Models of electron trapping and transport in polyethylene: Current–voltage

characteristics
J. A. Anta, G. Marcelli, M. Meunier, and N. Quirke

Citation: J. Appl. Phys. 92, 1002 (2002); doi: 10.1063/1.1489714

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 JOURNAL OF APPLIED PHYSICS VOLUME 92, NUMBER 2 15 JULY 2002

Models of electron trapping and transport in polyethylene:

Current–voltage characteristics
J. A. Anta,a) G. Marcelli, M. Meunier,b) and N. Quirkec)
Department of Chemistry, Imperial College of Science, Technology and Medicine,
South Kensington SW7 2AY, United Kingdom
共Received 2 January 2002; accepted for publication 6 May 2002兲
We present a unified method to estimate current–voltage characteristics of insulators starting from
ab initio electronic calculations of the properties of the dielectric material. The method consists of
three stages: 共1兲 computation of trap energy distributions for excess electrons by means of density
functional theory, 共2兲 computation of local electron mobilities from a multiple trapping electron
transport model which includes trap filling effects and 共3兲 macroscopic integration of the Poisson
and current–field equations, using local electron mobility data from stage 共2兲 to predict the current–
voltage characteristics for a material of a given width. The only input to this procedure is the
chemical composition of the insulating material. We compare our model results with experimental
studies of the current–voltage curve of cross-linked polyethylene. © 2002 American Institute of
Physics. 关DOI: 10.1063/1.1489714兴

I. INTRODUCTION decomposition.10 An understanding of space charge accumu-

Electrical supply companies use polyethylene as an in-
sulating material for high-voltage electric cables. Over time,
such insulators trap charge carriers and form a ‘‘space
charge’’ that is thought to be implicated in dielectric break-
down. There is now a considerable amount of literature con-
cerned with experimental characterization of space charge1– 8
and with phenomenological models of space charge forma-
tion and discharge. Most current theories of insulator failure
relate the eventual dielectric breakdown of polymeric insula-
tion to charge accumulation and displacement of one type or
another. For example, in the ‘‘space charge aging model’’ the
presence of both physical and chemical defects leads to the
accumulation of electrons in traps, thus forming a space
charge which alters local properties. It has been suggested9
that electron traps have a range of energies, from shallow
共⬍0.5 eV, perhaps arising from physical or conformational
‘‘defects’’ in the amorphous polymer兲 to deep 共of the order of
eV, associated, for example, with chemical defects or impu-
rities兲. The resulting electrostatic and electromechanical
forces are thought8 to lower the energy barriers to local con-
formational change and produce new free volume and micro-
voids, eventually initiating failure via a variety of mecha-
nisms such as impact ionization. Recently it has been
suggested that the detection of continuous electrolumines-
cence in polymers including polyethylene under dc condi-
tions is controlled by charge transport processes and that it
might signal the potential onset of bulk aging due to charge
recombination and subsequent local relaxation or chemical
reactions linked to excited states and subsequent chemical
a兲
Present address: Departamento de Ciencias Ambientales, Universidad
b兲
Pablo de Olavide, Crta. de Utrera Km.1, 41013 Seville, Spain.
Present address: Accelerys, 230-250 The Quorum Barnwell Road,
Cambridge CB5 8RE, UK.
c兲
Author to whom correspondence should be addressed; electronic mail:
n.quirke@ic.ac.uk
lation and discharge and its link to dielectric breakdown
would be a major scientific achievement as well as it would
facilitate the prediction of cable lifetimes and the design of
better cables.9 However space charge accumulation and dis-
charge together with related trapping-detrapping phenomena
are still poorly understood. Our current work is aimed at
clarifying the contribution of electrons to space charge trap-
ping and detrapping 共for now we assume that electrons are
the dominant charge carriers兲. In particular we wish to pre-
dict the current–voltage characteristics of polyethylene from
the electron trap distribution 共or density of localized states兲
determined from our earlier molecular modelling studies11,12
In a previous paper we have shown11 that by defining
defect 共conformational, chemical or impurity兲 energies in
terms of the molecular electron affinity, a relationship is es-
tablished between the putative electron trap and the local
properties of the material. In order to probe the contribution
of conformational disorder to electron trapping in polyethyl-
ene using molecular modeling we considered the condensed
phases of much smaller alkane molecules which have a band
structure very similar to that of polyethylene.13,14 We repre-
sented the local conformational disorder of segments of
polyethylene in the amorphous regions by configurations
taken from computer generated glassy phases of the tride-
cane (n-C13H26) wax. Our strategy has been to identify the
local electron traps 共localized states兲 in polyethylene with the
increase in electron affinity of the more distorted C13 mol-
ecules, conformationally trapped in the glass. This approach
has made it possible, using density functional theory, to pro-
vide estimates of the energy, number and residence times of
conformational electron traps in polyethylene. Typical physi-
cal trap energies were found to be of the order of 0.15 eV
and all are less than 0.3 eV. In a subsequent paper12 a similar
approach was used to estimate the trap energies of chemical
defects commonly present in polyethylene insulators. The
two sets of calculations provide a distribution of trap ener-

0021-8979/2002/92(2)/1002/7/$19.00 1002 © 2002 American Institute of Physics

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 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002 Anta et al. 1003

gies 关or density of localized states 共DOLS兲兴 for the material.
Chemical defects can be divided into two groups. The
first group 共impurities兲 includes the chemical defects found
on a polymeric chain, i.e., hydroxyl and ketone functions,
double or triple carbon–carbon bonds, branching, and so on.
This group of chemical defects was modeled as a chemical
modification of an alkane chain. The second group consists
of some of the by-products of the branching agent dicumyl
peroxide, an additive used in commercial cable manufacture
as a cross-linking agent. Recent luminescence experiments
have confirmed our theoretical predictions of their impor-
tance as trapping centers in polyethylene.15
In this article we combine the trap distribution 共or
DOLS兲 with a multiple trapping electron transport model to
estimate the current–voltage (CV) curve of polyethylene.
Thus we obtain the dc characteristics of an insulating mate-
rial using as input only information on its chemical compo-
sition. Charge transport is modeled as thermally activated
multiple trapping/detrapping between localized states de-
scribed by the trap distribution. A modified continuous time
random walk simulation technique16 is used to solve the
model and to estimate the local conducting properties of the
material, that is, the mobility as a function of the local field
and the density of carriers 共in this case, electrons兲. The mo-
bility is a strong function of the electron density due to trap
filling. As more electrons are injected into a system with a
distribution of trap energies, traps with larger energies with
respect to the conduction band level 共deep traps兲 are progres-
sively filled, leaving only shallow traps available for conduc-
tion. Because the residence times of electrons in deep traps
are much longer than those in shallow traps, the net mobility
of the electrons is enhanced as the electron density increases.
These simulation results are used to validate a theoretical
expression for the mobility that can be used at all densities.
This is particularly important at low densities where the
simulation procedure in its present form would be impracti-
cal. Finally, the field and density dependent mobility is used
in a macroscopic calculation that takes into account space
charge effects: the space charge limited conduction 共SCLC兲
model.17 We present results for the case of macroscopic
samples of cross-linked polyethylene 共XLPE兲, 150 and 200
␮m wide, for which experimental data are available.18,19 The
degree of agreement indicates the viability of our ‘‘first-
principles’’ method for predicting current–voltage character-
istics in real electrical devices, however it seems likely that
in the high-field regime ionic impurities and holes introduced
through the anode may play a very important role. The con-
sideration of these carriers will require generalization of the
models for local mobilities.20
This article is organized as follows. In Sec. II we sum-
TABLE I. Trap energies and relative concentration of traps for model poly-
ethylene 共after Ref. 12兲 or the density of localized states. Each trap energy is
represented in the calculations by a Gaussian of standard deviation of 0.05
eV.
Trap energy Fraction of traps
共eV兲 with a given energy
0.1 9.9800⫻10⫺4
0.12 1.4946⫻10⫺1
0.16 6.4766⫻10⫺1
0.2 2.0028⫻10⫺1
0.5 9.9800⫻10⫺4
0.7 5.0061⫻10⫺4
0.9 9.9800⫻10⫺5
1.1 9.9800⫻10⫺6
II. DISTRIBUTION OF TRAP ENERGIES
The trapping of electrons in polyethylene is assumed to
be caused by 共a兲 physical, that is conformational, defects
originating from local disorder21 found in the amorphous part
of the material, and 共b兲 by chemical defects arising from
chemical impurities due to industrial processing and to
breakdown products. We identify a trap as being present in
the material where the electron affinity of a molecule is
larger than the electron affinity of the crystalline host 共EA c
⫽⫺E c where E c is the energy of the bottom of the conduc-
tion band兲.
E 共 trap兲 ⫽EA defect⫺EA c .
An excess electron present in the material will prefer to lo-
calize on the trap site rather than remain in the conduction
band. The electron affinities have been computed using den-
sity functional theory and are reported elsewhere.11,12,22
From the density of conformational traps estimated from mo-
lecular dynamics and the reported densities of chemical im-
purities a representative electron trap energy distribution has
been obtained. Physical traps are numerous (2⫻1027 m⫺3 )
and shallow 共the distribution is centered around 0.16 eV with
a dispersion of 0.05 eV兲. Chemical defects are scarce
(1021 – 1025 m⫺3 ) and can be much deeper 共⭐1.1 eV in our
calculations兲. In Table I the concentrations and characteristic
energies of some of the most important chemical traps in
XLPE insulation are displayed. The data are summarized in
Fig. 1.
III. MODELS OF CHARGE TRANSPORT
We assume that transport of charge occurs by the trans-
fer of electrons between localized states or traps. In the sim-
plest situation, all traps will have the same energy 共i.e., a
density of states with the shape of a Dirac delta function兲. In
this case, it can be shown that the mobility is given by9

冉 冊 冉 冊
marize the main features of the ab initio calculation of the
2 ␯ 0a E eE"a
trap energy distribution 共the DOLS兲. In Sec. III we describe ␮⫽ exp ⫺ sinh , 共1兲
the computational technique employed to simulate multiple lE kT 2kT
trapping transport of electrons and present results for elec- where ␯ 0 is the attempt-to-jump frequency, a is the average
tron mobilities in polyethylene. In Sec. IV we describe the distance between traps, l is the number of equivalent neigh-
SCLC model with density dependent mobilities and report boring sites to which the carrier is allowed to jump,23 E is
the results for the current–voltage characteristics of samples the field applied, E is the trap depth 共activation energy兲, e is
of XLPE. Our conclusions are presented in Sec. V. the elementary charge, k is the Boltzmann constant and T is

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 1004 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002
FIG. 1. Trap energy density distribution or DOLS 关density of localized
states g(E) 共eV⫺1 m⫺3兲兴 predicted by our calculations for model PE 共see
Ref. 12兲 关in order to represent the likely effects of conformational disorder
on the energies of the chemical traps 共see Ref. 28兲, the chemical traps are
distributed in energy around the values given in Table I using a Gaussian
distribution with a standard deviation of 0.05 eV兴. Thick line: Physical de-
fects; thin lines: chemical defects 共500⫻兲.
the absolute temperature. Although the original model was
for ionic transport,17 it can be used to describe conductivity
of any kind of carrier24 provided there are no tunneling ef-
fects.
In the limit of very small fields (eE"aⰆkT), Eq. 共1兲
reduces to
冉 冊
␯ 0a 2e E fies detailed balance, i.e., the rate of emission of electrons
␮⫽ exp ⫺ , 共2兲
lkT kT
and in the absence of traps the mobility is given simply by
␯ 0a 2e
␮ ⬅ ␮ rw ⫽ , 共3兲
lkT
which corresponds to the mobility of a carrier performing a
simple random walk with time step t 0 ⫽1/␯ 0 in a network of
lattice constant a and coordination number l.
A. Multiple trapping random walk method and the
TRAM code
For a system with an arbitrary distribution of trap ener-
gies 共localized states兲 we employ a multiple trapping random
walk 共MTRW兲 method and its associated code transport in
amorphous materials 共TRAM兲. This approach has been de-
scribed in detail elsewhere for the case of electron transport
in dye sensitized nanocystalline TiO2 . 16 In brief, the method
simulates transport of charge by thermally activated multiple
trapping of carriers in traps whose energies are distributed
according to a given density of states 共the trap distribution兲.
The calculations consider several electrons simultaneously
with the condition that only one electron is allowed per trap.
The simulation is based on trapping times between two sites
i and j calculated via the expression
t i j ⫽⫺ln共 r 兲 t 0 e 关 E i ⫹eE"aui j /2兴 /kT , 共4兲
where r is a random number uniformly distributed between 0
and 1, E i is the trap depth 共energy兲 of the starting site, i, a is
the lattice parameter 共distance between the sites兲, ui j is the
unit vector linking sites i and j, E is the field applied.
The MTRW method is implemented on a three-
dimensional 共3D兲 lattice of sites with periodic boundary con-
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Anta et al.
FIG. 2. Comparison of mobility vs electron density from simulation 共TRAM:
䊉兲 and from the mobility model 关Eqs. 共1兲, 共6兲, and 共7兲:- - -兴 for the distri-
bution in Table I. The cutoff in the trap energy distribution was set to 1.15
eV in the simulation. The field applied was 30 kV/mm, T⫽28 °C.
ditions enforced in all directions. Carriers crossing any of the
boundaries of the sample are automatically re-injected
through the opposite boundary. This leads to mobilities
which are independent of the size of the simulation lattice.16
In addition, the TRAM code is run under the restriction that no
more than one particle is allowed per site. With this restric-
tion the electrons obey Fermi–Dirac statistics with a quasi-
Fermi level for the injected charge and the simulation satis-
from traps is equal to the rate of capture by traps.16 The
resulting mobility of the carrier is density dependent; trap-
filling effects, that is, the enhancement of the conducting
properties at larger concentrations of carriers, are explicitly
considered. The MTRW algorithm and hence TRAM can be
applied to any kind of conducting carrier 共electrons, holes,
ions兲 providing that the energy distribution of the corre-
sponding traps is known.
B. TRAM results for polyethylene
We have carried out TRAM calculations for polyethylene
using as input the trap energy distribution of Fig. 1. In the
calculations, the energy of the chemical traps is represented
by Gaussians centered at the values reported in Table I with
a dispersion of 0.05 eV. Figure 2 shows the mobility as a
function of density obtained using a system of 80⫻80⫻80
sites separated by a distance a⫽8.1 Å 关corresponding to
cross-linked polyethylene 共or XLPE兲 peelings25 with a crys-
tallinity of 40%兴 and a value of t 0 ⫽2.4⫻10⫺15 s 共this value
is obtained from the ground state frequency of the 3D square
well of width 8.1 Å and is comparable to the phonon fre-
quencies in polyethylene reported兲.26
The mobilities become progressively larger as the den-
sity of the electrons increases. This is the well-known trap-
filling effect,16,27 a consequence of the occupation of the
deepest traps. At very low electron densities the simulation is
dominated by the deepest traps 关see Eq. 共10兲 below兴. In order
to properly represent this part of the trap distribution several
of the deep traps must be included in the simulation cell. The
concentration of deep traps is however very low and as a
consequence a very large number of trap sites would be re-
 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002 Anta et al. 1005

冒兺
quired to give the correct concentration. This requires that n

the total number of lattice sites and hence the simulation cell exp共 ⫺ ␤ E F 兲 ⫽ 共 ␳ /N t 兲 c i exp关 ␤ 共 E i 兲兴 . 共8兲
i⫽1
size be very large indeed.
If we use a Gaussian representation of the trap distribu- For the case E n ⰇE n⫺1 only the deepest trap contributes to
tion in order to represent the likely effects of conformational the sum in Eq. 共8兲 and we have
disorder on the energies of the chemical traps28 then, at low
exp关 ␤ 共 E F ⫺E n 兲兴 ⫽N t c n / ␳ .
electron density, the states on the high energy side of the
Gaussian 共cf. Fig. 1兲 that represent the deepest traps will At low density the right-hand side must be Ⰷ1 so that E F
become significant. In this case the introduction of an energy ⬎E n 关note also that E F ⫺E n ⫽kT ln(Ntcn /␳) so that E F ⫽E n
cutoff in the trap energy distribution in order to avoid having at T⫽0 K兴.
too large a cell will modify the mobilities at the lowest den- From these considerations we can write the Fermi–Dirac
sities. We estimate the space charge densities in polyethylene distribution as
as being of the order of 1020 m⫺3 compared to the density of
f 共 E i 兲 ⫽1/兵 1⫹exp关 ␤ 共 E F ⫺E i 兲兴 其 ⬃exp关 ␤ 共 E i ⫺E F 兲兴 .
⬃1022 m⫺3 for the deepest traps. Hence electron mobilities
will be dominated by the deepest traps and the current simu- Using ␴ ⫽ ␳ e 具 ␮ 典 with Eqs. 共2兲 and 共6兲 共the zero field case兲
lation method may require very large cell sizes. In Sec. III C we have
we consider an approximate model which agrees with the n
TRAM simulations at moderate electron density but which can
also be used to make predictions at low electron densities.
␴ ⫽eN t ␮ RW 兺 c i exp共 ⫺ ␤ E i 兲 f 共 E i 兲 ⬃eN t ␮ RW
i⫽1

C. Mobility model results for polyethylene ⫻ 兺 exp共 ⫺ ␤ E i 兲 exp关 ␤ 共 E i ⫺E F 兲兴

i⫽1
To describe the effect of the occupancy of the traps on
⫽eN t ␮ RW exp共 ⫺ ␤ E F 兲 .
the conductivity, we start from a formula for the conductivity
of a system with intraband localized states16,29 and write the From Eq. 共8兲 the Fermi level is determined by the term in n
average mobility as the weighted average of the energy de- only and
pendent mobility. In Eq. 共6兲, g( ⑀ ) is the density of localized ␴ ⫽e ␮ RW ␳ exp共 ⫺ ␤ E n 兲 / 关 c n 兴 ,
states 共the number of electron traps per unit volume with
energy ⑀兲, ␮共⑀兲 is the energy dependent mobility and f ( ⑀ ) is hence
the probability of a trap of energy ⑀ being occupied. In Eqs. 具 ␮ 典 ⫽ ␮ RW exp共 ⫺ ␤ E n 兲 / 关 c n 兴 . 共9兲
共5兲 and 共6兲, E F ( ␳ ) is the density dependent quasi-Fermi level
for the injected charge and ␳ is the electron density, Equation 共9兲 makes clear the all-important role of the size

冕␮
and concentration of the deepest traps in situations where the
⬁
␮⬅具␮典⫽ 共 E 兲 g 共 E 兲 f 关 E,E F 共 ␳ 兲 ,T 兴 dE/ ␳ , 共5兲 density of electrons is much smaller than the density of deep
0 traps. The deepest traps determine the electron quasi-Fermi

冕 ⬁
level and hence the fraction of thermally excited electrons in
␳⫽ g 共 E 兲 f 关 E,E F 共 ␳ 兲 ,T 兴 dE. 共6兲 the conduction band.
0

The mobility ␮ (E) is given by Eq. 共1兲, or for zero field Eq.
共2兲. For a given electron density Eq. 共6兲 is solved for the
quasi-Fermi level and the result is used in Eq. 共5兲 to predict
the mobility. Figure 2 compares the mobilities calculated in
this way with the TRAM results for the same system 共but with
an energy cutoff兲. There is good agreement but, as expected,
the simulations begin to deviate from the new results at the
lowest densities due to finite size effects. In what follows we
use Eqs. 共5兲 and 共6兲 to predict mobilities.
1. Delta function DOLS
The dependence of the mobility 共conductivity兲 on the
deepest traps at low density is very evident if we approxi-
mate the DOLS by a set of n delta functions with energy E i .
n
In this case g(E)⫽N t 兺 i⫽1 c i ␦ (E⫺E i ) with N t the total
number of localized states 共traps兲, c i ⫽N i /N t , E i⫹1 ⬎E i 共all
E are taken as positive with respect to the conduction band兲.
We look at the low density case ␳ /N t Ⰶc n .
n increasing the concentration of the remaining traps propor-
␳ ⫽N t 兺 c i exp关 ␤ 共 E i ⫺E F 兲兴 ,
i⫽1
共7兲
2. Mobility as a function of trap depth and
concentration
Figure 3 shows the variation of mobility at low density
calculated using the mobility model 关Eqs. 共2兲, 共5兲 and 共6兲兴
for various trap distributions 共DOLS兲. The average mobility
increases as the deepest traps are filled. Since we have a
finite number of deep traps, the mobility shows a significant
increase at a density that coincides with the density of the
deepest traps in each DOLS. The increase is one or two
orders of magnitude and is not sharp because the energies of
the deepest traps have been assigned a Gaussian distribution
共as expected the curve for the DOLS with a standard devia-
tion of 0.01 eV shows the sharpest features兲. For larger den-
sities, the mobility tends stepwise 共as the traps represented
by Gaussians are filled兲 towards the value that corresponds to
multiple trapping between shallow traps 共all chemical traps
are filled兲.
By reducing the concentration of the deepest traps 共and
tionally to their concentration to compensate兲 the effect of
trap filling on mobility can be produced at lower electron

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 1006 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002 Anta et al.

FIG. 3. Mobility as a function of the density from the mobility model 关Eqs.
共1兲, 共6兲, and 共7兲兴. Curve 共a兲 DOLS of Table I with a standard deviation of
0.05 eV; curve 共c兲 fraction of deepest traps in Table I reduced by a factor of
14 共and the concentration of the remaining traps increased proportionally to
their concentration to compensate兲; curve 共d兲 fraction of deepest traps re-
duced by a factor of 2000. Curve 共b兲 DOLS of Table I with standard devia-
tion of 0.001 eV. The field applied was 30⫻106 V/m and the temperature T
was 20 °C.

densities. Lower concentrations and/or trap depths lead to

higher limiting mobilities. For the DOLS given in Table I,
with the deepest trap E n ⫽1.1 eV, Eq. 共9兲 predicts a limiting
mobility of 1.4⫻10⫺17 m2 V⫺1 s⫺1 , consistent with the re-
sults for the 0.001 eV standard deviation DOLS in Fig. 3.

IV. CURRENT–VOLTAGE CHARACTERISTICS OF

XLPE SAMPLES
The results discussed in Sec. III correspond to the prop-
erties of a material with a given distribution of trap energies
at a fixed applied field. To model real materials we must
include the modification of the local field in a conducting
device by the space charge. The SCLC17 method includes
this effect by solving the Poisson equation.
Using the SCLC technique the following equation for
the current density in the absence of diffusion and polariza-
tion currents,
J⫽ ␳ 共 x 兲 e ␮ 关 E 共 x 兲 , ␳ 共 x 兲兴 E 共 x 兲 ,
FIG. 4. 共a兲 Density profiles from the SCLC model 关DOLS from Table I,
contact density ␳ c ⫽1020 m⫺3 , polyethylene dielectric constant, ⑀ r ⫽2.3
共Ref. 30兲兴 with sample width of 200 ␮m; from top to bottom J⫽2.50
⫻10⫺15, 1.25⫻10⫺15, and 4.17⫻10⫺17 A/mm2 共to obtain A/m2 divide by
106 兲. T⫽20 °C. 共b兲 Field magnitude profiles 共multiply by ⫺1 for the sign
and by 106 to obtain the field in V/m兲 from the SCLC model therein 共a兲.
From top to bottom J⫽2.50⫻10⫺15, 1.25⫻10⫺15, and 4.17
⫻10⫺17 A/mm2 共to obtain A/m2 divide by 106 兲. T⫽20 °C. 共c兲 Mobility
profiles from the SCLC model in 共a兲. From top to bottom J⫽2.50
⫻10⫺15, 1.25⫻10⫺15, and 4.17⫻10⫺17 A/mm2 共to obtain A/m2 divide by
共10兲 106 兲. T⫽20 °C.

is solved in conjunction with the Poisson equation,

⑀ dE 共 x 兲 where d is the thickness of the device.
⫽␳共 x 兲, 共11兲
e dx If the procedure described above is performed for a con-
stant ␮ ⫽ ␮ 0 we reproduce the Mott–Gurney law,
where J is the current density, ⑀ (⫽ ⑀ 0 ⑀ r ) is the dielectric
constant of the material, ␳ (x) is the density of electrons at 9 V2
distance x from the electrode and ␮ is the local mobility, J⫽ ⑀␮ 0 3 . 共14兲
8 d
considered a function of field E and the density. Equations
共10兲 and 共11兲 are integrated for each current density J with In this work we have used density and field dependent
the boundary condition mobilities obtained by solving Eqs. 共1兲, 共5兲 and 共6兲 as dis-
cussed in Sec. III. Solving the SCLC model for current den-
␳ 共 x⫽0 兲 ⫽ ␳ c , 共12兲 sities typical of experiment we obtain density, field and mo-
where ␳ c is the density at contact 共the cathode, for electrons兲. bility profiles, examples of which are displayed in Fig. 4 共for
The voltage is then obtained by integration of the field, a 200 ␮m sample we take the contact density as ␳ c ⫽7.5
⫻1019 m⫺3 estimated from the charge profiles given in Ref.
V⫽ 冕 0
d
E 共 x 兲 dx, 共13兲 26兲. From Fig. 4共a兲 it is clear that the density inside the
sample falls very rapidly from the value at contact ( ␳ c ). This

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 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002
FIG. 5. Log–log plot of the CV characteristics of two different samples of
XLPE of 200 共Ref. 18兲 共closed circles兲 and 150 ␮m 共Ref. 19兲 共closed tri-
angles; the dashed line is to guide the eye兲. Symbols correspond to the
experiment, and the lines correspond to DOLS as follows: curve 共a兲 the
DOLS of Table I for a 200 ␮m sample ( ␳ c ⫽7.5⫻1019 m⫺3 ); curve 共d兲
DOLS of Table I but with the mole fraction of the deepest traps divided by
2000 for a 200 ␮m sample; curve 共b兲 DOLS of Table I for 200 ␮m sample
( ␳ c ⫽7.5⫻1019 m⫺3 ); curve 共c兲 DOLS of Table I for 150 ␮m sample ( ␳ c
⫽4.4⫻1020 m⫺3 ) with the fraction of the deepest traps divided by 14 and
10, respectively. These two lines are indistinguishable at lower fields in this
plot. The contact densities were estimated from experiment 共Refs. 26 and
27兲, and the polyethylene dielectric constant, ⑀ r ⫽2.3 共Ref. 29兲. T⫽20 °C.
is in agreement with space charge profiles seen
experimentally.10,18 From Fig. 3 we see this contact value is
well below the value at which significant trap filling occurs
for the trap distribution of Table I, as a consequence the
mobility profile across the sample is essentially density inde-
pendent. For the lowest current density, J⫽4.17
⫻10⫺17 A/mm2 , i.e., low applied field, the mobility is also
almost field independent 关see Fig. 4共c兲兴, and meets the con-
ditions of constant mobility appropriate to Mott–Gurney law
关Eq. 共14兲兴. At higher current densities 共higher fields兲, the
mobility increases as a function of the field, leading to field
dependence of the current density 共seen at the highest fields
in Fig. 5兲. By changing the DOLS the low density mobility
can be changed and the trap filling regime can be moved
down in density towards values of the space charge density
seen in the experiment. However due to the rapid fall in
density as a function of the distance from the electrode our
results in Fig. 5 are not sensitive 共for reasonable values of
␳ c 兲 to the choice of contact electron densities. The results are
sensitive however to the limiting low density values of the
mobility, i.e., to the depth and concentration of the deepest
trap 关cf. Eq. 共9兲兴.
In Fig. 5 we compare the resulting current–voltage char-
acteristics with the experimental XLPE current–voltage
characteristics reported by Montanari and Ginello18 共set A,
200 ␮m thick sample兲 with the data of Teyssedre et al.19 共set
B, 150 ␮m sample兲. The best fit is for the case in which the
concentrations of the deepest trap in the DOLS of Table I
共Fig. 1兲 have decreased by a factor of ⬃10 共14 for set A and
10 for set B, since the trap concentrations are not known to
high accuracy12 these changes are certainly within the uncer-
tainty of the data兲. In this case at low fields 共⬍20 kV/mm兲
the predicted current density follows Mott–Gurney law with
slope of 2.0. As the field increases the exponent increases
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Anta et al. 1007
FIG. 6. CV characteristics of a sample of a 150 ␮m 共Ref. 19兲 XLPE 共closed
circles兲. Symbols correspond to the experiment, and the line corresponds to
the DOLS of Table I with the fraction of deepest traps divided by 14 共data
from Fig. 5兲.
共for the 150 ␮m sample predictions兲 until after 60 kV/mm,
the exponent is 2.5, reflecting the effect of the applied field
in increasing the electron mobility in the sample 关see Fig.
4共c兲兴. The experimental data in set A show at least three
distinct regimes, below 13 kV/mm the slope is almost linear
共0.8兲,18 between 13 and 21 kV/mm the slope is ⬃2.0, after
21 kV/mm the current density increases very rapidly. Mon-
tanari and Ginello observed significant buildup of space
charge for fields in excess of the ‘‘threshold field’’ of 14
kV/mm. Our model matches the Montanari and Ginello data
in the interval of 14 –21 kV/mm where the slope is ⬃2, but
does not match the rapid increase in current at higher fields.
There are two ways in the current model that we can achieve
the rapid increase seen in set A after 21 kV/mm: one would
be if there were a sudden loss of the deepest trap sites at this
field 共say, a reduction of the fraction of deepest traps by a
factor of 2000, cf. Fig. 5兲 with a corresponding two orders of
magnitude increase in mobility 共see Fig. 3兲. Whether this is
possible due to mobilization of the filled chemical traps 共now
anions兲 in the field applied is an open question which we do
not consider further here. The second would be if the tem-
perature of the sample were to increase by 20 K, leading to
higher mobilities.
The data in set B have a different structure with two
regions, one below about 20 kV/mm with a slope of ⬃0.5
共i.e., not ohmic兲 and then another region which is in apparent
agreement with the model curve 共an average slope of ⬃2.5兲.
However Fig. 6 shows that, although 共on a linear plot兲 the
space charge limited conduction agrees well with data set B
below 共say兲 60 kV/mm, above this point different curvature
is apparent. As Teyssedre et al.19 pointed out, for this sample
60 kV/mm marks the onset of continuous electrolumines-
cence under dc conditions and significant charge injection.
Clearly then we have three regions and a new threshold for
dynamic space charge behavior at 60 kV/mm. At a higher
field of 80 kV/mm charge packet formation takes place with
negative charge fronts moving from cathode to anode and
 1008 J. Appl. Phys., Vol. 92, No. 2, 15 July 2002
1
positive charge fronts moving in the opposite direction. Such
dynamic effects are completely missing from the current
SCLC calculations although they may well be accessible us-
2
3
ing TRAM in a transient mode with electrode charge injection 4
and electron and hole transport. 5
6
V. CONCLUSIONS 7
In this work, a general method to estimate the current–
voltage characteristics of an insulating device was described 8
and applied to a real material. The only input to the proce-
9
dure is the chemical composition of the material. We have
used density functional theory to obtain a trap energy distri-
10
bution for electrons and a Monte Carlo technique to simulate
multiple trapping transport of electrons through an energy- 11
disordered network of traps. These simulation results were 12
used to validate a theoretical model for the local mobility
that can be used at low densities. A modified version of the 13
SCLC model was used with the local mobilities to obtain the
current–voltage curves for various trap energy distributions.
14
15
We have employed this general procedure to obtain the
current–voltage curve of XLPE insulation. Our calculations
are in overall agreement with the experimental data in the 16
low field 共e.g., for set B 10⬍E⬍60 kV/mm兲 regime. It is 17
clear that, for these fields, trap-filling effects are not impor-
tant. However the current–voltage characteristics are very
18
sensitive to the depth and concentration of the deepest traps.
Given the good agreement in the low field regime we are 19
confident that the current procedures provide a method of
predicting the effects of adding or removing traps of various 20
21
types to polyethylene.
Our procedure does not reproduce features in the current
density observed in the experiment at high fields. A more
22
23
accurate description of the conducting properties of the ma-
terial may require the consideration of many types of carrier.
In the experimental work of Montanari and Ginello this jump 24
in the current–voltage curve is associated with a space 25
charge profile that shows the formation of heterocharge, and
in the work of Teyssedre et al19 it is charge packet dynamics.
Thus it seems likely that in the high field regime charge
separation, ionic impurities as well as holes introduced
through the anode may play a very important role. The con-
sideration of these contributions in the procedure presented
here requires the extension of our models to holes and to
dynamic effects.20 26
27
ACKNOWLEDGMENTS 28
29
This work was supported by EPSRC through Grant No.
gr/r18222 and by Electricité de France. 30
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1.86⫻1027 m⫺3 , from which a⫽ ␳ ⫺1/3 t ⫽8.1⫻10⫺10 m and t 0
⫽8m e a /3h⫽2.4⫻10
2 ⫺15
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