Journal of Non-Crystalline Solids 458 (2017) 137–140

Contents lists available at ScienceDirect

Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

Fractal explanation of Meyer–Neldel rule

Samy A. El-Sayed
Phys. Dept., Faculty of Science, University of Beni-Suef, Beni-Suef, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The relation between Meyer–Neldel rule (MNR) and fractal is investigated. Using very simple and elementary
Received 10 November 2016 mathematics, it is proved that the (MNR) is one of Mandelbrot sets form. The dc conductivity in temperature
Received in revised form 14 December 2016 range 1.7 K–300 K of structural disordered germanium irradiated fast neutrons with fluencies
Accepted 19 December 2016
1016 cm−2 ≤ Φ ≤ 1.2 × 1017 cm−2 is measured. From analysis, the dc conductivity results, the obtained EMN values
Available online 11 January 2017
is proportional with dc activation energies of each mechanisms of conduction. From the three values of EMN re-
PACS:
lated to each mechanism of conduction the second stage of EMN is obtained. The second stage of EMN value is
72.15.Cz lower than EMN obtained from ΔE1 or ΔE2. This result confirms the smaller replicas of self-similar distribution
72.80.Ng of impurity centers in germanium disordered fast neutrons irradiation. EMN is postulated as the loss of energy dis-
71.23.An sipated in formation certain fractal system in a medium.
71.55.Jv © 2016 Elsevier B.V. All rights reserved.

1. Introduction semiconductors, amorphous and polycrystalline semiconductors. A

In investigation of disorder materials, several properties, e.g., con-
ductivity and diffusion are found to show exponential thermally activat-
ed (Arrhenius) behavior [1].


−ΔE
X ¼ X0 exp
KT
Here X is the absolute rate of a thermally activated process, X0 the
preexponential factor, ΔE the activation energy and k the Boltzmann
constant. Meyer and Neldel detected that X0 is linked to ΔE by the fol-
lowing relation:


ΔE
X0 ¼ X00 exp
EMN
where X00 and EMN are positive constants. EMN is known as the Meyer–
Neldel energy for the process in question. This pragmatic relation is
known as the MN rule (MNR) or the compensation effect [2]. This rela-
tion known as the constable law which has been observed in many dif-
ferent materials for a number of phenomena [3–6]. The MNR is
observed in numerous thermally activated phenomena e.g. kinetics
(hopping) and thermodynamics, in crystalline, amorphous, and liquid
semiconductors. Innumerable different models have been suggested
to explain the MNR in different systems such as extrinsic
E-mail address: samy.abdelhameed@science.bsu.edu.eg.
model, called the statistical shift model, in which the Fermi level shifts
with temperatures because of asymmetry between the density of states
(DOS) above and below it, has been used to account for the MNR in elec-
tronic semiconductors. However, it could not answer the question of
why some non-electronic conductors follow the MNR, where crystalline
silicon does not? Also, Busch suggested that the MNR in extrinsic broad
ð1Þ
band semiconductors is due to a freezing of the donor concentration
during cooling after the preparation [7]. The MNR in amorphous or poly-
crystalline semiconductors may derive from an exponential tailing of
the majority band states as suggested by Roberts and by Cohen et al.,
or it may be due to a long-ranged electrostatic random potential. As
regards the MNR in organic semiconductors, Kemeny and Rosenberg
proposed a model where electrons or polaron tunnel through intermo-
lecular barriers from activated energy states of the organic molecules.
ð2Þ
For ionic conductors it has been argued that the MNR is an approximate
relation valid for ionic crystals with either Frenkel, Schottky or intersti-
tial disorder. It has even been suggested that the MNR may be a spurious
effect due to a thin rectifying layer at the electrode-solid interface. For
the explanation of problems associated with MNR, Yelon and Movaghar
[8] have proposed a model called as YM model. According to this model,
the MNR arises for kinetic procedures in which ΔE is the energy of kinet-
ic barrier and for which ΔE is large compared to the energies excitations
which contribute to the activations as well as KT. Yelon et al. suggested
the optical phonons are the source of excitation energy in such process.
It is assumed that many phonons engage in trapping and detrapping of
electrons either by cascade or by multi phonon process. They have de-
scribed MNR with entropy term which may fluctuate the pre-factor by
many orders of magnitude as it goes in equally well to crystalline or

http://dx.doi.org/10.1016/j.jnoncrysol.2016.12.026
0022-3093/© 2016 Elsevier B.V. All rights reserved.
138 S.A. El-Sayed / Journal of Non-Crystalline Solids 458 (2017) 137–140
amorphous material, [9]. Also Fang [10] proved the equivalence of MNR
with the Schewiedler relaxation distribution.
“Clouds are not spheres, mountains are not cones, coastlines are not
circles, bark not smooth, nor does lightning travel in a straight line” [11].
Fractal structures are found everywhere in nature [12]. The possible
simplest definition of fractal is an object which appears self-similar
under varying degrees of magnification [13]. Some disordered materials
possess fractal structure over a certain range of length scales. Introduc-
tion of the fractal concept has been successful in the identification of
many of the physical properties in disordered systems [14]. Static (geo-
metric) properties of fractals have been widely accepted as describing
properties of large collection physical objects that exhibit some kind of
self-similarity [15]. Fractals may be found in nature or generated using
a mathematical recipe [13]. The word fractal was coined by Benoit Man-
delbrot, sometimes referred to as the father of fractal geometry. Man-
delbrot realized that it is very often impossible to describe nature
using only Euclidean geometry. Mandelbrot proposed that fractals and
geometrical fractals could be used to describe real objects [16].
The term percolation connected with a new class of mathematics
concerned with the flow of a liquid through a random maze [17].
Shklovskii and Efros on the basis of the percolation theory derived the
following formula:
σ ¼ σ 3 eE3 =KT
where
−Nα a
σ 3 ¼ σ 03 e D ; α ¼ 1:74  0:02;
and E3 is the hopping conduction energy. To describe the conductivity
(σ) at hopping conduction region (at low temperatures), where ND is
the donor concentration and (a) Bohr radius of impurity electron
wave, i.e.:
α
ln σ 03 ¼ σ 003 −
1=3
ND a
Here we have to notice the similarity between Eq. (2) and Eq. (3), in
that the two equations having exponent form. But Eq. (3) deduced using
percolation theory. In case of random resistance networks the essential
role played by randomness of current carrying properties. When ran-
domness is strong as embodied by a network consisting of random mix-
ture of resistors and insulators, this random resistor network undergoes
transition between a conducting phase and insulating phase when the
resistor concentration passes through a percolation threshold [18]. In
Germanium doped irradiation defects the critical behavior of activation
energy and also the parameters which define them, i.e. the dielectric
constant, localization radius, and the coefficient To are found and com-
pared with predictions of scaling theory [19]. Is there any relation be-
tween MNR and the fractal?
2. Theoretical
Since Meyer–Neldel Rule has the form
ΔE
x ¼ x0 e−KT ;
ΔE
x0 ¼ x00 eEMN
eiπ ¼ −1; einπ ¼ ð−1Þn
But from Euler's formula
Multiplying denominator and numerator of the exponent of Eq. (5)
pffiffiffiffiffiffiffiffi
by i = −1
iΔE
ð−1Þx0 ¼ x00 eiEMN  eiðϑþπÞ
iðΔE
þπÞ=
−x0 ¼ x00 e iEMN
ΔE
Let ϑ ¼ −i ð6Þ
EMN
ln θ ¼ ln ΔE þ i ln EMN
−x0 ¼ x00 eiðϑþπÞ ; ð1−Þn x0 ¼ x00 einðϑþπÞ
And by using Demoiver's theorem, it is easy to prove that:
z ¼ ð−1Þ1−n zn ð7Þ
where z is the complex number equation.
It is obvious that Eq. (7) belong to Mandelbrot sets [10]:
z ¼ z2 þ c ð8Þ
Latt'es 1918, has pointed out that two collections of functions of
complex variables share the property that the doubling formula yielding
f (2z) is a rational function of f(z). On such collection centers, the func-
tion tanθ, tanhθ, and cosθ, involve only minor modifications. Historically
the study of global properties of iterations began with Cayley 1879 used
the Newton–Raphson method to solve the equation f (z) = z2 – 1 = 0.
That method consists in iterations of rational function g (z) =
(z2 – 1) / 2z = λ(z + 1 / z) [15]. Levinshtien et al. [20] suggested an ap-
proach based on an extension of the scaling hypothesis. They assumed
that as we approach the percolation threshold the large-scale structure
ð3Þ of the network remains similar to itself in in the sense that its topology
remains the same and its linear dimension change proportionally with
the correlating distances L = ∣τ∣−υ, where τ = x − xc. The critical expo-
nents of Insulator-Metal transition in germanium disordered neutron ir-
radiation was determined [19] and were found to be ≤2 as predicted by
scaling theory.
3. Experimental
ð4Þ
Five samples of non-doped germanium with carrier density no =
3 × 013 cm−3 were irradiated with fast reactor neutrons with energies
E ≥ 0.1 MeV in the range 6 × 1016 cm−2 ≤ Φ ≤ 1.2 × 1017 cm−2. As a re-
sult of irradiation all samples become disordered p-type [21,22]. In
order to reduce the transmutation doping effect all samples were placed
in 1 mm thick cadmium containers. During irradiation in the reactor the
ratio between thermal neutrons fluency and the fluency of fast neutrons
was about ten. So, it was possible to obtain samples of germanium
“doped” with acceptor-like radiation defects {Ge (RD)}. To ensure that
the electrical properties controlled by the transmutation doping, a com-
plete annealing is performed at 450 °C for 24 h. For electrical conductiv-
ity measurements a special double wall glassy cryostat is designed. The
cryostat is attached with vacuum pump has evacuation rate faster than
the evaporation rate of He4 gas, thus the pressure inside the cryostat is
decreases and cause decrease the temperature inside the cryostat. For
electrical resistivity measurements, the conventional four prop method
is used. The electrochemical deposition technique (cold method) is used
for precipitating Ni electrode in the desired position on the samples.
Thin Cu wires are fixed above the Ni electrodes using indium. The sam-
ples were in parallelepiped shape with length about 8–12 mm, thick-
ness about 1–2 mm, width about 2–3 mm and the electrode apart
about 3–4 mm. Resistivity of Ge (RD) was measured in the temperature
range from 1.7 K up to 300 K. The temperature was determined with a
ð5Þ semiconductor thermistor in the interval 77.4–4.2 K, from saturated
vapor pressure of He4 in the interval 4.2–1.5 K. The voltage across sam-
ples always ≤1 V and the current across the sample decreases from μA to
nA as the temperature lowered. The electrical properties of Ge (RD) are
determined solely by acceptor-like radiation defects in spite of fairly
 S.A. El-Sayed / Journal of Non-Crystalline Solids 458 (2017) 137–140 139

high concentration impurities introduced by transmutation doping. The

least square method fitting, using a computer program, is used to anal-
ysis the data extracted.

4. Experimental results and discussion

Fig. 1 shows the dependence of conductivity on temperature. This

figure shows that the conductivity increases as the irradiation fluency
increases. The three regions of conductivity are apparent, satisfying
the thermally activated conductivity relation [22–24]:

E ¼E  −ðEA −E F þW1 Þ W2
σ ¼ σ 1 e− KT þ σ 2 e
C F
KT þ σ 3 e− KT ð9Þ
Fig. 2. Shows ln (σo) = f (ΔE) for the three mechanisms of electrical conductivity.

where the term (σ1 exp. − (EC − EF) / KT) represents transport by car-
riers excited beyond the mobility edges into non-localized (extended)
states at EC or EV. And σ is the conductivity, σ1 is the pre-exponential
factor. A plot of lnσ versus 1 / T will yield a straight line if (EC − EF) is
a linear function of T over the temperature range measured, and the in-
tersection of line extension with the ordinate gives the σ1. As the tem-
perature decreases transport carriers excited into localized states at
the band edges and the conductivity is given by σ2exp. − (EA −
EF + W1) / KT, where W1 is the activation energy for carriers hopping,
W1 should decrease with decreasing temperature on the account of var-
iable - range nature of the hopping transport. However, as the temper-
ature dependence is through the carrier activation term, an
approximately linear dependence of lnσ versus 1 / T is again expected.
As the temperature lowered more, there will be a contribution from car-
riers with energies near EF which can hop between localized states. This
contribution is described by σ3 exp. (−W2) / KT, where σ1 ≥ σ2 and W is
the hopping energy, of the order of half the width of the band of the
states. The nominators of the exponentials of Eq. (9) are simply labeled
in the present article by the respective symbols ΔE1, ΔE2 and ΔE3.
Fig. 2 shows lnσi = f (ΔEi), i = 1: 3, for the three mechanisms of con-
ductivity. It is clear that the slope is positive for all mechanisms of con-
ductivity i.e. the applicability of (MNR) in germanium structural
disordered fast reactor neutrons (Table 1).
The MNR fitting equations of the three mechanisms of dc conduction
for the samples under investigations are
ð10Þ
By plotting the obtained values of (EMN)−1 of the three mechanisms
of conduction versus the intersection with the ordinate as seen in Eq.
(10), Fig. 3 is obtained from which the energy EMN value of second
stage of MNR is calculated and equal to 0.0007 eV. Here it worth to no-
tice that the EMN values of the first stage of MNR is decreases as the
mechanism of conduction changes from Band to band conduction
mechanism ΔE1, to hopping by carriers into localized states at the
band edges of energies close to band edges ΔE2, and hoping of charge
carriers with energies near Fermi level ΔE3. It is also noticed that the
EMN is directly proportional with value of dc conductivity activation en-
ergy of each mechanism of conduction. Since ΔE1 N ΔE2 N ΔE3 the ob-
tained EMN is also decreases with change the mechanism of
conduction which is changes from mechanism to another as the tem-
perature decreases [22]. The value of the second stage of EMN is lower
than the values of EMN related to ΔE1 or ΔE2 But much higher than
EMN related to ΔE3. This results confirm the postulation that Meyer–
Neldel Rule (Eq. (2)) is one of the Mandelbrot's sets form. The most im-
portant property of fractals is their self- similarity, or their symmetry
under dilation. Construction of fractal begins with initiator and proceeds
with set of operations is called generator. The initiator is replaced by
smaller replicas of itself and fractals build inwardly, towards ever small-
er length scale [12]. Since ϑ ¼ −i EΔEMN
, from Eq. (6) ΔE is a real value, one
can interpret EMN as the energy dissipated in formation certain fractal
system (certain impurity distribution in a certain medium). The de-
crease of experimentally obtained values EMN from stage one to stage
two confirms the smaller replicas of self-similar distribution of impurity
centers in germanium irradiated reactor neutrons. Using standard tran-
sient capacitance spectroscopy and C-V measurements Fourches [23,24]
proved the existence of P-type regions with significant spatial extension
in fast neutrons irradiated with high purity germanium. Also,
Muramatsu et al. [25], used the fractal theory for explanation the medi-
um range order of amorphous thin film samples.

Table 1
The radiation fluency (φ), and the three activation energies (ΔE1, ΔE2 ,ΔE3) for the three
mechanisms of conductivity.

Sample no. φ, n.cm−2 ΔE1, eV ΔE2, eV ΔE3, eV

1 6.00E + 16 0.01 ± 1E−3 0.002 ± 3E−4 0.001 ± 5E−4

2 6.90E + 16 0.012 ± 1E−3 0.006 ± 3E−4 0.00015 ± 5E−4
3 9.00E + 16 0.012 ± 1E−3 0.004 ± 3E−4 0.001 ± 5E−4
4 1.10E + 17 0.007 ± 1E−3 0.001 ± 3E−4 0.0006 ± 5E−4
5 1.20E + 17 0.009 ± 1E−3 0.001 ± 3E−4 0.0008 ± 5E−4
Fig. 1. The dependence of dc conductivity on temperature.
140 S.A. El-Sayed / Journal of Non-Crystalline Solids 458 (2017) 137–140

for ΔE3. EMN is postulated as the loss of energy dissipated in formation

certain fractal system in a medium.

References
[1] M. Meyer, H.Z. Neldel, Tech. Phys. 18 (1937) 588.
[2] N. Mehata, S.K. Agraharia, A. Kumar, Phys. Scr. 74 (2006) 579–583.
[3] K. Shimakawa, F. Abdel-Wahab, Appl. Phys. Lett. 70 (1997).
[4] A. Delvi, N.P. Reddy, S.C. Agrwal, Solid State Commun. 152 (2012) P612–P615 and
references therein.
[5] T. Drusedau, R. Bindemann, Phys. Status Solidi B K61 (1986) 136.
[6] J.C. Dyre, J. Phys. C Solid State Phys. 19 (1986) 5655–5664 and references therein.
[7] G. Busch, Z. Angew. Math. Phys. 1 (1950) 81.
[8] A. Yelon, B. Movaghar, H.M. Branz, Phys. Rev. B 46 (1992) 12244–12250.
[9] A. Kumar, A. Kumar, Journal of Non-Cryst. Solids 386 (2014) 51–55.
[10] P.H. Fang, J. Non-Cryst. Solids 85 (1986) 251–254.
[11] B.B. Mandelbrot, The Fractal Geometry of Nature, Freeman and Company, New York,
1983 1–6.
[12] B.D. Avraham, S. Halvin, Diffusion and Reactions in Fractals and Disordered Systems,
Fig. 3. Shows ln (ρoo) = f (1 / EMN) as obtained from the least square method applied on Cambridge University Press, 2000 1–31.
the data represented in Fig. 2. [13] P.S. Addison, Fractals and Chaos, Institute of Physics Publishing, Bristol and Philadel-
phia, 1997 1–5.
[14] S.A. El-Hakim, Philos. Mag. B 82 (8) (2002) 963–968 and references therein.
[15] D. Raf, A. Komoda, A. Marein, A. Stella, Phys. Scr. T29 (1989) 230–233.
5. Conclusions [16] B.B. Mandelbrot, Fractals and Chaos the Mandelbrot Set and Beyond, Springer-
Verlag, New York, 2004 100–107.
The overall results show that; the Meyer–Neldel rule may be belong to [17] B.I. Shklovskii, A.L. Efros, Electronic Properties of Doped Semiconductors, Springer-
Verlag, 1984 94–130.
Mandelbrot sets. The dc conductivity of germanium structural disordered
[18] R. Fogelhom, J. Phys. C 13 (1980) L571–L574.
fast reactor neutrons with fluencies 1016 cm−2 ≤ Φ ≤ 1.2 × 1017 cm−2 is [19] S.A. El-Hakim, J. Nonlinear Phenomena in Complex Systems 3 (2) (2000) 174.
measured is measured in the temperature range 1.7 K–300 K. The three [20] M.E. Levinshtein, M.S. Shut, A.L. Efros, Sov. Phys. JETP 42 (1975) 1120.
[21] V.P. Debrego, O.P. Ermolaev, V. Tkachev, Phys. Status Solidi A 44 (1977) 435.
activations energies ΔE1, ΔE2 and ΔE3 of the three conventional mecha-
[22] N.F. Mott, E.A. Davis, Electronic Processes in Non-crystalline Materials, Oxford Uni-
nisms of conductivity are obtained. By applying MNR the EMN of the versity Press, 2012 209–215.
three mechanisms of conductivity are obtained. From the deduced EMN [23] H. Fritzche, J. Phys. Chem. Solids 6 (1958) 69.
and the intersection of the straight line with the ordinate the second [24] N. Fourches, J. Appl. Phys. 77 (1995) 3684.
[25] S. Muramatsu, S. Matsubara, T. Watanabe, T. Shimida, T. Kamiyama, K. Suzuki, J.
stage EMN is obtained. The obtained the value of second stage EMN is Non-Cryst. Solids 150 (1–3) (1992) 163.
lower than the EMN obtained for ΔE1 or ΔE2 but much higher than EMN