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Analysis of complex impedance of p-CuIn3Se5 by

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DOI: 10.1016/j.jallcom.2016.07.183

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Accepted Manuscript

Analysis of complex impedance of p-CuIn3Se5 by impedance spectroscopy

L. Essaleh, G. Marín, S.M. Wasim, S. Lahlali, H. Chehouani

PII: S0925-8388(16)32210-1
DOI: 10.1016/j.jallcom.2016.07.183
Reference: JALCOM 38352

To appear in: Journal of Alloys and Compounds

Received Date: 3 May 2016

Revised Date: 12 July 2016
Accepted Date: 17 July 2016

Please cite this article as: L. Essaleh, G. Marín, S.M. Wasim, S. Lahlali, H. Chehouani, Analysis of
complex impedance of p-CuIn3Se5 by impedance spectroscopy, Journal of Alloys and Compounds
(2016), doi: 10.1016/j.jallcom.2016.07.183.

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 ACCEPTED MANUSCRIPT
Analysis of complex impedance of p-CuIn3Se5 by impedance spectroscopy

L. Essaleh *

Laboratory of Condensed Matter and Nanostructures (LMCN), Cadi-Ayyad University.

Faculty of Sciences and Technology, Departement of Applied Physics, Marrakech, Morocco.

G. Marín

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Laboratorio de Estructura e Ingeniería de Materiales Nanoestructurados (LEIMN), Centro de
Investigación y Tecnología de Materiales (CITeMa), Instituto Venezolano de Investigaciones
Científicas (IVIC), Maracaibo 4011, Venezuela.

S. M. Wasim

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Centro de Estudios de Semiconductores, Facultad de Ciencias. Universidad de Los Andes, Mérida
5101, Venezuela.

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S. Lahlali

Laboratoire Procédés, Métrologie, Matériaux pour l’Energie et Environnement (LP2M2E),

Cadi-Ayyad University, Faculty of Sciences and Techniques, Departement of Applied Physics,

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Marrakech, Morocco.

H. Chehouani
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Laboratoire Procédés, Métrologie, Matériaux pour l’Energie et Environnement (LP2M2E),
Cadi-Ayyad University, Faculty of Sciences and Techniques, Departement of Applied Physics,
Marrakech, Morocco.
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Abstract

Both complex impedance and electric modulus formalisms are considered to study the contribution of
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dominant electrical conduction mechanisms in bulk p-type CuIn3Se5 semiconductor. An equivalent electrical
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circuit has been proposed to explain the impedance results that show semicircle arcs at different temperatures.
Two different conduction mechanisms were obtained by fitting the data to Cole-Cole equation. The values of
calculated resistances for the “grain” and “grain-boundary” contributions were found to decrease with
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increasing temperature, in agreement with the Arrhenius law associated with activation energy of 179 meV
and 199 meV for the “grain” and “grain-boundary” conduction, respectively. The activation energies for
relaxation mechanisms were estimated and compared with those obtained from the analysis of electric
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modulus.
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Keywords: Semiconductor Compounds; Electrical Conductivity; Impedance Spectroscopy; Electric Circuit Model;
Process Identification.

* Corresponding author: Pr. L. Essaleh, Phone: (+212) 6 68 05 13 56, Fax: (+212) 5 24 43 31 70, E-mail:
lessaleh@gmail.com, l.essaleh@uca.ma

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1. Introduction

Studies on single crystal materials have the advantage that grain boundary phenomena
should be absent and a more detailed analysis of bulk properties can be made. In order to
assign the electrical inhomogeneities in disordered semiconducting materials, gain
boundaries and often other effects must be taken into account [1] and can be studied by the
non destructive impedance spectroscopy (IS) technique [2]. The ternary compound

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semiconductor CuIn3Se5 (CIS135) with chalcopyrite-like structure, a promising
photoabsorber material due to its band gap of the order of 1.3 eV [3-4], is an example of

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these materials. CTS135 is usually called ordered vacancy compounds (OVC) because an
array of vacancies may orderly occupy particular crystallographic sites in the cation

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sublattice [5]. These compounds are also referred to in the literature as ordered defect
compounds (ODC). To our knowledge, no detailed studies of impedance and modulus

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measurements are reported for bulk CIS135. Only few works are published for thin films
[4]. In our previous work [6] on the present material, relaxation times for the grain and
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grain boundaries were studied from the second derivative of imaginary part M” of complex
electric modulus M* versus frequency at various temperatures. Activation energies for the
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relaxation process of the order of 111 and 401 meV are thus deduced for the two
contributions, respectively. However, an alternative formalism of complex impedance have
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been found to be very useful in distinguishing the grain and grain boundary contributions to
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the total electrical conductivity of polycrystalline materials having different time constant
[7]. In this impedance formalism, each contribution “i” is represented by a resistance Ri
mounted in parallel with a capacitance Ci (or constant element phase CPEi due to
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distribution of relaxation time). Therefore, the aim of the present work is to determine
relaxation times by means of an adequate equivalent circuit using several RC elements. To
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be consistent, the number of adjustable parameters (Ri, Ci, …) to be considered in fitting

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experimental data of real part Z’ and imaginary part Z” of complex impedance Z* versus
frequency at different temperatures must be reduced. For this reason, values of grain
resistance Rg for a given temperature are obtained from the maximum in M” in the high
frequency range. The temperature dependence of the electrical resistances and the
activation energies for the “grain” and “grain-boundary” contributions were thus estimated
and compared with those obtained from the analysis of electric modulus that are reported in
reference 6.

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2. Experimental details

Single crystal of CuIn3Se5 sample, used in the present work, was obtained from ingot
grown by vertical Bridgmann technique. Its chemical composition was determined by
energy dispersive X-ray spectroscopy (EDX) using a Kevex model Delata-3 system

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connected to a Hitachi model S-2500 scanning electron microscope. Representative values
of Cu:In:Se were as 9.47 : 29.24 : 61.28. The resulting stoichiometry was thaus very close

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to 1:3:5, with slight excess of Se. The error in the standardless analysis was around 5% [8].
The powder diffraction pattern was registered with a Rigaku D/Max-IIIB diffractometer,

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operated at 45 kV and 30 mA, using a Cu-target tube and a graphite monochromator. The
intensity data was recorded by continuous scan in a 2θ/θ mode from 5° to 90° with a step
size of 0.02° and a scan speed of 0.3°/mn. The position of each peak was established using

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the α1 component (λCuKα1 = 1.5406 Å). The intensity was expressed as a percentage of the
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strongest peak of the pattern [9]. As shown in table 2 of reference 9, all the peaks with
relative intensity above 1 % were identified. This confirms the absence of any detectable
M

secondary phase. The a and c parameters obtained were 5.7541(5) and 11.538(3) Å,
respectively. The p-type conductivity of the material was established by a thermal probe
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analysis and. Impedance measurements were carried using the HP 4284A spectrometer in
the frequency range of 20 Hz–1 MHz. A source of 50 mV was applied to the electrode
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pellet samples. The temperature variation was achieved using a programmable Thermolyne
heater with a temperature stability of ± 0.1°C. Silver electrodes were deposited at the end
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parts of the sample to get the impedance shaped sample.

3. Results and discussion
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The frequency dependence of the real (Z’) and imaginary (Z”) parts of the complex
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impedance (Z* = Z’ – jZ”) at representative temperature of 308 K is shown in Fig 1. As

frequency increases, Z’ decreases and Z” increases. With increasing temperature, the
maxima in Z” versus frequency at some representative temperatures, as shown in Fig 2,
shifts towards higher frequencies and satisfies the theoretical model [10] in which the
energy difference Ea between the trap level and the valence band is given in
− Ea
f max = f o exp( ) (1)
k BT

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Where fmax is the frequency at which Z” is maximum, T is the absolute temperature and kB
is the Boltzmann constant. The linear behavior of Ln(fmax) versus the inverse of absolute
temperature (1/T) is represented in the insert of Fig 2. Ea is estimated from the slope of the
straight line to be 172 ± 8 meV. To explain the contribution of the bulk (or grain) and the
“grain-boundary” to the total electrical conduction, the impedance spectra Z” versus Z’
(Nyquist diagram) for some representative temperatures is shown in Fig 3. The shape and

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the width of the arcs indicate the type of relaxation mechanism for the system: Debye
relaxation (single relaxation time) appears only in perfect crystals. The arc can be fitted

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using an ideal capacitor C. The corresponding complex impedance is then of the form
[11,12]

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Rg
Z* = (2)
1 + jωτ
where ω=2πf is the angular frequency and τ = RC is the relaxation time. In this case, the

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Cole-Cole plot (Z” versus Z’) is a half-circle of diameter equal to Rg, centered on the Z’
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axis ( Fig. 4a). Most compounds in the solid state exhibit non-Debye relaxation and exhibit
broad relaxation time distribution. In this case, the center of a semicircle in the plot of Z”
M

versus Z’ for a given temperature T is displaced below the Z’ axis making a certain angle φ
[13] (See Fig.4b). The relaxation time can be characterized in this case by the pre
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exponential factor and by the activation energy [14]. Usually depressed semicircles were
observed, a distribution of the relaxation time suggests that the arc cannot be fitted using an
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ideal capacitor C, and should be replaced by a constant phase element whose impedance
[11,14] is
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 = (
) (3)

where Q is a constant that is independent of frequency, and n is the empirical exponent that
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is the measure of distortion of Z”(Z’) characteristics. The value of n varies from 0 to 1; for
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an ideal capacitor n=1 and for an ideal resistor it is 0.

In materials with a single time constant (or relaxation time), the response of electric
polarization of the removal of a steady field exhibits a simple exponential decay [11,14]
with time

() = exp (−  ) (4)

In disordered materials, the electrical conduction cannot be attributed to a single relaxation

time. By including process with more than one relaxation times and by choosing a
distribution of relaxation times with appropriate frequencies, it is possible to parameterize

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the response of any material [11-13]: A number of empirical relaxation functions have been
proposed to explain the non-Debye dielectric response that can be observed in several
complex systems such as porous glasses and composite materials [15,16]. The majority of
non-Debye spectrum cases have been described by the so-called Havriliak–Negami (HN)
distribution function [17-19]. In this case, the expression of ϕ (t ) becomes [11-13]
 
() = exp −    with 0< β ≤1 (5)


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The value of the exponent β, considered to give a measure of the distribution of relaxation
time, is related to the angle φ that corresponds to the displacement of the center of a

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semicircle in the plot of Z” versus Z’ (Fig. 4b) below the Z’ axis given as [13]

∅ = (1 − ) 

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(6)

The corresponding complex impedance is then of the form [20]

!"

∗ = #$%&'( )

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(7)

The smaller the value of β, the more asymmetric the resulting semicircle becomes. As β
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approaches 1, then the form of the Debye single relaxation model is re-gained. The values

of β are obtained by measuring the angle (   ) between Z’ axis and the tangent to Z”
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versus Z’ plot at the point of origin (Z’=0, Z”=0). This is shown, for illustration, in Fig. 4a
for the Debye single relaxation model where β = 1 and in Fig.4b if there is distribution of
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relaxation time (0<β<1). The corresponding plot of  versus temperature for our material is
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represented in the insert in Fig.5. It can be seen that β becomes smaller as the temperature
is increased, indicating a large width of the distribution of relaxation time and a greater
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deviation with respect to the Debye-type relaxation.

In polycrystalline materials with grain and grain boundary contributions, the equivalent
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circuit related to the impedance data of Z’ and Z” versus frequency is considered in terms
of four elements which consist of two blocks of resistance Ri mounted in parallel with a
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capacitance Ci [21]. The subscript i refer to grain “g” and to grain boundary “gb”
contributions. The impedance Z* of the circuit is given by [21]
0 0
    
Z∗ = + + / +1 + 3 where
4 = (8)
!" -." !"2 -."2
4

The corresponding equivalent circuits and Nyquist plots are represented in Fig. 4c.
The frequency at the semicircle maxima, ωmax, and, correspondingly, at the Debye peak
maxima, for each RC element is given by

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5678 = 2:;678 = (<= >= )0 = ?=0 (9)

where the τi is the time constant of the RiCi element.
If there is distribution of relaxation time, the capacities Cg and Cgb in Fig. 4c are replaced
by constant phase elements CPEg and CPEgb, respectively. Their corresponding
impedances, given by eq.(3) are of the form [11,14,21]
 

@ = and
@A = 
@ (
)@
(10)
@A (
) @A

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are introduced to replace ZBC and ZBCD in eq. (8). The corresponding relaxation times for

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the two contributions are [6,21]
G G

?E = (<E FE ) @
and ?EH = (<EH FEH ) @A
(11)

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From eq. (8) and (10), relationships of a real (Z’) and imaginary (Z”) parts of the complex
impedance Z* are deduced to be
L Q L Q
K4 ($K4 4
LM NOP( M )) K4 ($K4 4
LM NOP( M ))

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I = J L Q
R
S +J L Q
R
S (12)
$K4 4
LM NOP M $(K4 4
LM )R $K4 4
LM NOP M $(K4 4
LM )R
R =T"E" R =T"EH"
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L Q L Q
K4 R 4
LM PVW M  K4 R 4
LM PVW M 

II = J L Q
R
S +J L Q
R
S (13)
$K4 4
LM NOP M $(K4 4
LM ) R $K4 4
LM NOP M $(K4 4
LM )R
M

R =T"E" R =T"EH"

Qi and ni are related to the impedance of CPEi (i = ”g”, “gb”) element through eq. (10).
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It is well known that in the high frequency limit in the Nyquist diagram, near the origin (Z’
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= 0, Z” = 0), the intra-grain resistance Rg represents the diameter of the corresponding

semicircle and the semicircle on the high part of Z’, related to low frequency limit,
represents the grain-boundary resistance Rgb [11-13, 21]. A study of the temperature
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dependence of Rg and Rgb with the corresponding relaxation times τg and τgb permits to
evaluate the activation energies for relaxation process that is useful in understanding charge
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transfer phenomena. To fit the experimental data of Z” and Z’ versus frequency by using
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eqs. (12) and (13), the values of Rg are estimated from the maxima in M”(ω) in the high
frequency range. This corresponds, for example, to frequency fg = 141,5 kHz at 308 K [see
the Table 1 in reference 6]. As indicated in Fig 1, this value of fg corresponds to Z’(fg)=
11.176 kΩ. The corresponding value of Rg can be estimated from the peak in Z” versus Z’
plot that corresponds to fmax = fg, as can be seen from Fig. 4c, where Rg ≈ 2 Z’(fg). Thus Rg
is deduced to be of the order of 22.352 kΩ at 308 K in CIS135. This procedure is then
repeated for other temperatures and the corresponding values of Rg that are considered as
fixed parameters in the next fits of Z” and Z’ versus frequency are given in Table I.

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Good agreement between experimental and calculated curves of Z’ and Z” given by (12)
and (13) versus frequency is shown in Fig 1 for a representative temperature of 308 K. This
agreement is also represented in Fig 3 for different values of temperature. Percentage errors
between experimental and fitted results of impedance analysis are less than 5%. Figure 6
shows the deconvoluted grains and grain-boundaries contribution to Z” at 308 K, with a
peak at high frequency side that corresponds to the “grain” response. This deconvolution is

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obtained by using the Zview Software that allows to separate the contribution of grain to
that of grain boundaries. The values of adjustable parameters considered in these fits are

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listed in the Table I. As we can see from the table, the values of exponent ng and ngb are less
than unity, indicating the distribution of relaxation times. It is also observed that ng and ngb

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decrease with the increase of temperature. A semiconducting behavior is shown in Fig 7
where Ln(Rg) and Ln(Rgb) are plotted against 1/T. The corresponding activation energies,
obtained from linear fits, are estimated to be 179 and 199 meV for the “grain” and “grain-

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boundary” contributions, respectively, with errors less than 5%. The relaxation time is
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calculated with eq. (11) for these two different contributions with τg lower than τgb. This is
also shown in the Table I. In fact, the relaxation time obeys the well known Arrhenius law
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[22]
\]^_`
?XYZ78 = ?[ exp   (14)
ab c
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where τo is the relaxation time at infinite temperature and Erelax is the activation energy for
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relaxation process. The relaxation parameters Erelax can thus be determined by plotting
Ln(τrelax) as a function of the inverse of temperature. This is shown in Fig 8(a) and Fig 8(b)
for the “grain” and “grain-boundary” contributions, respectively. Data of relaxation times
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τg and τgb that are obtained from the analysis of the frequency dependence of electric
modulus [6] are also introduced in Fig 8 for comparison. For each contribution, the straight
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lines are nearly parallel indicating the same value of relaxation activation energy and thus
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the proposed equivalent circuit is the most adequate for our material.

4. Conclusion
In this study, we used impedance spectroscopy technique to analyze the contribution of
dominant electrical mechanisms to the electrical conduction in bulk p-CuIn3Se5
semiconductor material. From the proposed equivalent circuit, the “grain” and “grain-
boundary” resistance is found to decrease with increasing temperature, manifesting the
semiconducting behavior of the compound. Relaxation times were found to decrease with

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increasing temperature. Activation energies obtained for the relaxation process are in
agreement with those estimated from the analysis of frequency dependence of imaginary
part of electric modulus.

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RI
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M
D
TE
C EP
AC

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References
[1] J. T.S. Irvine, D.C. Sinclair, A. R. West, Advanced Materials 2 (1990) 132.
[2] B.V. Bahuguna Saradhi, K. Srinivas, G. Prasard, S.V. Suryanarayana, T. Bhimasankaram, Mater. Sci.
Eng. B98 (2003) 10.
[3] K. Laes, S. Bereznev, A. Tverjanovich, E.N. Borisov, T. Varema, O. Volobujeva, A. Öpik, Thin Solid
Films 517 (2009) 2286.

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[4] K. Laes, S. Bereznev, R. Land, A. Tverjanovich, O. Volobujeva, R. Traksmaa, T. Raadik, A. Öpik,
Energy Procedia 2 (2010) 119.
[5] C. Rincón, S. M. Wasim, G. Marín, J. M. Delgado, J. R. Huntzinger, A. Zwick, J. Galibert, Appl. Phys.

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Lett. 73 (1998) 441.
[6] L. Essaleh, G. Marín, S.M. Wasim, A. Alimoussa, A. Bourial, Superlattice Microst 92 (2016) 353.

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[7] A. Kumara, B.P. Singha, R.N.P. Chodhary, A.K. Thakur, J Alloy Compd 394 (2005) 292.
[8] G.Marín, S.Tauleigne, R.Guevara, J.M.Delgado, S.M.Wasim, P.Bocaranda, G.Sanches Perez, J.Diaz,
Inst.Phys.Conf.Ser. 152 (1998) 573. IOP Publishing Ltd.

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[9] G. Marín, S. Tauleigne, S.M. Wasim, R. Guevara, J.M. Delgado, C. Rincón, A.E. Mora, G. Sánchez
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Pérez, Mater. Res. Bull. 33 (1998) 1057. Also see references 12 and 13 cited in this reference.
[10] S. Hamrouni, M.F. Boujmil, K. Ben Saad, Adv Mat Phys Chem 4 (2014) 224.
[11] E. Barsoukov, J.R. Macdonald, Impedance Spectroscopy: Theory, Experiment, and
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Applications, New York, John Wiley & Sons, 2005.

[12] J.R. Macdonald, Impedance Spectroscopy: Emphasizing Solid-State Material
and Systems, Wiley, New York, 1987.
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[13] K.S. Rao, P.M. Krishna, D. M. Prasad, Phys Status Solidi B 244 (2007) 2267.
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[14] A.K. Jonscher: Dielectric Relaxation in Solids, Chelsea Dielectric Press Ldt., 1983, London.
[15] A. Maaroufi, O. Obai, B. Lucas, Physica B 492 (2016) 31.
[16] Z. Wang, W. Zhou, L. Dong, X. Sui, H. Cai, J. Zuo, Q. Chen, J Alloy Compd 682 (2016) 738.
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[17] N. E. Hill, W. E. Vaughan, A. H. Price, M. Davis, Dielectric Properties and Molecular Behavior, Van
Nostrand, London, 1969.
[18] C. F. Bo¨ttcher, P. Bordewijk, Theory of Electric Polarisation, Vol. 2, 2nd ed., Elsevier
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Science B.V., Amsterdam, 1992.

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[19] S. Havriliak, S. Negami, J. Pol. Sci.: Part C 14, 99 (1966).

[20] D.W. Davidson and R.S. Cole, Journal of Chemical Physics, 19, 1483 (1951).
[21] D. Mančić, V. Paunović, Z. Petrušić, M. Radmanović, Lj. Živković, Electronics 13 (2009) 11.
[22] T. Nagata, T. Shimura, A. Ashida, N. Fujimura, T. Ito, J Cryst Growth 237–239 (2002) 533.

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Table captions

Table I: Temperature dependence of adjustable parameters considered in the fit of Z”

versus Z’ with the corresponding relaxation times.

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Figure captions

Figure 1: Variation of Z’ and Z” as a function of frequency for a representative temperature

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of 308 K. The calculated data are represented by continuous curve. Values of frequency fg
for the grain contribution and its corresponding Z’ value are indicated.
Figure 2: Variation of Z” as a function of the frequency for some representative

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temperatures. The insert represents the variation of Ln(fmax), deduced from the maximum of
Z”, as a function of 1/T.
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Figure 3: Equivalent circuit and Nyquist diagram at different temperatures. The calculated
data are represented by continuous curve.
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Figure 4: Nyquist plots for the Debye single relaxation model (a), if there is distribution of
relaxation time (b) and in (c), the equivalent circuit consisting of two parallel RC elements
in series [ref. 19].
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Figure 5: Nyquist diagram at different temperatures. The insert: the parameter β as a

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function of temperature.
Figure 6: The deconvolution of the “grain” and “grain-boundary” contributions to Z” for a
representative temperature of 308 K: (a) in Z” versus frequency plot and (b): in Z” versus
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Z’ plot.
Figure 7: Variation of Ln(Rg) and Ln(Rgb) with inverse of temperature. The continuous
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straight lines represent the agreement with the Arrhenius law.

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Figure 8(a): Relaxation time for the “grain” contribution obtained separately from electric
modulus and from equivalent circuit model. The continuous straight lines represent the
agreement with the Arrhenius law.
Figure 8(b): Relaxation time for the “grain-boundary” contribution obtained separately
from electric modulus and from equivalent circuit model. The continuous straight lines
represent the agreement with the Arrhenius law.

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T(K) Ω)
Rg(Ω Qg ng Ω)
Rgb(Ω Qgb ngb τg(µs) τgb(µs)
-9 -8
308 22352 1,72 10 0,78049 23205 4,98 10 0,58502 2,20835 9,52355

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-9 -8
312 20122 1,78 10 0,78269 23576 5,00 10 0,58117 2,09088 9,14456

-9 -8
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318 17032 2,65 10 0,7619 20501 6,47 10 0,56721 1,9793 8,46874

-9 -8
326 15318 4,47 10 0,72931 16272 9,12 10 0,55419 1,94725 7,86478

-9 -7
339 12042 8,49 10 0,69955 12844 1,70 10 0,51839 1,97626 7,34017
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-8 -7
350 9334 1,27 10 0,68676 9422 2,99 10 0,48576 1,92776 5,62796
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Table I: Temperature dependence of adjustable parameters considered in the fit of Z”

versus Z’ with the corresponding relaxation times.
C EP
AC

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5
10

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308 K
Z' ( Ω )

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4
1,0x10
Experimental

Z'' ( Ω )
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4
10
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Z' ( fg ) = 11,176 kΩ 5,0x10
3

Fits to eqs. (12) and (13)

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fg = 141,5 kHz
0,0
3
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10 1 2 3 4 5 6
10 10 10 10 10 10
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Frequency (Hz)
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Figure 1: Variation of Z’ and Z” as a function of frequency for a representative temperature

of 308 K. The calculated data are represented by continuous curve. Values of frequency fg
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for the grain contribution and its corresponding Z’ value are indicated.
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12

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)

Ln(fmax) from Z''

Ln ( fmax (Hz)

Linear fit
308 K
4
1,2x10 312

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11

318
326
Z '' (Ω )

10
339

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-3 -3 -3
2,8x10 3,0x10 3,2x10
1 / T ( K -1 ) 350
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3
6,0x10
M
D
TE

0,0
2 3 4 5 6
10 10 10 10 10
EP

Frequency (Hz)
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Figure 2: Variation of Z” as a function of the frequency for some representative

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temperatures. The insert represents the variation of Ln(fmax), deduced from the maximum of
Z”, as a function of 1/T.

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Rg R gb Calculated
curves

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4
2x10
>C P>Eg >>
C P Eg b

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Z " (Ω)

Experimental data

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308K
4
1x10 312
AN
318
326
339
350
M

0
D

4 4
0,0 2,0x10 4,0x10
Z ' (Ω)
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Figure 3: Equivalent circuit and Nyquist diagram at different temperatures. The calculated
data are represented by continuous curve.
C EP
AC

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AN
M
D
TE
C EP
AC

Figure 4: Nyquist plots for the Debye single relaxation model (a), if there is distribution of
relaxation time (b) and in (c), the equivalent circuit consisting of two parallel RC elements
in series [ref. 19].

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 ACCEPTED MANUSCRIPT

4
2,0x10

PT
0 ,8

0 ,7
Experimental data

RI
35 °C 0 ,6

4
1,5x10 39 °C 0 ,5

45 °C
Z " (Ω )

SC
0 ,4
300 320 340 360
53 °C T (K )

66 °C
4 77 °C

U
1,0x10 AN
3
5,0x10
M

66 °C

β π/2
D

77 °C
0,0
TE

4 4
0 1x10 2x10
Z ' (Ω)
C EP

Figure 5: Nyquist diagram at different temperatures. The insert: the parameter β as a

function of temperature.
AC

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 ACCEPTED MANUSCRIPT

308 K (a)

4
1,0x10
Z '' ( Ω )

Fit to eq. (13)

PT
3
5,0x10

RI
0,0 "Grain" "Grain-boundary"

SC
1 2 3 4 5 6
10 10 10 10 10 10
Frequency (Hz)

U
AN
4
1.5x10
308 K (b)
M
Z " (Ω )

"Total"

4
D

1.0x10
Calculated curves
TE

"Grain"
3
5.0x10 "Grain
EP

boundary"
C

0.0
4 4
0.0 2.0x10 4.0x10
AC

Z ' (Ω)

Figure 6: The deconvolution of the “grain” and “grain-boundary” contributions to Z” for a

representative temperature of 308 K: (a) in Z” versus frequency plot and (b): in Z” versus
Z’ plot.

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 ACCEPTED MANUSCRIPT

PT
11,0

10,0

RI
Ln.Rg
Ln ( Rg ( Ω ) )

Ln.Rgb

Ln ( Rgb ( Ω ) )
10,5 Linear Fit

SC
10,0

U
AN 9,5

9,5
M

9,0
-3 -3 -3
2,8x10 3,0x10 3,2x10
D

-1
1/T (K )
TE
EP

Figure 7: Variation of Ln(Rg) and Ln(Rgb) with inverse of temperature. The straight
continuous lines represent the agreement with the Arrhenius law.
C
AC

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 ACCEPTED MANUSCRIPT

-12
from equivalent circuit
from electric modulus

-13
Ln ( τ relax, g )

PT
RI
-14

SC
-15
-3 -3 -3
2,8x10 3,0x10 3,2x10
-1
1/T (K )

U
Figure 8(a): Relaxation time for the “grain” contribution obtained separately from electric
AN
modulus and from equivalent circuit model. The straight continuous lines represent the
agreement with the Arrhenius law.
M

-10
D

from equivalent circuit

from electric modulus
-11
TE
Ln ( trelax, gb )

-12
EP

-13
C
AC

-14
-3 -3 -3
2,8x10 3,0x10 3,2x10
-1
1/T(K )

Figure 8(b): Relaxation time for the “grain-boundary” contribution obtained separately
from electric modulus and from equivalent circuit model. The straight continuous lines
represent the agreement with the Arrhenius law.

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 ACCEPTED MANUSCRIPT

• Complex impedance formalism is considered for the bulk p- CuIn3Se5.

• An equivalent electrical circuit has been proposed.
• Electrical resistance for the “grain” and “grain-boundary” contributions is analyzed.
• Activation energies for relaxation mechanisms were estimated.
• Results are compared with those obtained from electric modulus analysis.

PT
RI
U SC
AN
M
D
TE
C EP
AC

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