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Vacuum 80 (2006) 631635 www.elsevier.com/locate/vacuum

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Studies on p-type copper (I) selenide crystalline thin lms for hetero-junction solar cells
R.S. Manea, S.P. Kajveb, C.D. Lokhandeb, Sung-Hwan Hana,
a

Inorganic Nano-materials Laboratory, Department of Chemistry, Hanyang University, Sungdong-Ku, Haengdang dong 17, Seoul, 133-791 Republic of Korea b Thin Film Physics Laboratory, Department of Physics, Shivaji University, Kolhapur-416004, India Received 21 May 2005; received in revised form 9 August 2005; accepted 13 August 2005

Abstract Deposition of polycrystalline copper (I) selenide thin lms onto glass substrates at relatively low temperature (95 1C) have been carried out by chemical route using optimized preparative conditions. The XRD pattern conrmed the formation of copper (I) selenide semiconducting lms with orthorhombic structure. A direct-type transition with band gap energy of 1.73 eV was reported from optical absorption studies. p-Type behavior conrmed from sign of thermally induced voltage (thermo-emf), which may nd interesting applications in hetero-junction solar cells as an absorber layer. r 2005 Elsevier Ltd. All rights reserved.
Keywords: Copper selenide; Optical properties; Thermo-emf; Solar cells

1. Introduction Nanocrystalline materials in the form of thin lms have recently attracted large interest due to its semiconducting behavior and have successfully been applied to the electroluminescent devices, eld-effect transistors, photovoltaic cells, etc. These lms are also found to have numerous applications including quantum electronics, optoCorresponding author. Tel.: +822 2292 5212; fax: +822 2299 0762. E-mail addresses: rsmane_2000@yahoo.com (R.S. Mane), shhan@hanyang.ac.kr (S.-H. Han).

electronic, sensors, etc. [1,2]. As far as nanometer size is concerned, chemical methods give better orientation, which are least expensive, non-polluting and easy to incorporate suitable doping materials for altering the lm properties. These processes are the low-temperature processes which enables formation of thin lms onto plastic as well as glass substrates in addition to the conducting lms (substrates), such as uorine-doped-tin-oxide (FTO), stainless steel, etc. This property can potentially lead to a new generation of photovoltaic devices that are light in weight, foldable, exible and moldable. Copper selenide semiconducting material nds number of applications in

0042-207X/$ - see front matter r 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.vacuum.2005.08.021

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solar cells, photo-detectors, etc [3]. The literature highlights very little work for the deposition of copper selenide thin lms using chemical methods with different copper releasing sources i.e. copper acetate, copper chloride, tetra-amine copper [46], etc. Copper selenide usually exists as Cu2Se, Cu2xSe, CuSe or Cu3Se2 i.e. degenerating semiconductor material. In the present study, nanocrystalline thin lms of copper selenide have been deposited by chemical deposition methods onto glass substrate. The preparative conditions were optimized to get adherent, uniform, and pinholefree thin lms of copper (I) selenide. These lms were characterized for their structural, optical and thermoelectric measurements by means of X-ray diffraction (XRD), UV/VIS spectrophotometery, thermo-emf techniques, etc.

2. Experimental procedure Microscopic glass slides were cleaned with a suitable cleanser, scrubbed with soft cotton, washed thoroughly with de-ionized water followed by rinsing and drying in air. The substrates were kept in an airtight box in order to avoid contact of moisture. The preparation of 1 M solution of copper chloride (CuCl2) was carried out by dissolving 6.722 g of CuCl2 in 50 mL of distilled water and 0.1 M solution of sodium selenosulphate (Na2SeSO3) solution was prepared for the supply of Se2 ions. For sodium selenosulphate solution preparation, we adopted a procedure, reported earlier in our published work [7,8]. For preparation of copper (I) selenide nanocrystalline lms, 20 mL (1 M) solution of CuCl2 was taken in a 75 mL beaker; 4 mL triethanolamine (TEA) was added to form a complex. The solution was stirred for a few seconds. The pH of the resultant solution was 8 for the as-prepared solution, which was increased to 8.5 by drop-wise addition of excess ammonium hydroxide solution (7%). A 20 mL (0.1 M) solution of Na2SeSO3 was added nally to it for the lm formation. The glass substrates were xed to the circular holder and allowed to rotate with a speed of 20 rpm. The deposition bath was maintained at 95 1C in which the beaker containing the

substrates was placed. After a time duration of 30 min, the copper selenide lms with reddishblack color coated on both the sides of the glass substrate were taken out, washed well with deionized water, dried and kept in an airtight container for further analysis. Chung and Rubner [9] have reported that after a certain thickness (100 nm) of the lm, there is a linear growth which implies that the species adsorbed to the surface of the substrate are consistent and constant throughout. Therefore, the molecular architecture through the bulk of the thin lm should be uniform, in terms of density. Thickness of the as-deposited copper (I) selenide thin lms was calculated as 210 nm by the weight difference method, using a sensitive microbalance (nanogram) and assuming the lm density 6.303 gm cm3. The structural characterization of copper selenide lms was carried out by XRD pattern recorded by PW-1710, (Cu-Ka radiation, ( unit. An optical spectrum was l 1:5426 A) recorded by using UV/VIS spectrophotometer (Hitachi model-330, Japan) in the wavelength range of 450780 nm. Use of silver paste was preferred for good electrical contacts. The thermoemf generated across the sample was measured by a digital voltmeter by maintaining one junction at cold and the other at hot.

3. Results and discussion 3.1. Reaction mechanism Here, we propose the reaction mechanism for the formation of copper selenide thin lms. CuCl2 precursor in the presence of TEA as a complexing agent can be written as CuTEA ! Cu TEA: (1)

Hydrolysis of sodium selenosulphate takes place in solution which releases Se ions as Na2 SeSO3 OH ! Na2 SO4 HSe : Now, HSe OH ! H2 O Se2 : (3) (2)

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Cu+ ions react with Se2 ions to form copper selenide as 2Cu Se2 ! Cu2 Se: (4)

The above-mentioned reaction is based on the concept of the ionic product (IP) and the solubility product (SP). When the IP of Cu+ and Se2 exceeds the SP of copper selenide, copper selenide nucleon formation occurs, that grows with time onto an appropriate substrate resulting in the lm formation and precipitate, respectively [10]. 3.2. Structural and optical studies The XRD pattern of as-deposited copper (I) selenide lm onto glass substrate is shown in Fig. 1. The existence of wide and sharp peaks [11] conrmed the crystalline nature of as-deposited lm. The 15401 broad hump is due to the glass ) substrate. The calculated interplanar distance d (A values were in close agreement to that of standard d (JCPDS data le no. 19-400), suggesting that the material formed in the form of a thin lm onto the glass substrate was copper (I) selenide. The orthorhombic crystal structure is notied. The optical absorption spectrum of as-deposited copper (I) selenide lm was studied at room temperature by using another glass as a reference as mentioned earlier. Fig. 2(a) shows the variation of optical absorbance with the wavelength of incident photons. The band gap energy, Eg was calculated using the standard relation [12]. Fig. 2(b) shows the variation of (ahn)2 vs. hn, (where a is the
3k cps
Relative Intensity (A.U) (0,2,0)

absorption coefcient which was obtained from an earlier data) for copper (I) selenide lm. The linear nature of the plot indicates the existence of the direct transition. The band gap, Eg was determined by extrapolating the straight portion to the energy axis at zero absorption coefcient. The estimated band gap energy was 1.73 eV, which is in good agreement with the value reported for Cu2Se thin lms [13]. An increase in band gap energy in relation to its bulk value (1.39 eV), suggests occurrence of size quantization in Cu2Se thin lms. 3.3. Thermo-emf studies The developed thermo-emf across the hot and cold junctions was measured for copper (I)

Absorbance, t (cm-1)

1.2

0.8

0.4

0.0 600 (a) 25

(h)2 x 108 (eV- cm1)2

800

Incident photon wavelength (nm)

20 15 10 5 0 1.6 2.0 h (eV) 2.4

(2,1,1) (2,0,0)

(1,2,2)

(2,1,2)

20.00

40.00

60.00

80.00

90.00

(b)

Fig. 1. XRD pattern of deposited copper (I) selenide onto glass substrate.

Fig. 2. Plot of absorption (at) versus wavelength of incident light (l) (a), and determination of its band gap energy from (ahn)2 vs. hn (b).

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selenide thin lm in the range of 300500 K with the help of digital, sensitive nano-voltmeter (see Fig. 3(a)). The polarity of the developed voltage is found to be positive, conrming p-type semiconducting behavior [14]. p-Type conductivity is attributed to the acceptor levels created by copper during the formation of thin lms, which is one of the interesting as well as an important candidate for designing pn heterojunction solid-state solar cells. The thermopower (emf) measurements showed p-type conduction for a given sample. This data was used to compute the charge carrier concentration, P (cm3). The charge carrier concentration, P can be expressed as (Fig. 3(b)) [15] P T 3=2 1015 9:7604 a0 =17:6735,
1.6

9.2
Log (cm - V - S )
2 1

8.8

8.4

8.0

2.6

2.8

3.0

3.2

1000/ T (K 1)

Fig. 4. Mobility of charge carrier variation in logarithmic scale with reciprocal of the temperature difference.

(5) where a0 is the magnitude of thermo-emf (mV) and T is the absolute temperature (K). The present data is further used to calculate the charge carrier density and mobility from which one can determine the carrier concentration energy and the potential barrier, respectively. The calculated activation energy was found to be 0.12 eV. It may be noted that in Fig. 4 the mobility of the charge carriers decreases with an increase in the temperature difference because of an increased scattering of carriers by phonons or lattice vibrations which increases at high temperatures [16].

Thermo-emf (mV)

1.2

0.8

0.4

0.0 0 (a) 20.0 40 80 120 Temperature difference (C) 160

4. Conclusions
19.9

19.8

19.7 2.2 (b)

2.4

2.6

2.8
1

3.0

3.2

1000 / T (K )

Fig. 3. Induced thermo-emf as a function of temperature difference (a), and variation of log of carrier concentration (P) with (1000/T) (b).

This paper presents the synthesis of a p-type copper (I) selenide thin lm onto a glass substrate by the chemical bath deposition method at relatively low temperature. As-deposited copper (I) selenide lm was nanocrystalline with orthorhombic structure. The optical absorption study shows that the copper (I) selenide lm has a direct optical band transition with a band gap energy of 1.73 eV. Thermoelectric measurement conrms p-type conductivity with activation energy of 0.12 eV and thus can be considered as a potential candidate for pn hetero-junction solidstate solar cells.

3 Log P (cm )

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Acknowledgements The authors wish to put on record their sincere thanks to the reviewer for the suggestions and modications for the improvement of the text of the paper. RSM, one of the authors, wishes to express gratitude to the Brain Korea 21 project and the National R&D Project for Nano-Science and Technology, Korea for the award of postdoctoral fellowship during the period of 20042005. References
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