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Temperature-dependent activation energy and variable range hopping in semi-insulating GaAs

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2006 Semicond. Sci. Technol. 21 1681 (http://iopscience.iop.org/0268-1242/21/12/030) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING Semicond. Sci. Technol. 21 (2006) 16811685

SEMICONDUCTOR SCIENCE AND TECHNOLOGY

doi:10.1088/0268-1242/21/12/030

Temperature-dependent activation energy and variable range hopping in semi-insulating GaAs

R M Rubinger1, G M Ribeiro2, A G de Oliveira2, H A Albuquerque2, R L da Silva2, C P L Rubinger1, W N Rodrigues2 and M V B Moreira2
1

Departamento de Fsica e Qumica, Instituto de Ci ncias, Universidade Federal de Itajub , e a Itajub , MG, CP 50, CEP 37500-903, Brazil a 2 Departamento de Fsica, Universidade Federal de Minas Gerais, ICEx, Belo Horizonte, MG, CP 702, CEP 30123-970, Brazil E-mail: rero@unifei.edu.br and alfredo@sica.ufmg.br

Received 7 June 2006, in nal form 25 August 2006 Published 18 October 2006 Online at stacks.iop.org/SST/21/1681 Abstract We measured resistivity in the range of 30390 K on four semi-insulating low-temperature grown molecular-beam epitaxy GaAs samples. The growth temperature range was from 215 C to 315 C. Arrhenius ttings with T 1 and hopping tting with T 1/4 do not permit us the denition of the temperature ranges controlled by band and hopping conduction, respectively. This leads to major errors in the calculation of both activation energies and hopping parameters. We have used the differential activation energy in order to clearly identify the temperature range for the different transport mechanisms. Hopping dominates at low temperatures and band conduction at high temperatures. In-between, a mixed conduction regime is observed. We introduce a criterion to clearly dene the temperature range of hopping, band and mixed conduction. The lower temperature at which mixed conduction is identied decreases for samples with increasing growth temperature. Only the sample grown at 215 C presents both forms of hopping conduction before entering the mixed conduction regime. Hopping parameters were obtained from the ttings of the differential activation energy and the values are in good agreement with the usual method of calculating them if the correct temperature range is used.

1. Introduction
In a previous work [1] we reported hopping conduction on low-temperature molecular-beam epitaxy (LT-MBE) GaAs samples using temperature-dependent van der Pauw resistivity measurements. In the present work we extended the measurements both to higher and to lower temperature limits and present results for further samples. The main aim of this work is to use the differential activation energy as a method to access the precise temperature range associated with different conduction regimes [2] and to calculate the variable range hopping [3] (VRH) parameter whose differential activation energy varies with T 3/4 . For
0268-1242/06/121681+05$30.00

high temperatures characterized by band conduction the differential activation energy is constant. We must also consider the presence of nearest neighbour hopping (NNH) conduction mechanism whose differential activation energy is also constant. At intermediary temperature values, a mixed conduction involving hopping and one of the bands is observed and it has an effective conductivity weighted by different mobilities and carrier densities. In this mixed conduction regime we have a pseudo activation energy that is neither constant with temperature nor follows the T 3/4 dependence. In this work, we will be particularly looking for the temperature range where the activation energy varies with T 3/4 , which identies the VRH conduction. Other features associated with 1681

2006 IOP Publishing Ltd Printed in the UK

R M Rubinger et al

the differential activation energy will also be considered as secondary results of this work. In SI GaAs, VRH is a deep level [4] related conduction mechanism, which is the central point for improving the semiinsulating (SI) characteristic. The search of high quality SI GaAs layers grown by molecular-beam epitaxy (MBE) has been pursued for at least two decades [57]. The main intrinsic deep defects in As-rich low temperature (LT) MBE GaAs are arsenic antisites (AsGa) [8, 9] which are mid-gap donors that trap free carriers resulting in the intrinsic SI GaAs. The deep level defects density can be tuned with the growth temperature but this is not a trivial relationship. Indeed, the lowering of the growth temperature increases the deep level defect density [10], which results in the reduction of the conduction at the band but, on the other hand, increases hopping conduction. [11] Also, the role of acceptors such as gallium vacancies (VGa) [12] cannot be neglected. In this work, through the differential activation energy, we have identied some features of the contribution of deep levels to the transport characteristics that were not previously clear. To exemplify the diversity of conduction mechanisms that can be found in SI LT-MBE GaAs we studied four samples grown at temperatures ranging from 215 C to 315 C. These samples were not subjected to annealing at high temperatures. Annealing a LT-MBE GaAs sample (i.e. grown at 200 C) at higher temperatures is another method of producing GaAs samples with different AsGa densities [11, 13]. This method, however, has some limitations since at higher annealing temperatures arsenic precipitates and VGa are formed in high densities. By using a growth temperature in the range of 200350 C the AsGa density on the LT-MBE GaAs samples presents a variation similar to that of samples annealed in the range of 350600 C [11, 13]. Since our growth temperatures are lower than those of annealed samples the VGa density is expected to be lower. In addition to its technological implications, the study of hopping conduction among deep level defects in SI GaAs presents interesting features in basic science that expands the studies of hopping conduction via shallow levels. In this sense, SI LT-MBE GaAs offers a fruitful platform for the study of hopping conduction near room temperature. Look et al [11, 13] found, for LT-MBE GaAs samples annealed at temperatures up to 600 C, good agreement with the = 0 exp(T0 /T )1/4 law below 200 K, which has been assigned as VRH conduction. For resistivity measurements between 300 K and 500 K they also suggested a mixed electrical conduction mechanism involving VRH and band conduction. The precise denition of the temperature range for VRH is however difcult since good ttings with T 1 are also possible even at temperatures between 200 K and 300 K. The work of Look et al [11, 13] incited us to the realization of the present work which consists of measuring the resistivity on four SI LT-MBE GaAs samples. In this work we used the calculation of the differential activation energy as a tool to distinguish the VRH regime from NNH and band conduction. A similar approach was previously proposed by Zabrodskii et al [14, 15] in which a log plot of a reduced activation energy was applied in order to t power law VRH exponents. They were particularly interested in changes in the VRH regime from T 1/4 to T 1/2 at very low temperatures. The present work is focused in the explicit dependence of the activation 1682

energy on the temperature in order to indicate its value and at the same time changes of its functional dependence on the temperature associated with changes in the conduction regime, including mixed conductivity with free carriers. For this task, our approach is more suitable and we were able to identify the precise temperature range for VRH. In this range, the value 1/4 of T0 , obtained from both the differential activation energy by the T 3/4 tting and from the law = 0 exp(T0 /T )1/4 , is basically the same. We claim that the differential activation energy dependence on T 3/4 allows better identication of the temperature range where VRH is a dominant phenomenon and consequently a reliable method in order to distinguish the temperature range of VRH from that of NNH and mixed conduction. Also, this method allows the identication of the thermal activation energy associated with the pinning position of the Fermi level at the impurity band of the dominant deep level trap and the conduction band. As additional features of the differential activation energy plot we identify at least the following two: the lower temperature at which mixed conduction is identied decreases for samples with increasing growth temperature; increase in the activation energy for thermally activated carriers at the conduction band means that the compensation ratio between donors and acceptors (the best acceptor candidate being VGa) increases.

2. Experiments and results

In the present work, we report on the identication of conduction mechanisms with emphasis on VRH conduction in four SI LT-MBE GaAs samples. The samples were grown on (1 0 0) SI liquid encapsulated Czochralski GaAs substrates, in a RIBER 2300 MBE system. After the standard desorption procedures, a 0.21 m thick buffer layer was grown at 610 C under an As overpressure of 3.2 105 Torr and 0.81 monolayer/s. After that, the substrate temperature was ramped down at 10 C min1 to the nal desired temperature while growing. After reaching the set temperature, a 2.4 m thick GaAs epilayer was grown. In this work, the four samples were labelled from 1 to 4 with the respective growth temperatures of 315 C, 300 C, 265 C, 215 C. The resistivity measurements were done using van der Pauw geometry on as-grown samples. The samples were cut into 5 5 mm2 squares and the contacts were made of indium drops. After depositing the contacts and gold wires with a soldering station at a temperature of 250 C the samples were not post-annealed. The measurements were carried out in the low electric eld regime, i.e., in the ohmic regime that was identied from I (V ) conductivity measurements, carried out from negative to positive bias, giving us a certainty about the linearity of the contact resistance in all the measured samples. For each of the four SI LT-MBE GaAs wafer, we prepared at least seven samples from different parts of the wafer and for a same wafer the results did not vary signicantly. For carrying out the resistivity measurements, we used a Keithley automated Hall System model 7065, the standard current source and the requested meters. All contacts between the cryostat and the Hall system were done with triaxial cables in guarded-mode measurements to avoid parasitic capacitance. Inside the cryostat, 2 mm diameter 50 Teon insulated

Temperature-dependent activation energy and variable range hopping in semi-insulating GaAs

Table 1. Comparative hopping parameters and activation energies obtained from different methods. T0 (K 1/4 ) Sample 1 2 3 4
a 1/4

Activation energy, a (eV)b At high T (0.85 0.01) (0.73 0.01) (0.93 0.02)
a

From = 0 exp(T0 /T )1/4 (108 3) (75 2) (99 1) (87 1)

From 1/4 a = k T0 T 3/4 4 (98 1) (82 4) (97 1) (88 1)

At low T (0.124 0.005) (0.077 0.002) (0.094 0.001) NNH (0.072 0.001) VRH (0.033 0.001)

Not calculated due to the absence of the high temperature plateau. Both the mean value of the DAE plateaus and the Arrhenius ttings gave the same numerical values.

(a)

(b)

Figure 1. (a) Arrhenius plots for the resistivity. The abscissae correspond to (kT )1 in units of eVK1. Fittings are represented by straight lines. (b) The same resistivity measurements but with the abscissae axis as T 1/4 . Fittings for the VRH regime are indicated by straight lines. The symbols corresponding to each sample are indicated in the gure.

Figure 2. Differential activation energy calculated from resistivity measurements for samples 14. Three conduction mechanisms and four regimes are identied. For the VRH mechanism we present an inset in which the abscissae is T 3/4 with linear ttings as in equation (3).

coaxial cables were used. The electric transport measurements were carried out at temperatures ranging from about 45 to 400 K. The lower measurement temperature was limited by the sample resistivity and the higher limit by the cryostat characteristics. Semi-log plots of the resistivity as a function of (kT )1 and T 1/4 are shown in gure 1. Standard Arrhenius plots, i.e., the plots with (kT )1 to obtain the activation energy, show good accuracies for ttings at the two extremes of the graph. The activation energies, listed in table 1, were obtained from gure 1(a). The values can roughly be grouped into two sets: high values, i.e. above 0.5 eV, and low values, i.e. near 0.1 eV, i.e. in an attempt to split process involving conduction band activated carriers from process involving impurity band hopping carriers. Good accuracy ttings were also obtained at low temperatures using plots with T 1/4 . All ttings are 1/4 indicated by straight lines and the values of T0 obtained from gure 1(b) are listed in table 1 and are in the range of 75 108 K 1/4 . We stress that the temperature range related to VRH produces good ttings with the Arrhenius law and vice-versa due to the fact that the y-axis is logarithmic and, therefore, the distinction between Arrhenius and VRH is attenuated as is

evident in gure 1. The high values of the activation energy obtained by Arrhenius coincide with the mean values obtained from the plateau at the highest temperatures of gure 2. d(ln ) In gure 2, we present a plot of d(kT )1 [2] obtained from a numerical derivation of natural logarithm of the resistivity, given in gure 1, as a function of (kT )1 . We ensure that the experimental points have constant temperature increments so that the result is smooth differential activation energy (DAE). In this plot we selected the temperature range where DAE varies with T 3/4 as indicated by the linear ttings shown in 1/4 the inset of gure 2. The T0 values obtained from these ttings are listed in table 1 and they are in the range of 8298 K 1/4 , basically the same values found by the standard method. Figure 2 shows three clear regimes for the DAE. For increasing temperature they are: the T 3/4 sub-linear region, followed by a rapid enhancement region and, nally, a constant value. For sample 4, the constant higher value was not achieved due to temperature limit of the experimental setup but the data signs for a saturation value of the DAE value at about 0.65 eV. The constant value of DAE for samples 1, 2 and 3 are 0.85 eV, 0.73 eV and 0.93 eV, respectively. 1683

R M Rubinger et al

3. Discussion
The differential activation energy (DAE) associated with VRH conduction can be calculated using the following equations [2]: T0 = c = , kg()a 3 (1) (2) (3)

1/4 , 3 g()kT a d(ln ) dc k 1/4 = = T0 T 3/4 . a = 1 1 d(kT ) d(kT ) 4 1/4

In (1), T0 is the hopping parameter, is a dimensionless percolation parameter, k the Boltzmann constant, a the localization radius of the wave function and g() the density of states near the Fermi level. In (2), c is the critical exponent of the VRH resistivity deduced from a percolation theory. In (3), a is the differential activation energy (DAE) for VRH and it can be obtained from experimental data. Hopping conduction involves those energy levels within a narrow energy range at the Fermi level. This range shrinks for decreasing temperatures [2] which results in a decrease of the defect density active for hopping. This shrinking effect is the key mechanism behind the exp(T0 /T )1/4 law for VRH. It contrast the standard Arrhenius regime, i.e., (exp(C/T )) associated with bands and the NNH regimes, i.e., (exp(C /T )), where C and C are constants. The shrinkage of the energy range implies in a DAE for VRH that follows the T 3/4 dependence according to (3). The temperature dependence of DAE for VRH is a good method for distinction between VRH and NNH or band conduction because the last two do not present temperature dependence. The DAE method for calcu1/4 lating T0 and for dening the VRH range is, therefore, more reliable than that involving resistivity due to the exponential temperature dependence of the resistivity for conduction mechanismsVRH, NNH and band conduction. Therefore, concerning DAE, we claim that three conduction mechanisms were identied characterizing four distinct regimes. The rst regime is characterized by the dominance of the VRH mechanism in the low temperature region where DAE varies with T 3/4 . The second regime is NNH, characterized by a plateau, only present in sample 4. NNH is absent in samples 1, 2 and 3 since they enter directly into the third regime which is mixed conduction. The fourth regime is characterized by the band conduction mechanism identied by a plateau at the high temperatures but not present in the data of sample 4, as mentioned before. The distinction between the four regimes can be clearly identied in gure 2 but not in gure 1 where it is a hard task to dene the limit between two consecutive regimes. The 1/4 T0 values obtained by tting resistivity from gure 1 can present wrong and very high values if they incorporate part of the mixed conduction regime. That is the reason why we have used the same set of points for both methods in order to 1/4 calculate the T0 values that are listed in table 1. Our work indicates that in order to clearly identify the temperature range dominated by VRH conduction it is not enough to nd a linear tting in a ln() versus T 1/4 plot. This restriction can be overcome by eliminating the exponential dependence through the plot of the differential activation 1684

energy as a function of the temperature. This is proved in gure 2, which shows up to four distinct regimes that permits a better denition of the dominant conduction mechanisms in each case. Based on this criterion for dening the different conduction regimes we identied the set of points of the plateau in gure 2 for samples 1 to 3 and used them in order to calculate the Arrhenius activation energy, which are listed in table 1. These are the values that should be compared with those reported in the literature for the AsGa which are in the range of 0.540.81 eV [11, 16]. For sample 3, for example, we have used 12 points (from 335 K to 390 K) to calculate the Arrhenius activation energy of 0.93 eV and if we have used twice the numbers of points (i.e. from 275 K to 390 K) the energy value would reduce to 0.78 eV although both Arrhenius ttings (with 12 or 24 points) are visually indistinguishable. Thus, it is very important to ensure that the points of the mixed conduction regime are out in order to fairly calculate the activation energy. Observe also that both methods, Arrhenius and DAE, present the same values if the mixed conduction regime is cut out of the calculations. Thus the set of DAE values and Arrhenius activation energies are basically identical and just one value for each activation energy was presented in table 1. It was not possible to obtain the value for sample 4 since its results do not present the high temperature plateau. The Arrhenius activation energies for VRH are pseudo-values of the activation energy since they are temperature dependent. They give however a rough gure of the hopping energy. They sit near 0.1 eV for samples 1, 2 and 3 and, for sample 4, the pseudo-value was smaller, i.e., near 0.033 eV. For sample 4 it was possible to determine the value of 0.073 eV for NNH. Another characteristic that results from the higher contrast between the four conduction regimes observed in the DAE plot when associated with the growth temperature is that we can obtain some qualitative information regarding the deep level defect density and compensation factor. For this we consider a mixed conductivity of the type T = e(nB B + nh h ) with subscripts T, B and h being total, band and hopping contribution respectively, and assuming that the mobilities B and h have roughly the same temperature dependence for samples 14. At the lower temperature limit of mixed conductivity the hopping contribution is stronger. The increase in this limit from samples 14 indicates that, in this condition, the hopping carrier density nh increases more than the band carrier density nB for reducing growth temperatures. On the other extreme of mixed conduction, in which the band contribution is stronger, there is no clear trend in the temperature limit. The role of acceptors, i.e. basically the VGa, affects the competition between band and hopping contributions to the conductivity. nB depends, not only on the AsGa density, which increases with reducing growth temperatures, but also strongly on the activation energy which is related to the compensation ratio VGa/AsGa. The more the compensation the higher is the activation energy. Sample 3 presents the highest activation energy but not the highest temperature limit for mixed conduction. Sample 4 presents the strongest hopping conduction and the lower activation energy. To investigate those intricate relationships is not the aim of

Temperature-dependent activation energy and variable range hopping in semi-insulating GaAs

the present work. But we have introduced this discussion in order to exemplify the richness of details that the DAE plot can provide.

References
[1] Albuquerque H A, de Oliveira A G, Ribeiro G M, da Silva R L, Rodrigues W N and Rubinger R M 2004 J. Appl. Phys. 95 35536 [2] Shklovskii B I and Efros A L 1984 Electronic Properties of Doped Semiconductors (Springer Series in Solid-State Sciences vol 45) (Berlin: Springer) [3] Shklovskii B I 1973 Sov. Phys. Semicond. 6 105375 [4] Look D C 1993 Thin Solid Films 231 6173 [5] Smith F W, Calawa A R, Chen C L, Manfra M J and Mahoney L J 1988 IEEE Electron Device Lett. 9 7780 [6] Ballingall J M 1996 Semiconductor Characterization ed W M Bullis, D G Seiler and A C Diebold (New York: AIP Press) p 578 [7] Fang Z-Q and Look D C 1993 Appl. Phys. Lett. 63 21921 [8] Yu K M, Kaminska M and Liliental-Weber Z 1992 J. Appl. Phys. 72 28506 [9] Tkach I, Krambrock K, Steen C, Kiesel P and Spaeth J M 2001 Physica B 308310 74952 [10] Krambrock K, Linde M, Spaeth J M, Look D C, Bliss D and Walukiewicz W 1992 Semicond. Sci. Technol. 7 103741 [11] Look D C, Walters D C, Manasreh M O, Sizelove J R, Stutz C E and Evans K R 1990 Phys. Rev. B 42 357881 [12] Gebauer J, Krause-Rehberg R, Eichler S, Luysberg M, Sohn H and Weber E R 1997 Appl. Phys. Lett. 71 63840 [13] Look D C, Fang Z-Q and Look J W 1994 J. Electrochem. Soc. 141 74750 [14] Zabrodskii A G and Zinoveva K N 1984 Sov. Phys.JETP 59 425 [15] Zabrodskii A G, Andreev A G and Egorov S V 1998 Phys. Stat. Sol. B 205 618 [16] Yano R, Hirayama Y, Miyashita S, Uesugi N and Uehara S 2003 J. Appl. Phys. 94 396671

4. Summary
We have carried out high-precision van der Pauw resistivity measurements on four semi-insulating GaAs samples grown by low temperature molecular-beam epitaxy. Our work indicates that in order to clearly identify VRH conduction it is not enough to carry out a linear tting in a ln() versus T 1/4 plot. Our results show that variable range hopping signatures can be obtained using the = 0 exp(T0 /T )1/4 law and the differential activation energy having T 3/4 dependence. 1/4 The differential activation energy tting for T0 we have used is a more reliable method since the transition between band activated conduction and hopping activated conduction becomes more evident in this plot. Mixed conduction was observed in a broad temperature range and it should be excluded of the calculation in nding the hopping parameter 1/4 T0 and the activation energy of the deep level.

Acknowledgments
The authors acknowledge the Brazilian Agencies CNPq and FAPEMIG for nancial support.

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