Surface Science 532535 (2003) 351358

www.elsevier.com/locate/susc

The eects of doping a grain boundary in ZnO with

various concentrations of Bi
Johan M. Carlsson
a

a,*

, Bo Hellsing a, Helder S. Domingos b, Paul D. Bristowe

Experimental Physics, School of Physics and Engineering Physics, Chalmers University of Technology and Goteborg University,
SE-41296 Gothenburg, Sweden
b
Department of Materials Science and Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK

Abstract
We have made a systematic study of the Bi-decoration process in a R 13 [0 0 0 1] tilt grain boundary in ZnO by
rst-principles calculations. This grain boundary is taken as a model system for studying the microscopic properties of
commercial Bi-doped ZnO-varistors. The calculations show that the decoration process is strongly site dependent and
that there is a considerable segregation energy for the Bi-atoms at low concentration. Increasing the concentration
lowers the segregation energy which sets an upper limit of approximately 32% for the Bi-concentration in this grain
boundary. This implies that the Bi-atoms stay in the grain boundary region rather than diusing into the ZnO grains
during the manufacturing process, but the maximum Bi-concentration is limited which is consistent with the experimental observations. Bi-impurities in ZnO act as donors at low impurity concentration, but a localized BiBi-bond is
formed at higher Bi-concentration in the grain boundary. This Bi-state is located in the band gap of ZnO and it may be
responsible for the varistor eect observed in Bi-decorated grain boundaries.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Grain boundaries; Zinc oxide; Interface states; Density functional calculations

1. Introduction
Zinc oxide is receiving increased interest today
due to its range of applications, but it is also
considered as a prototype material for studying the
properties of metal oxides. The wide direct optical
band gap makes single crystalline ZnO suitable for
optical applications [1] and the polycrystalline
form has been used for a long time in varistors [2].
A varistor is a voltage dependent resistor which
*
Corresponding author. Address. FritzHaber -Institut der
Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin,
Germany, Tel.: +49-30-8413 4830; fax: +49-30-8413 4701.
E-mail address: johanc@fhi-berlin.mpg.de (J.M. Carlsson).

exhibits a highly non-linear IV characteristic [2].

These devices are manufactured by liquid sintering
of ZnO mixed with a number of additives such as
Bi, Sb, Mo, Co and Cr [3]. The sintering produces
a polycrystalline ZnO material where the additives
accumulate in the grain boundaries [3,4]. It is assumed that interface states in the grain boundaries
create a depletion region, which leads to the formation of a double Schottky barrier (DSB) [2].
The barrier limits electron transport through the
grain boundary but an applied eld is able to
manipulate the population of the interface states.
The non-linearity is therefore the result of the
dramatic current increase when the DSB is removed by the applied eld.

0039-6028/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0039-6028(03)00193-6

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J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

Bismuth is the most important additive which

contributes to the formation of the DSB [2]. A
majority of the Bi-atoms accumulate into Bi2 O3 phases at the triple junctions between the ZnO
grains in varistor materials [5] but the Bi-atoms
may also diuse out to become incorporated in the
grain boundaries. These Bi-atoms appear either as
isolated Bi atoms decorating the grain boundary
[6] or as a thin amorphous Bi2 O3 -layer [3] depending on the cooling process [2]. It has been
debated in the literature which of these two types
of Bi congurations give rise to the most pronounced non-linearity.
We have therefore studied the Bi-decoration
process in a R 13 [0 0 0 1] tilt grain boundary in
ZnO by rst principles calculations. This particular
grain boundary is a convenient model system since
its atomic structure has been determined previously by both high resolution electron microscopy
(HREM) [7,8] and rst principles calculations [9].
The study involves a systematic investigation of
the most favourable substitution sites for the Biimpurity atoms in the grain boundary and the Biinduced eects on the electronic structure.

states (PDOS) was calculated by projecting the

wavefunctions on the atomic orbitals provided by
the ultrasoft pseudopotentials.
The formation energy of a defect is dened as
the change in Gibbs free energy due to the inclusion of the defect in the system [17]. The formation
energy of the Bi impurity is therefore:
Eform EZnO : nBi  EZnO
nlZn  lBi  ne le ;

where n is the number of substituted atoms and lBi

and lZn indicate the chemical potentials of the Bi
and Zn atoms respectively. The number of electrons added to or removed from the impurity is
denoted ne and le is the electron chemical potential. However, in the present work we have not
varied the charge state of the impurity and therefore the last term in Eq. (1) is zero. The segregation
energy Eseg is the dierence in formation energy of
the impurity in the grain boundary and in the bulk:
Eseg EGB ZnO : nBi  EGB ZnO
 nEbulk ZnO : Bi  Ebulk ZnO;

where the impurities in bulk are considered in the

dilute, non-interacting limit.
2. Methods
The rst-principles calculations were based on
density functional theory (DFT) [10,11] using the
PW-91 GGA exchange-correlation functional [12]
implemented in the Dacapo code [13]. A plane
wave basis set with an energy cuto of 300 eV was
used together with ultrasoft pseudopotentials [14].
The R 13 [0 0 0 1] tilt grain boundary was constructed in the supercell using two unit cells of the
coincidence site lattice (CSL) in which the crystals
were misoriented by 32.2. The supercell therefore
contains 104 atoms and the periodic boundary
condition produces two grain boundaries per supercell. The Brillouin zone was sampled at 3 kpoints along the c-axis parallel to the grain
boundary plane according to the MonkhorstPack
scheme [15]. The electronic population factor was
smeared by 0.01 eV [16] to improve convergence
and the atomic relaxation was performed using the
BFGS-algorithm until the forces on the atoms
. The projected density of
were less than 0.05 eV/A

3. Results and Discussion

The results and discussion are divided into two
sections. The atomic structures and segregation
energies for the Bi impurities in the grain boundary are presented rst. This is followed by a description of the impurity induced eects on the
electronic structure of the system.
3.1. Segregation
The calculated R 13 grain boundary structure
which most closely matches the observed structure
[7,8] consists of a zig-zag chain of structural units
in the form of 10 atom rings [9]. These structural
units contain two 3-coordinated neck sites and
eight 4-coordinated Zn-sites per atom ring and
there are two structural units per CSL-cell as can
be seen in Fig. 1. Two of the atoms in each
structural unit are common to both rings giving a

J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

353

0.5

(AA) B

(AA)

0.5

A(AB)C

seg

[eV]

(AA) B
(AA)B

C
B

(AA)

(AA) (AA)

A(AB)

1.5
AA

2
5

10

A(AA)

15

20

25

30

35

40

Bi-conc [% Bi/Zn-sites]

Fig. 2. The variation of the segregation energy for Bi-atoms in

a R 13 [0 0 0 1] tilt grain boundary in ZnO. The letters refers
to the substitution sites indicated in Fig. 1 and AAr indicates
that a BiBi bond is formed. The solid line shows the lowest
energy conguration at each doping concentration.

Fig. 1. The relaxed geometry for the Bi-doped R 13 [0 0 0 1]

tilt grain boundary at a Bi-concentration of 18.75%. The Bi
substitution sites are indicated by the letters A, B and C and the
encircled A marks the Bi atom for which the PDOS is shown in
Fig. 3. The 3-coordinated sites are indicated by A and the two
dierent 4-coordinated sites are marked by B and C. The dashed lines indicate the limits of the supercell and the dashdotted line indicates the grain boundary plane.

total of 16 Zn-sites per CSL-cell in the core of the

R 13 grain boundary. The substitution of one Bi
atom in the supercell then corresponds to
1=16 6:25% Bi-concentration in the grain
boundary.
Three dierent substitution sites, denoted by A,
B and C in Fig. 1 have been considered for the Bisubstitution. A is the 3-coordinated site at the neck
of the structural unit, where one of the tetrahedral
bonds is broken and B and C are two dierent 4coordinated sites. Fig. 2 shows that the segregation
energy of one Bi atom in the grain boundary favours the 3-coordinated A site whereas the segregation energy for B and C-sites is close to zero.
This can be understood from the fact that the 4coordinated B and C-sites have maintained the
tetrahedral coordination of the bulk lattice giving
a more or less bulk like environment. The relax-

ation of the atoms in the grain boundary results in

a lattice expansion around the Bi-atom occupying
B or C-sites in the same way as was observed for
Bi-doping in the bulk [18]. The 3-coordinated Asite, on the other hand, permits an asymmetric
relaxation into the structural unit. The Bi-atom in
 in
the A-site utilized this freedom to move 0.7 A
this direction [18] resulting in large strain relief.
Increasing the Bi-concentration results in
stronger BiBi interaction. Previous bulk calculations [18] indicate a repulsive Bi impurityimpurity
interaction which suggests that the Bi atoms would
prefer a dispersed or dilute phase in the grain
boundary thus maximizing the BiBi distance.
Comparing the segregation energy in Fig. 2 for the
dispersed phase to the clustered phase where two
Bi atoms occupy the adjacent 3-coordinated neck
sites in the same structural unit also shows that the
dispersed phase is more favourable at 12.5% Biconcentration. Another indication of the repulsive
BiBi interaction is that the segregation energy at
12.5% Bi-concentration is less than double the
value at 6.25%, which would be the case for two
non-interacting Bi-atoms.
A Bi-concentration of 18.75% results in more
than one Bi-atom in every second structural unit.
The additional Bi-atom, occupying either a 3- or a

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J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

4-coordinated site, forms a bond with the 3-coordinated Bi-atom on the opposite side of the
structural unit which will be discussed in detail
below. The 3-coordinated site remains more favourable than the 4-coordinated site, but the gain
upon adding a second Bi-atom in the structural
unit is much less than occupying the rst 3-coordinated sites as can be seen in Fig. 2. This is related
to the fact that the Bi-atoms restrict the freedom
for the other Bi atoms to relax. The presence of
another Bi atom in the structural unit reverses the
movement of the Bi-atoms back towards the initial
Zn-sites due to the repulsive BiBi interaction.
This can be seen by comparing the relaxation of
the Bi atoms in the structural unit containing one
or two Bi atoms in Fig. 1. The reversal of the relaxation is particularly evident at 25% Bi-concentration where the most favourable conguration
corresponds to lling all 3-coordinated sites. The
Bi-relaxation at this concentration is less than 0.1
 with respect to the initial Zn-positions in the
A
undoped grain boundary for all four Bi-atoms.
The relaxed BiBi distance across the structural
 which is very close to the correunit is 2.93 A
 in the undoped
sponding ZnZn distance of 2.91 A
grain boundary.
The segregation energy starts to decrease as the
Bi concentration approaches 25%. The BiBi interaction is then so strong that the energy gain in
substituting the Bi-atoms in 3-coordinated sites is
substantially reduced by the repulsive interaction.
A further increase in the impurity concentration
beyond 25% in addition means that the less favourable 4-coordinated sites have to be occupied.
The segregation energy at 31.25% is consequently
close to zero which indicates that the repulsive Bi
Bi interaction completely outweighs the energy
gain due to the improved bonding environment in
the grain boundary. Around 32% is therefore the
limit when further increase of the Bi-concentration
is no longer favoured compared to substitution in
the bulk.
The bismuth decoration process can be summarized as strongly site dependent. The 3-coordinated sites are the preferred substitution sites and
the repulsive BiBi interaction strives to maximize
the BiBi distance. This means that the 3-coordinated sites are populated by placing one Bi atom in

each structural unit before another Bi atom can be

placed in the same structural unit. However, the
increased Bi-concentration forces the Bi-atoms to
occupy the adjacent 3-coordinated neck sites in
spite of the strong BiBi repulsion. Twenty ve
percent Bi-concentration marks the limit when all
3-coordinated sites are populated and going beyond this concentration results in a signicant
decrease in segregation energy. There is a maximum Bi-concentration in the boundary of approximately 32% and this is consistent with
experimental measurements on doped ZnO polycrystals which report upper limits that are less than
a complete monolayer of Bi [4].
3.2. Electronic structure
The isolated Bi-impurity acts as a donor in bulk
ZnO, since it donates a signicant fraction of its pelectrons to the neighbouring O-atoms. The behaviour is similar when the Bi-atom resides in a
grain boundary at low impurity concentrations
[18]. In order to investigate the eect of increasing
Bi-concentration in the grain boundary, the calculated PDOS for a Bi-atom has been plotted for a
variety of Bi-concentrations in the range 6.25
37.5% in Fig. 3. The dispersive conduction band
unfortunately appears as isolated peaks instead of
a continuous region due to the nite k-points
sampling. The position of the bottom of the conduction band at each Bi-concentration is therefore
indicated by the dashed dotted vertical line in Fig.
3. The gure shows that no Bi-induced states appear in the band gap of ZnO at 6.25% and 12.5%
Bi-concentration. Instead, a majority of the pstates on the Bi atom are located in the conduction
band and these p-states have energies well above
the conduction band minimum. The Fermi level
for these systems is consequently located in the
conduction band resulting in metallic character for
the system but it is expected that the metallicity is
localized in the grain boundary plane.
Increasing the Bi-concentration beyond 12.5%
forces the Bi atoms to start occupying both of the
3-coordinated neck sites in the structural units.
The PDOS for 18.75% Bi-concentration (Fig. 3)
shows that some Bi-induced p-states then appear
in the bandgap of ZnO and the donation from the

J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

CBi=12.5%
PDOS

PDOS

CBi=6.25%
0.5

0
1

0.5

C =18.75%
PDOS

PDOS
0

PDOS

PDOS

Bi

0.5

C =37.5%

Bi

0.5

C =31.25%

Bi

0.5

C =25%

Bi

355

E E [eV]

0.5

E E [eV]

Fig. 3. The PDOS for the Bi-atom indicated by a circled A in Fig. 1 as function of Bi-concentration CBi , in the R 13 tilt grain
boundary in ZnO. The dashed and solid lines indicate the s- and p-components, respectively. The top of the valence band in the
dierent systems are taken as the reference of the energy scale. The vertical solid and dash dotted lines mark the position of the Fermi
level and the bottom of the conduction band at the various Bi-concentrations.

Bi-atom decreases. This behaviour is most pronounced at 25% Bi-concentration when all 3-coordinated neck sites are occupied. Analyzing the
variation of the PDOS for the atoms in the supercell as a function of the distances from the grain
boundary shown in Fig. 4 reveals that the Bi-induced states are localized both in space and in
energy. The dispersion of the Bi-induced state is
limited and the energy lies within the bandgap of
ZnO. The weight of the PDOS is concentrated to
the Bi-atoms and the closest neighbours in the
grain boundary region. The corresponding wave
function shown in Fig. 5 furthermore reveals that
these states are, in fact, associated with a BiBi
bond. This bond comes from the Bi 6p-electrons
associated with the two Bi atoms in the 3-coordinated neck sites which pair up across the structural
unit. The wave function shown in Fig. 5 has the
character of a r-bond and the large amount of
electric charge in between the two Bi-atoms suggest that it has bonding character. The electron

transfer from the Bi-atoms is concentrated into the

r-bonds at 25% Bi-concentration which means
that donation to the conduction band of the surrounding atoms reaches a minimum. The Fermi
level in Fig. 4 is accordingly positioned between
the energy level of the r-bond and the conduction
band minimum which gives the material semiconducting character. Photoemission experiments for
a Bi-covered ZnO-surface have revealed a state 0.9
eV above the valence band maximum [19]. It was
interpreted as an acceptor state connected to an
oxygen vacancy but in the light of the of present
calculations it seems as likely that the observed
state is a BiBi bond in the Bi-adlayer.
Increasing the Bi-concentration further leads to
the occupation of 4-coordinated sites. These additional Bi-atoms are not taking part in the r-bond
but instead donate a fraction of their p-electrons to
the conduction band which again gives the material
metallic character in the grain boundary plane. In
addition, the 4-coordinated Bi-impurities contribute

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J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

Fig. 4. The PDOS for the individual atoms in the supercell as function of the perpendicular distance z, to the R 13 [0 0 0 1] tilt grain
boundary in ZnO doped with 25% Bi. The solid line indicates the Fermi level and CB denotes the conduction band edge. The arrow
labeled Bi shows the position of the BiBi-r bond in the bandgap.

Fig. 5. The amplitude of the wave function jwj2 for the BiBi-r bond in the grain boundary containing 25% Bi, indicated by the Bi3 ]. The dashed lines indicate
arrow in Fig. 4. The wave function is shown as an isodensity surface at an electron density of 5 103 [eA
the limits of the supercell and the dashed dotted line shows the position of the grain boundary plane.

to a less localized state in the grain boundary which

overlaps both the 3- and 4-coordinated Bi-atoms.

This state is just visible near the Fermi level at

31.25% Bi-concentration as seen in Fig. 3.

J.M. Carlsson et al. / Surface Science 532535 (2003) 351358

The transfer of electrons from the Bi impurity

and its dependence on the Bi-concentration could
be described by a simple model for impurities in
semiconductors. The most convenient way of incorporating Bi atoms into ZnO at low concentration is by donating the excess charge of the
impurities to the conduction band of the surrounding material. However, increasing the
Bi-concentration enhances the repulsive BiBi interaction due to the dierent charge on the impurity compared to the cations (Zn) in the lattice.
The Bi atoms are then trying to counteract the
electrostatic interaction by lowering their ionic
charge. The p-states of the Bi-atoms are therefore
repopulated. When both of the 3-coordinated neck
sites in the structural unit are occupied by Biatoms, these atoms get close enough for the
wavefunctions to overlap. It is then favourable to
form a BiBi bond which diminishes the electrostatic repulsion between the two neighbouring
impurity atoms. This diers from the undoped
grain boundary where the electron density inside
the structural unit is very low because no ZnZn
bond is formed. The absence of a ZnZn bond is
probably connected to the fact that the ZnZn
distance is 1.5 times the ZnO distance in ZnO, but
also to the spherical symmetry of the 4s valence
electrons which limits the tendency to form directional bonds. It is therefore more favourable to
enforce the three remaining ZnO bonds than to
form a ZnZn bond across the structural unit.

4. Conclusions
The segregation of Bi-impurities to the R 13
tilt grain boundary in ZnO is strongly site dependent. The 3-coordinated sites are favourable for
segregation since they provide large freedom for
relaxation. Higher Bi-concentrations increase the
repulsive BiBi interaction which counteract the
energy gain from the improved bonding environment in the grain boundary. The BiBi interaction
therefore sets an upper limit for the Bi-concentration in the grain boundary, which is estimated from
Fig. 2 to be 32% in the R 13 tilt grain boundary.
In addition, the BiBi interaction also forces the
neighbouring Bi atoms to form a BiBi bond

357

across the structural unit. This BiBi bond constitutes a state highly localized to the grain
boundary region and the energy of this state is
located in the band gap of ZnO. It is therefore
possible to manipulate its population by varying
the stoichiometry of the system or by applying an
external eld. The occupation and depletion of this
BiBi state may then be related to the varistor
eect observed in Bi-decorated grain boundaries
[6]. The relatively high Bi-concentration needed in
the grain boundary to form the Bi-bond is also
consistent with the observation of a threshold for
the onset of the non-linearity as function of the
impurity concentration [3]. An investigation of the
interaction between the Bi-impurities and native
defects in the grain boundary is under way, which
aims at further clarifying the role of Bi in the
varistor materials.

Acknowledgements
J.C. has been supported by the Swedish Natural
Science Research Council and HSD acknowledges
grant PRAXIS XXI/BD/13944/97. The calculations were performed using the UNICC resources
at Chalmers, Gothenburg, Sweden.

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