetic Metals 63, 213-216 (1994).
6. R.N.O’Brien and K.S.V. Santhanam, Journal of the
Electrochemical Society 139, 434-437 (1992).
Copper Selenide thin films of composition Cu7Se4 7. Z.A. Talib, L.Y.C Josephine, W.M.M. Yunus, Z.Zainal,
are successfully deposited on glass substrates under S.A.Halim, M.M. Moksin, K.P. Lim and W.D.W.
optimized deposition conditions using reactive Yusoff, Solid State Science and Technology 16, 147-152
evaporation. XRD shows that the prepared films are (2008).
polycrystalline in nature. The films possess a simple 8. V.M. Garcia, P.K. Nair and M.T.S. Nair, Journal of
cubic structure. Structural parameters such as lattice Crystal Growth 203, 113-124 (1999).
constant, particle size, dislocation density; number of 9. L.Thousin, S.Rouquette- Sanchez and J. Vedel,
crystallites per unit area and strain in the film are Electrochimica Acta 38, 2387-2394 (1993).
10. J. Ying Chyi Liew, Zainal. A. Talib, W. Mahmood M.
estimated. PL spectrum of the sample is recorded at
Yunus, Zulkarnain Zainal, Shaari A. Halim, Mohd M.
room temperature. PL emissions are observed at Moksin, Wan Mohd Yusoff and K. Pah Lim, Central
energies 2.1eV, 1.9eV and 1.5eV. The excitation European Journal of Physics 7, 379-384 (2009).
wavelength given is 550nm. The film shows p-type 11. Santhosh.K.Haram and K.S.V. Santhanam, Journal of
conductivity, which on further work, can be Electroanalytical Chemistry 396, 63-68 (1995).
considered as an absorber layer in solar cell 12. Ming-Zhe Xue, Yong- Ning Zhou, Bin Zhang, Le Yu,
fabrication. Hua Zhang and Zheng-Wen Fu, Journal of the
Electrochemical Society 153, A2262-A2268 (2006).
13. Karl-Georg Gunther, “Interfacial and Condensation
ACKNOWLEDGMENTS Processes Occurring with Multicomponent Vapours”, in
The Use of Thin Films in Physical Investigations, edited
The first author (UKS) would like to thank Cochin by J.C. Anderson, London: Academic press, 1996, pp.
University of Science and Technology for financial 213-232.
support in the form of Research Fellowship. Second 14. M.C. Santhosh Kumar and B. Pradeep, Semiconductor
author (NAT) would like to thank UGC for financial Science and Technology 17, 261-265 (2002).
assistance in the form of research fellowship RFSMS. 15. M. Dhanam, P.K. Manoj and Rajeev. R. Prabhu,
Journal of Crystal Growth 280, 425-435 (2005).
16. Urmila K.S, Namitha Asokan. T and B.Pradeep,
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