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Thin Solid Films 423 (2003) 103107

Studies on Seebeck effect in spray deposited CuO thin film on glass substrate
M. Muhibbullah, M.O. Hakim*, M.G.M. Choudhury
Department of Physics, Rajshahi University, Rajshahi 6205, Bangladesh Received 23 October 2001; received in revised form 26 July 2002; accepted 18 September 2002

Abstract Undoped thin films of cupric oxide have been prepared by a simple chemical spray technique. Obtained samples were mostly polycrystalline and p-type semiconductor. Thermopower of a set of as-deposited samples with thickness between 340 and 620 nm have been measured in the temperature range 300450 K. The thermovoltages were found to change sign with thickness. The dominating carrier scattering process that can limit the electrical conductivity or the Hall mobility values at room temperature may be the lattice phonon scattering. The observed variations of the position of Fermi level with the film thickness have been qualitatively explained invoking the principle of modulation of the acceptor density profile by the density of donors during the time of growth of film. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Spray pyrolysis; CuO; Thermoelectric power; Fermi level

1. Introduction It is known that CuO (-ic) and Cu2O (-us) materials are in general p-type semiconductors, and therefore may be useful to fabricate junction devices such as pn junction diodes. In the literature, some studies on this material were available on advanced preparation techniques w1,2x and on the electrical properties w3,4x. Apart from semiconducting applications of this material, it is also useful for the preparation of microwave dielectric materials w5x, high Tc superconductors w6,7x, gas sensing pn heterocontacts w8x etc. CuO material in pure condition with good stoichiometry is almost like an electrical insulator. But this material when prepared by a chemical spray method, a lot of defects like constitutional faults, point defects, impurities from the reactants and from substrate materials are got associated with the otherwise pure crystalline state of the material and cause deviation from stoichiometry. This deviation although is not deliberate
*Corresponding author. E-mail address: mohakimbd@yahoo.com (M.O. Hakim). 0040-6090/03/$ - see front matter PII: S 0 0 4 0 - 6 0 9 0 0 2 . 0 0 9 7 0 - 7

but it leads to important semiconducting characteristics of the prepared CuO samples, and are interesting to study. Seebeck effect or thermoelectric power (TEP) is an interesting property because it is a sensitive tool for detecting any change or distortion of the Fermi surface, which helps mapping the energy band pattern of the charge carriers during electrical conduction. To study Seebeck effect in CuO the experimental samples were prepared on glass substrates (corning microscope slides) by applying not an advanced method but by a simple chemical spray method using a low cost indigenous equipment w9x. We know electrical conduction processes are dependent on the composition as well as on the structure of the sample as prepared. Sample preparation conditions and the technique have therefore a significant role to influence the samples properties. In the present study, however we have given attention only on the temperature and thickness dependent behaviors of TEP of the samples. The aim is to observe the nature of variation of the position of Fermi level at room temperature in the energy band pattern of CuO, and to throw some light on the type of dominating carrier scattering mechanism.

2002 Elsevier Science B.V. All rights reserved.

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Fig. 1. XRD patterns of CuO thin films at various substrate temperature, Ts , and film thickness, t; (a) Tss200 8C, ts310 nm; (b) Tss200 8C, ts510 nm; (c) Tss225 8C, ts500 nm; (d) Tss275 8C, ts490 nm.

2. Experimental 2.1. Sample preparation Starting material for the preparation of CuO samples was cupric chloride CuCl22H2O in the form of aqueous solution of concentration 0.050.25 M. This was sprayed pneumatically over a heated clean glass substrate using air as carrier gas in normal air ambient. Substrate temperature and solution concentration optimization procedures for our setup showed that 200225 8C substrate temperature and 0.2 M concentrations with 1 mlymin of spray rate could be appropriate for good quality polycrystalline films. We have prepared samples for the present study following the above conditions. 2.2. Structural properties X-ray diffraction (XRD) patterns of the films prepared at substrate temperature Tss200 8C with thicknesses 310 and 510 nm are shown in Fig. 1a and b, and at Tss225 and 275 8C having nearly equal thicknesses 500 and 490 nm are shown in Fig. 1c and d, respectively. The XRDs show fine crystalline structure with clear characteristic peaks of CuO phase in all the samples as found by comparison with standard (ASTM) XRD patterns of the pure CuO material. Some of the smaller peaks are common to both the Cu2O and CuO phases. But as we know chemical reaction of CuCl2 with H2O at approximately 200 8C does not favor the formation of Cu2O, the possibility of Cu2O formation is therefore

less. In a defect lattice however there may be a small fraction of other phases than CuO but they are not deliberate and may be considered as crystal imperfections. Cu2O has a prominent peak at 2us36.458, which we do not find in any of our samples. The CuO (1 1 1) reflection at 2us35.4958, observed with the highest intensity, in addition to all the other peaks of CuO phase confirm that the crystal lattice is chiefly copper (II) oxide. The structure is monoclinic with lattice parame ters as4.704 A, bs3.414 A and cs5.004 A. 2.3. The thermoelectric power Measurement of TEP was carried out by the integral method. The experimental setup w10x has been illustrated schematically in Fig. 2. Reference metal was pure copper whose TEP is negligible (1.7 mVyK) with respect to CuO samples (100500 mVyK). The reference low temperature (0 8C) was an ice bath in which one of the CuOyCu junctions was immersed, and the temperature of the other junction was varied by attaching it to a flat resistant heater driven by a controlled electrical power supply. The temperature of the hot junction was monitored by a thermocouple whose thermovoltages and the generated thermovoltages in the sample both were measured by digital voltmeters. Possible leakage of emf between the terminals in the ice bath was protected by proper insulation. The generated thermovoltage followed almost reversible path during thermal cycling of the samples. Film thickness was measured by Tolansky interferometric method using monochromatic light.

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energy surface under thermal equilibrium, is given by w11x Qskyew(5y2ys)yE9FykTz y ~


x |

(1)

where Q is thermopower, E9F is the Fermi energy for the holes with reference to EV, the valence band edge, and can be expressed by E9FsyEgqEF. (2)

Fig. 2. Experimental setup for TEP measurement.

3. Results and discussion Fig. 3 shows TEP, Q, vs. 1yT plots for films of different thicknesses. It shows that TEP becomes almost temperature independent at higher temperatures, which may be due to the characteristic of the pinning of Fermi levels at these temperatures. Some of the samples show negative TEP at room temperature even they are p-type. The carrier concentrations of the samples were measured separately and were found to be of the order of 1021 1022 my3. All the samples were therefore considered nondegenerate at room temperature. Since the measurement of thermopower was limited in the temperature range from room temperature up to 450 K, the contribution from phonon drag to TEP can therefore be considered negligible. The electron drift contribution to TEP for a p-type nondegenerate semiconductor with spherical constant

here EF is the Fermi energy with reference to the conduction band edge EC, and Eg is the optical band gap. The carrier scattering index, s, is related to the relaxation time and energy as tsaEys. In the absence of any detailed knowledge of the temperature dependence of Eg we may put for a limited temperature range E9FsE(0)ygT (3)

where E(0) is the low temperature limit of E9F and is the chemical potential. It is often interpreted as half of the band gap but is not always true. g is the appropriate temperature coefficient w12x. Using Eq. (3) and As(5y 2ys), Eq. (1) can be rewritten as Qs(Akqg)yeyE(0)yTe The Peltier coefficient is then psw(Akqg)TyeyE(0)yex (5) (4)

Fig. 3. Variation of TEP of CuO with inverse of temperature for film thickness ranging from 347 to 612 nm.

Eq. (1) indicates that A corresponds to the value of Q at infinite temperature limit. From Fig. 3 it is observed that the high temperature side of all the curves when extrapolated to 1yTs0 give almost a common intercept on the ordinate and an average value of As1.1 can be obtained. This shows that s3y2, and the predominant scattering mechanism is the lattice phonon scattering in the room temperature range. At the same time a T y1.5 dependence of Hall mobility (mH) may be expected. From the slopes of p vs. T plots, with Af1 in Eq. (5) the values of g and E(0) for the set of samples were determined using the measured values of p at room temperature. The values of Fermi levels E9F can then be calculated from Eq. (3) or EF from Eq. (2) by using the experimentally measured values of Eg. Obtained values of E(0), E9F, and g for our samples are plotted as a function of inverse of thickness in Fig. 4. From this figure, we observe that the curves are almost straight line. The extrapolated values may correspond to the values of those quantities for the bulk CuO crystals having the same composition and structure as that of the films. We obtain E(0)s1.6 eV, gsy4.15 meVyK, and E9Fs0.38 eV above the valence band edge. The values of E9F for different film thicknesses show that Fermi levels start from 0.118 eV above the valence band edge at higher film thicknesses and move towards the band edge, and finally entered the extended band at lower film thickness. The latter situation may

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Fig. 4. Fermi energy E9F , E(0), and g as a function of 1000yt at 300 K.

occur only when the density of the acceptors Na becomes very high in comparison to the density of donors Nd in the films. It has been widely believed that in CuO excess oxygen ions or copper ion vacancies in the lattice site are the main sources of acceptors, which produce p-type conductivity w1,13x. On the other hand oxygen ion vacancies or excess copper ions in the interstitial position can act as donors. In addition to those centers Cly ions in the samples, which may come from the spray solution, can also work as donors. In spray deposited films, all of these defects may be present at a time, but their relative concentrations depend remarkably on the preparation condition and the degree of physical stoichiometry of the sample. Some of the data from Fig. 3 have been replotted at four fixed temperatures in Fig. 5 to show TEP as a function of film thickness. In the room temperature side, strong thickness dependence of TEP can be noticed while at the elevated temperature only films of thickness below 420 nm show such thickness dependence. At higher film thickness TEP values decrease with the rise of temperature while at lower thickness this value shows a slight increase. Transport behavior therefore seems to experience a transition at some value of thickness (;420 nm). This transition may be due to two major reasons; (a) relative proportions of donor and acceptor densities Nd and Na in the film may vary with the film thickness as mentioned earlier, and (b) percolation of carriers through the amorphous tissue region at the grain boundaries may be affected by the change of film thickness. Since the crystalline structure of the film does not change appreciably with the change of film thickness, (as evident from the XRDs), the effect if any, due to self-broadening of the amorphous tissue region may be considered less. The mechanism, which seems to be

Fig. 5. Variation of TEP of CuO with film thickness for temperature ranging from 300 to 450 K.

more significant, is the oxygen chemisorptionydesorption at the grain boundary region. This can control the magnitude of the grain boundary potentials and thereby the percolation processes. Predominance of any one of chemisorption or desorption at the grain boundary depends on the relative concentration of the chemisorbed species present in the ambient and in the chemisorptions site. In absence of any quantitative formula, the variation of the position of Fermi level with film thickness, as mentioned above, can be qualitatively explained if we consider Fig. 6. It is observed that at the initial stage of spraying the growth rate of film remains higher i.e. the chemical reaction rate is faster, therefore at low film thickness there is high possibility of creation of Cu ion vacancy in the lattice site (or excess oxygen from air may be trapped) and the condition Na4Nd may hold

Fig. 6. Physical growth rate of CuO thin film as a function of deposition time.

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good. But as the film thickness gradually increases and the chemical reaction rate becomes slower while the reactant supply rate remains sensibly constant as before, a considerable amount of unreacted Cu ions got trapped in the lattice, which enhance the donor concentration Nd in the films. This may lead to NafNd, and the Fermi level is pulled out of the band edge at higher film thickness w11x. As mentioned earlier, the samples are all p-type but at low film thickness, some of them anomalously show negative TEP at room temperature. This is again a consequence of the fact that the compensation ratio, Nd yNa, for a p-type sample remains less than 0.5 as pointed out by Mott w12x, and is also consistent with the explanation given above. 4. Conclusions The method of chemical spray with aqueous CuCl2 solution can be used to produce polycrystalline films of CuO, and the films so produced are p-type semiconductors. Sign of thermopower of the samples having thickness above 350 nm is positive, and the position of Fermi level shows that samples having thickness below 350 nm are mostly uncompensated in which the density of acceptors is very large in comparison to the density of the donors. The compensation ratio slowly increases as thickness increases. It is not only the temperature but the film thickness have also been found to play an important role in controlling the position of Fermi level in the energy band pattern of the film having various

defect states in as-deposited condition. In the room temperature region, lattice phonon scattering may be the dominating scattering process that can limit the electrical transport process. References
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