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Journal of Non-Crystalline Solids 351 (2005) 3547-3550 www.elsevier.com/locate/jnoncrysol

Electrical properties of bulk amorphous semiconductor (GaSb)38Ge
A.I. Kolyubakin, V.E. Antonov *, O.I. Barkalov, A.I. Harkunov
Institute of Solid State Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow, Russia Received 15 July 2004; received in revised form 28 July 2005 Available online 21 September 2005

24

Abstract Temperature dependences of the dc conductivity and thermopower of a (GaSb)38Ge24 homogeneous bulk amorphous alloy are investigated at 110-425 K and at 180-400 K, respectively. The samples were prepared by spontaneous solid-state amorphization of a quenched crystalline high-pressure phase heated from 77 to 430 K at ambient pressure. In contrast to the parent amorphous GaSb compound exhibiting an unusual combination of electrical properties, amorphous (GaSb)38Ge24 is found to be a typical p-type semiconductor well described by the conventional Mott-Davis model. Ó 2005 Elsevier B.V. All rights reserved.
PACS: 71.23.Cq; 72.80.Ng

1. Introduction A number of crystalline high-pressure phases transform, at least partly, to a metastable amorphous state when the pressure is released [1,2]. The most effective means to produce bulk homogeneous amorphous samples free of crystalline inclusions is to retain such a high-pressure phase at ambient pressure by cooling it to liquid nitrogen temperature prior to releasing the pressure and then to heat this phase over the temperature interval of its spontaneous amorphization at ambient pressure [3-6]. Today, the electrical properties have been studied for three amorphous (a-) semiconductors prepared in this way: a-Zn41Sb59 [7], a-Al32Ge68 [8] and a-GaSb [9]. The a-Zn41Sb59 alloy was found [7] to be a typical amorphous semiconductor with an activated behavior of the electrical conductivity r and a linear increase in the thermopower S with increasing 1/T. By contrast, the a-Al32Ge68 [8] and a-GaSb [9] alloys showed combiCorresponding author. Tel.: +7 095 993 2755; fax: +7 096 524 9701. E-mail address: antonov@issp.ac.ru (V.E. Antonov). 0022-3093/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2005.08.005
*

nations of r(T) and S(T) dependences never observed in amorphous semiconductors. The unusual electrical properties of these alloys were described semi-quantitatively [8,9] in terms of a modified Mott-Davis model assuming that the Fermi level lies inside the valence band tail. The composition of the a-Zn41Sb59 and a-Al32Ge68 alloy cannot be varied since it is limited by the narrow homogeneity range of the corresponding high-pressure phase. The metallic high-pressure phase of GaSb forms a continuous solid solution with the metallic high-pressure phase of Ge, and samples of this crystalline GaSb-Ge solution transform into amorphous semiconductor state when the pressure is released [10,11]. As the first step to studying the effect of varying composition in the GaSb-Ge system, this paper reports on the electrical properties of amorphous (GaSb)38Ge24 semiconductor. Stable and metastable transformations in the (GaSb)38Ge24 alloy were earlier investigated in a wide pressure and temperature range and a procedure to produce homogeneous amorphous samples was worked out [12]. The structure of bulk amorphous samples prepared by this procedure was studied by neutron diffraction and


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analysed using reverse Monte Carlo simulations [6]. The samples were shown to be homogenous amorphous compounds free of any crystalline phases. The average nearest-neighbour co-ordination number equals 4.25 that exceeds 4 and therefore points to a noticeable distortion of the tetrahedral arrangement in the alloy. The Ge atoms randomly substitute the Ga and Sb atoms in the network characteristic of amorphous GaSb semiconductor investigated in [5]. The arrangement of the Ga and Sb atoms in a-(GaSb)38Ge24 demonstrate approximatelythe same degree of disorder as in a-GaSb, and about 30% nearest neighbours are the atoms of the same kind (Ga-Ga or Sb-Sb pairs).

8.0

7.5

7.0

2. Experimental To prepare amorphous (GaSb)38Ge24 samples in the present work, we used the same starting alloy and the same procedure as in Refs. [6,12]. The ingot of the (GaSb)38Ge24 alloy was melted from 99.999% Ga, Sb and Ge, crushed into powder in an agate mortar and pressed into pellets 8 mm in diameter and 5 mm thick. Each pellet was placed in a Teflon container and exposed to 7.7 + 0.3 GPa and 250 + 7 œC for 24 h in a toroid-type high-pressure chamber. The chamber was then cooled to 100 K, the pressure was lowered to atmospheric, the pellet was taken out of the chamber and X-rayed at 100 K to check that it consisted of the high-pressure metallic phase only. The recovered pellet was brought to the amorphous state by heating to 150 œC = 423 K at a rate of 20 œC minÀ1, then cooled to room temperature at 200 œC minÀ1 and X-rayed to check for the absence of crystalline inclusions. Three samples in the form of bars 1 ž 1 ž 5 mm3 were cut out of different amorphous pellets with an abrasive wire saw. Copper electrodes were stuck to the samples with silver paste. The dc conductivity, r, and the thermoelectric power, S, were measured at temperatures from 110 to 425 K and from 180 to 400 K, respectively.

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3

4

5

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Fig. 1. A representative dependence of the thermopower S vs. reciprocal temperature for (GaSb)38Ge24 amorphous semiconductor (open circles) and its linear fit (solid line). e is the elementary charge, k is the Boltzmann constant.

the conductivity, which is characteristic of most amorphous semiconductors. The thermopower increases approximately linearly with increasing reciprocal temperature. A linear dependence of S(TÀ1) in a wide temperature range is typical of many amorphous semiconductors and it is usually presented in the form: Se=k ? ES =kT þ C ; ð 1Þ where the values of ES and C are temperature-independent. In our case, the energy ES = 0.05 + 0.005 eV and the dimensionless constant C = 5 + 0.2. An inset to Fig. 2 shows the lg(r) vs. T À1 dependence for a-(GaSb)38Ge24. One can see that the conductivity is of an approximately activated character. The activation energy Eact(T) = Àd(lnr)/d(1/kT) varies from 0.16 to 0.37 eV with the temperature increasing from 110 to 425 K. If the temperature dependence of r is written in the standard form r(T)= A Æ exp(ÀEA/kT) with EA constant, the pre-exponentional factor A therefore increases with T. In the case of a-semiconductors, A(T) at high temperatures is usually approximated as BT n [13,14]: rðT Þ ? BT n Á expðÀEA =kT Þ.
n

3. Results Typical temperature dependences of S and r for a-(GaSb)38Ge24 are presented in Figs. 1 and 2. The dependences showed no hysteresis in the repeated cycles of heating and cooling of the samples. One of the samples was additionally exposed for 30 min to a temperature as high as 473 K, and its electrical properties did not change after this treatment either. Thus, the measured properties of a-(GaSb)38Ge24 were not changing in the course of experiment due to any relaxation processes that might occur in the metastable samples. As seen from Fig. 1, the thermopower of a-(GaSb)38Ge24 is positive. This points to the p-type of

ð 2Þ
À1 À9

Varying n in the experimental lg(r/T ) vs. T dependences gives n % 4, EA % 0.2 eV and B % 10


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excited into the band tails. The tails originate from the absence of the long-range order in amorphous substances and are assumed not to overlap with the Fermi-peak. The magnitude of S is determined by the average distance dEavr between EF and the conducting levels [13,15] Se=k ? dEavr =kT . ð 3Þ The distance dEavr for a-(GaSb)38Ge24 varies from 0.12 eV at 180 K to 0.22 eV at 400 K and it is 6 to 8 times greater than kT. Such magnitudes of dEavr are characteristic of conductivity in the band tail states. The conductivity is non-degenerate and charge carriers obey BoltzmannÕs statistics. The basic parameter of the Mott-Davis model is DE ? E F À E a ; ð 4Þ

-12

-13

-8 2 4 6 8

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-16 2 4 6 8

Fig. 2. A representative temperature dependence of the dc conductivity r for a-(GaSb)38Ge24 in the co-ordinates lg(r) vs. TÀ1 (inset) and lg(r/T4) vs. TÀ1 (main figure). The solid line is the linear fit to the experimental dependence at 180 6 T 6 400 K.

where Ea is the tail edge energy. In the p-type semiconductors, this is the valence band tail and therefore DE > 0. The density of states in the valence band tail is usually approximated as N(E) / (Ea À E)n with n > 0 [13,14] that leads to conductivity of an almost activated type r / T n exp?ÀðDE þ W Þ=kT ; ð 5Þ

XÀ1 cmÀ1 KÀ4 as the parameters of the best linear fit in the temperature interval 180-400 K where S is measured. With n = 4, our samples showed the scatter in the value of EA from 0.18 to 0.22 eV and in the value of B from 0.7 ž 10À9 to 1.4 ž 10À9 XÀ1 cmÀ1 KÀ4. The difference between the energies EA and ES characterising, respectively, the temperature dependence of conductivity and thermopower is about 0.2-0.05 = 0.15 eV.

where W is the average activation energy for hopping mobility in the band tail. In the same approximation [13,14] Se=k % DE=kT þ n þ 1. ð 6Þ The theory therefore gives a large value of thermopower (Se/k > 1) increasing linearly with reciprocal temperature. As seen from Fig. 1, the S(T À1) dependence of (GaSb)38Ge24 is nearly linear in the studied temperature interval from 180 to 400 K. A comparison of the parameters of fitting Eq. (1) to the experimental S(T À1) dependence with the parameters of Eq. (5) yields DE = ES = 0.05 eV and n = C À 1 = 4.0 + 0.2. A comparison of Eq. (2), that describes the conductivity of (GaSb)38Ge24 at the same temperatures, with the parameters of Eq. (4) gives DE + W = EA = 0.20 + 0.02 and n % 4. Similar values of n % 4 resulting from the measurement of two different properties, thermopower and conductivity, evidence that the electrical properties of (GaSb)38Ge24 at temperatures from 180 to 400 K are determined for the most part by hopping conductivity of holes thermally excited into the tail of the valence band. The average activation energy for hopping mobility is W = EA À ES % 0.15 eV. At temperatures lower than 150 K, the lg(r/T 4) vs. À1 T dependence for (GaSb)38Ge24 noticeably deviates from the straight line towards higher values of conductivity (Fig. 2). The deviation is likely to be due to the growing contribution from hopping conduction in the localized states near the Fermi energy that usually dom-

4. Discussion In a rather large temperature interval of 180-400 K, amorphous (GaSb)38Ge24 shows electrical properties typical of classic amorphous semiconductors, which are characterized by a nearly activation type of conductivity, by a nearly linear increase in the thermopower with reciprocal temperature and by the difference EA À ES on the order of 0.1 eV [13,14]. According to the conventional Mott-Davis model [13], the Fermi level EF in amorphous semiconductors is pinned in the mobility gap at a relatively narrow peak in the density of states N(E) for charge carriers. The peak is positioned near the middle of the gap and originates from defects in the random network, such as dangling bonds, vacancies, etc. In the framework of this model, the electrical properties of amorphous semiconductors at moderate temperatures are mainly determined by hopping conductivity of carriers thermally


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inates in amorphous semiconductors at low temperatures [13,14]. The electrical properties of amorphous GaSb-Ge alloys containing up to 80 mol% Ge were earlier studied in [10]. The results of that work significantly differ from ours, presumably, due to the inhomogeneity of samples prepared in a different way. The samples in [10] were heated to 1100 œC or to 400 œC at a pressure of 9 GPa and then rapidly cooled and decompressed at room temperature. The samples heated under pressure to 1100 œC were always multi-phase, showed a metallic type of conductivity and had a considerable fraction of unidentified superconducting phases. The samples heated to 400 œC were more homogeneous, demonstrated a semiconductor behavior, and those with P23 mol% Ge contained no crystalline inclusions. However, the degree of homogeneity of the samples remains questionable because the point (400 œC, 9 GPa) chosen in [10] for thermo-baric treatment was close to the T-P range of melting of the GaSb-Ge high-pressure phase [12]. This phase being a multi-component solid solution, its melting had to occur within a finite temperature and pressure interval according to the phase rule, and the samples in [10] therefore could be quenched from this very interval and inherit the inhomogeneous state.

energy at T = 0 K and W % 0.15 eV is the activation energy of hopping mobility in the valence band tail.

Acknowledgements This work was supported by the Grant No. 04-0217143 from the Russian Foundation for Basic Research. One of the authors (OIB) acknowledges financing from the Russian Science Support Foundation.

References
[1] E.G. Ponyatovsky, O.I. Barkalov, Mater. Sci. Rep. 8 (1992) 147. [2] S.M. Sharma, S.K. Sikka, Prog. Mater. Sci. 40 (1996) 1. [3] O.I. Barkalov, A.I. Kolesnikov, E.G. Ponyatovsky, U. Dahlborg, R. Delaplane, A. Wannberg, J. Non-Cryst. Solids 176 (1994) 263. [4] A.I. Kolesnikov, U. Dahlborg, M. Calvo-Dahlborg, O.I. Barkalov, E.G. Ponyatovsky, W.S. Howells, A.I. Harkunov, Phys. Rev. B 60 (1999) 12681. [5] M. Calvo-Dahlborg, U. Dahlborg, A.I. Kolesnikov, O.I. Barkalov, E.G. Ponyatovsky, A.C. Hannon, J. Non-Cryst. Solids 244 (1999) 250. [6] A.I. Kolesnikov, O.I. Barkalov, M. Calvo-Dahlborg, U. Dahlborg, W.S. Howells, E.G. Ponyatovsky, Phys. Rev. B 62 (2000) 9372. [7] V.E. Antonov, O.I. Barkalov, A.I. Kolyubakin, J. Non-Cryst. Solids 176 (1994) 58. [8] A.I. Kolyubakin, V.E. Antonov, O.I. Barkalov, A.F. Gurov, A.I. Harkunov, J. Non-Cryst. Solids 289 (2001) 30. [9] V.E. Antonov, O.I. Barkalov, A.I. Kolyubakin, E.G. Ponyatovsky, Phys. Stat. Sol. (b) 198 (1996) 497. [10] V.V. Brazhkin, S.V. Demishev, Yu.V. Kosichkin, D.G. Lunts, A.G. Lyapin, S.V. Popova, N.E. Sluchanko, S.V. Frolov, Zh. Eksp. Teor. Fiz. 104 (1993) 3126 [Engl. Transl.: Sov. Phys. JETP 77 (1993) 465]. [11] V.V. Brazhkin, A.G. Lyapin, S.V. Popova, N.V. Kalyaeva, J. Mater. Sci. 30 (1995) 443. [12] V.E. Antonov, O.I. Barkalov, E.G. Ponyatovsky, S.A. Zavolovich, High Pressure Res. 15 (1997) 201. [13] N.F. Mott, E.A. Davis, Electron Process in Non-Crystalline Materials, Clarendon, Oxford, 1979. [14] P. Nagels, in: Amorphous Semiconductors, in: M.H. Brodsky (Ed.), Topics In Applied Physics, vol. 37, Springer, New York, 1985. [15] H. Fritzsche, Solid State Commun. 9 (1971) 1813.

5. Conclusions The measured temperature dependences of thermopower S and electrical conductivity r of bulk amorphous (GaSb)38Ge24 can be interpreted in the framework of a conventional model often used for amorphous semiconductors [13]. Throughout the temperature interval 180-400 K of the thermopower measurement, the conduction of a-(GaSb)38Ge24 is dominated by thermally activated hopping of holes exited into the tail of the valance band. In this temperature range, the conductivity is well described by the equation r = BTnexp[À(DE + W)kT] and the thermopower by the equation Se/k = DE/kT + n + 1, where B % 10À9 XÀ1 cmÀ1 KÀ4 and n % 4. The value of DE % 0.05 eV is the difference between the Fermi energyand the tail edge