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Journal of Physics and Chemistry of Solids xx (2005) 13 www.elsevier.com/locate/jpcs

Temperature dependence of the Urbach energy in ordered defect compounds Cu-III3-VI5 and Cu-III5-VI8
Ismardo Bonalde a,*, Ernesto Medina a, S.M. Wasim b
a b

cas, Centro de F sica, Apartado 21874, Caracas 1020-A, Venezuela Instituto Venezolano de Investigaciones Cient rida 5101, Venezuela Facultad de Ciencias, Centro de Estudios de Semiconductores, Universidad de Los Andes, Me

Abstract Two previous models used with success in Cu-III-VI2 semiconductors have been employed to study the temperature dependence of the Urbach energy in ordered compounds Cu-III3-VI5 and Cu-III5-VI8. The model which contains two variable parameters seems to explain better the data over the whole temperature range studied. However, the ordered vacancy or the donor acceptor defect pair in the cation sublattice provides new features in these compounds that need further study. q 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Semiconductors; A. Electronic materials; D. Defects; D. Optical properties

1. Introduction The optical absorption coefcient at a given temperature in semiconductors and insulators is found to vary exponentially with the incident photon energy hn just below the band edge [1,2]. This behavior, referred to in the literature as the Urbach Martienssen or simply the Urbach rule, can be expressed as [3] aE Z a0 expK sE0 KE=kB T ; (1)

where a0 and E0 are the characteristic parameters of the material and s is the steepness parameter given by   h np 2k T s Z s0 B tanh : (2) hn p 2kB T Here, s0 is a temperature-independent parameter inversely proportional to the excition/electronphonon interaction [4]. The parameter hnp, associated with the Urbach tail, is considered to be the energy of phonons involved in the formation of photon absorption edge. Because of the proximity of the experimental hnp with the longitudinal or transverse vibrational modes in binary compound semiconductors, it was thought earlier that Urbach tail originates from excition phonon interaction that involves one of these modes [3].
* Corresponding author. Tel.: C58 212 504 1472; fax: C58 212 504 1148. E-mail address: bonalde@ivic.ve (I. Bonalde).

The Urbach energy kBT/s in Eq. (1), which represents the width of the exponential tail, was thought to be a direct measure of the temperature-induced and topological disorders [5]. Recently, this energy has also been associated to structured defects in crystalline compounds [6,7]. Wasim et al. [6] proposed a phenomenological model, an extension of a previous one by Cody et al. [5], which accounts for the structural-disorder contribution to the Urbach energy   k Q 1 CP N EU T Z B C : (3) s0 2 expQ=T K1 Here, Q is the Einstein characteristic temperature. The empirical parameters P and N were quantitatively correlated with disorder characterization of the samples in terms of deviation from molecularity and valence stoichiometry. Eq. (3) has very satisfactorily described the temperature dependence of the Urbach energy of a signicant number of samples of CuIII-VI2 [6], Cu-III3-VI5 [8,9], and Cu-III5-VI8 [1012] semiconductors. More recently, we have used a rst principle approach to relate the empirical model by Wasim et al. to the thermal/disorder broadening of a harmonic oscillator with average frequency associated with the measured phonon modes [7]. In this approach   hn p hn p EU T Z coth ; (4) 2s0 2k B T where hnp encodes the thermal and structural disorder contributions through either the regular modes of the defect

0022-3697/$ - see front matter q 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.jpcs.2005.10.002

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I. Bonalde et al. / Journal of Physics and Chemistry of Solids xx (2005) 13

free sample or the localized modes produced by disorder. Expression (4) describes very well the temperature dependence of the Urbach energy of Cu-III-VI2 semiconductors on the basis of the single tting parameter hnp [7]. In CuGaTe2 samples, this value of hnp was found to be quite close to the one obtained from a combined analysis of Raman and infrared spectra [7]. In the present work, we make a comparative study of the applicability of Eqs. (3) and (4) to Cu-III3-VI5 and Cu-III5-VI8 in order to explore new physics introduced by ordered arrays of cations vacancies or donor acceptor defect pairs (DADPs) 2 K 1 In; GaC Cu ; 2VCu present in these materials. Such arrays are the reason why these compounds are called ordered defect compounds (ODCs). All the data analyzed in this work and the sample preparation techniques have been previously reported [912]. 2. Results and discussion The Urbach energy as a function of temperature in a sample of CuIn3Te5 [9] is shown in Fig. 1, and in samples of CuIn5Te8 [11], CuIn5Se8 [10], CuGa5Se8 [12] in Fig. 2. The continuous lines in Figs. 1 and 2 are ts of Eq. (3) to the data. The three adjustable parameters Q, N, and P together with hnp of Eq. (2) are given in Table 1. These values were previously reported [10,12,13]. The dashed lines in the gures correspond to ts of Eq. (4) to the data, and the values of the only adjustable parameter hnp are also given in Table 1. For comparison hnp obtained from Eq. (2) is termed as 1 2 1 hn p , whereas that from Eq. (4) as hnp . It can be noticed that hnp 2 and hnp are in excellent agreement. The origin of the values of 1 2 hn p and hnp in CuIn3Te5 and CuIn5Te8 [13] and in CuIn5Se8 and CuGa5Se8 [14] can be explained by a combined analysis of Raman and infrared spectra [7]. It suggests that also in these materials hnp depends on the structural-disorder and other localized modes caused by the presence of ordered vacancies or donoracceptor defect pairs. Moreover, a comparison reveals that

52 48 Urbach's energy (meV) 44 40 36 32 28 24 0

Culn5 TeB Culn5 SeB CuGa5 SeB







Temperature (K)
Fig. 2. Urbach energy versus temperature of a samples of CuIn5Te8, CuIn5Se8, and CuGa5Se8. The solid line correspond to Eq. (3) and the dashed line to Eq. (4). The data of CuGa5Se8 and of CuIn5Se8 were shifted up by 4 and 8 meV, respectively, for the sake of clarity.

hnp in Cu-III-VI2 samples is, in general, relatively smaller than in the ODCs. This would support the assertion that ordered arrays of DADPs produce additional localized modes which increase the hnp associated with Urbach tail. From the gures, it is observed that, within experimental errors, the Urbach energy data are described quite well by both Eqs. (3) and (4) in the high temperature region. However, at lower T, the former follows the data down to the lowest reported temperature, whereas the latter does it only down to about 150 K. Because of the high values of hnp, it is expected from Eq. (4) that the data reached a plateau at relatively high temperatures. Such a behavior is not observed. However, a tendency is seen where the theoretical value of EU from Eq. (4) seems to saturate below 150 K. This contrasts with what is
Table 1 Phonon energies
1 hv p

36 Urbach's energy (meV)


2 hv p


as determined by tting Eqs. (2) and (4), respectively, to the EU(T) and s(T) data Compound
1 hvp (meV) 2 hv p (meV)

q (K) 130 162 160 213

N 0.58 0.48 0.57 0.50

P 3.80 2.55 1.45 1.72


CuIn3Te5a CuIn5Se8b CuIn5Te8c CuGa5Se8d

63 58 45 54

62 57 44 57

28 0 50 100 150 200 250 300 Temperature (K)

Fig. 1. Urbach energy versus temperature of a sample of CuIn3Te5. The solid line correspond to Eq. (3) and the dashed line to Eq. (4).

The values of the adjustable parameters q, N and P have been obtained by tting Eq. (3) to the EU(T) data reported previously. a See Ref. [9]. b See Ref. [10]. c See Ref. [13]. d See Ref. [12].

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found in Cu-III-VI2 semiconductors, in which the temperature dependence of the Urbach energy is described precisely by Eq. (4) down to the lowers reported temperatures in samples with high values of hnp [7]. It can also be mentioned that higher value of P and lower of N obtained from the t of Eq. (3) to the EU versus T data of the ODCs, as compared to Cu-III-VI2 compounds, would indicate greater disorder. However, a study based on several samples of the same ODC is required to establish a correlation between P, N, and hnp, as it was done in CuInTe2, CuGaTe2, and CuInSe2. It is well known that the temperature variation of the energy band gap EG is mainly due to the sum of the effect of electronphonon interaction and thermal expansion [5,12]. In Cu-IIIVI2, the former contributes to about 80% to the temperature shift in EG and is dominant at high temperature, whereas the latter is relevant below 100 K. The same electronphonon interaction is involved in the Urbach tail. Because it is very likely that in the ODCs the thermal expansion term starts to dominate at a relatively higher temperature in comparison to the Cu-III-VI2 compounds, it can be conjectured that the departure of Eq. (4) from the experimental data at low temperature could be related to the decreasing contribution of the electronphonon interaction. 3. Conclusions The temperature dependence of the Urbach energy of CuIII3-VI5 and Cu-III5-VI8 semiconductors was studied in the light of two models used previously with success in Cu-III-VI2 compounds. Although one of the models can account for the phonon energy hnp and the other can describe the temperature variation of the Urbach energy, further study which could incorporate specically the localized modes caused by the

DADPs in the theoretical models is required. This is because the vacancy or DADP sublattice of the ordered defect compounds appears to add unsuspected new features to the Urbach energy. Acknowledgements This work was nanced by the National Fund for Science and Technology of Venezuela (FONACIT) through project G-97000670. References
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