Ab-initio Ele

troni Band Stru ture Cal ulations for

Beryllium Chal ogenides
G. Kalpana

Department of Physi s, Cres ent Engg. College, Chennai-600 048, India.

G. Pari and Abhijit Mookerjee

S.N.Bose National Centre for Basi S ien es, Salt lake, Cal utta-700 091, India.
A.K. Bhatta haryya

Department. of Engineering, University of Warwi k, Coventry C477AL, UK.

Abstra t.
The rst prin iples tight-binding linear mun-tin orbital method within
the lo al density approximation (LDA) has been used to al ulate the ground state
properties, stru tural phase transition and pressure dependen e of the band gap of
BeS , BeSe and BeTe. We have al ulated the energy-volume relations for these
ompounds in the B 3 and B 8 phases. The al ulated latti e parameters, bulk modulus
and the pressure-volume relation were found to be in good agreement with the re ent
experimental results. We have also al ulated the ohesive energy for them and they
are onsistent with the bulk modulus. The al ulated B 3 to B 8 stru tural transition
pressure for BeS , BeSe and BeTe agree well with the experimental results. Our
al ulations show that these ompounds are indire t band gap ( -X ) semi ondu tors
at ambient onditions. The al ulated band gap values are found to be underestimated
by 20-30% whi h is due to the usage of LDA. After the stru tural transition to the
B 8 phase BeS ontinues to be indire t band gap semi ondu tor and ultimately it
be omes metalli above 100 GPa . BeSe and BeTe are metalli at B 3 to B 8 stru tural
transition.

Short title:

Ab-initio Ele troni Band Stru ture Cal ulations for Beryllium

Chal ogenides

July 9, 2001

2
1.

Introdu tion

In the last few de ades, the high pressure behaviour of alkaline-earth hal ogenides AX
(A=Be, M g , C a, S r, Ba; X =O, S , S e, T e) have been studied extensively. Among
the AX , ex ept BeX and M gT e all the other ompounds rystallize in the N aC l-type
stru ture while BeX (X =S , S e, T e) rystallizes in the zin blende stru ture, BeO and
M gT e rystallize in the wurtzite stru ture. Pressure-indu ed stru tural phase transition
from the N aC l(B 1) to C sC l(B 2) type stru ture has been observed in C aX , S rX and
BaX . BeX and M gX are the left out members of this series. Re ent high pressure
experiment shows that there exists stru tural phase transition from the zin blende(B 3)
to N iAs(B 8) type stru ture for BeS e and BeT e at pressures of 56 5 GPa and 35 5
GPa respe tively [? and from the experimental trends it has been suggested that BeS
would transform from the B 3 to B 8 phase at a pressure of 69 GPa . However, quite
re ently it has been observed that BeS undergoes a B 3 to B 8 stru tural transition at
a pressure of 49 6 GPa [?. This value is lower than the value suggested by Luo et al
[? and is also lower than the transition pressure of BeS e. It is not lear from our work
why there should be su h a deviation. When ompared to other AX ompounds very
few results have been reported for BeX . Re ently, the results of the pseudopotential
al ulations [?, ? were reported for these ompounds, where the stru tural stability of
BeS , BeS e and BeT e have been studied.
Be hal ogenides are found to be extremely promising materials for blue-green laser
diodes [? and they dier from other AX ompounds in having extremely small ations
size ompared to that of the anions with an ex eption of BeO. They are less ioni with
Philips ioni ities ranging from 0.169 to 0.312 and be ause of this the Be ompounds dier
from other AX by their stru ture and bonding [?. In these aspe ts, they are analogous
to Group I I I -V semi ondu tors in parti ular they are similar to B ompounds BN ,
BP and BAs in having same rystal stru ture, wide band gaps and high bulk moduli.
The band gap values for Be ompounds are found to range from 2.7 to 5.5 eV [?. In
this paper, we have made an attempt to understand the stru tural properties of BeS ,
BeS e and BeT e through the ele troni band stru ture al ulations performed using the
tight-binding linear mun-tin orbital (T B -LM T O) method [?. The al ulations were
done in B 3 and B 8 phases. In the following se tions we have des ribed the method of
al ulations, obtained results and dis ussion and on lusions.
2.

Method of Cal ulation

The total energies and its variation with volume in the B 3 and B 8 phases were obtained
using the T B -LM T O-AS A method within the frame work of density fun tional theory
(DF T ) [? in its lo al density approximation (LDA) [?. The ex hange- orrelation

3
potential has been al ulated using v on Barth and Hedin s heme [?. The energy
eigenvalues were al ulated for 172-~k points within the irredu ible part of the Brillouin
Zone (I BZ ). The density of states (DOS ) were al ulated by the method of tetrahedra
[?. The ombined orre tion terms were in luded whi h a ounts for the non-speri al
shape of the atomi ells and the trun ation of the higher partial waves (l >2). It is
well known that LM T O method gives a urate results for the densely pa ked stru tures
and sin e B 3 and B 8 stru tures are open, without breaking the rystal symmetry, we
have in luded empty spheres in both stru tures to get lose pa king. In parti ular,
this be omes important for the total energy al ulations where the stru tural energy
dieren e is only of the order of few mRy . In the ase of B 8 stru ture, we have al ulated
the total energy as a fun tion of =a ratio to minimize the =a value. Using this minimum
=a value we have al ulated the total energy as a fun tion of volume.

3.

Results and Dis ussions

The al ulated total energy/mole ule as a fun tion of volume for the B 3 and B 8 phases
were given in Figs.1(a) to 1( ). At ambient onditions, all the three ompounds are
stable in the B 3 phase and undergo a transition to the B 8 phase upon ompression as
eviden es from these gures, are quite onsistent with the experiments. The al ulated
total energies as a fun tion of volume were tted to the Bir h equation of state to obtain
the ground state properties and the pressure - volume (P -V ) relation. The al ulated
latti e parameters and the bulk moduli in the B 3 and B 8 phases are given in Table
I along with the experimental and the earlier pseudopotential results, whi h shows an
ex elent agreement. It is to be noted from this table that the ohesive energy (E oh) and
B0 value de reases from BeS to BeT e, ie , from the lower to the higher atomi number.
This suggests that BeT e is more easily ompressible than the others.
Table I Latti e parameter (a) in A, ohesive energy (E oh) per mole ule in eV , bulk
modulus (B0 ) in GPa , transition volumes (V1 /V0 ) and (V2 /V0 ) and transition pressure
(Pt in GPa ).

4
BeS

Expt. Present Pseudo

4.865 4.839
4.745
10.534
106.2 102.8
113.4
3.319
3.198
1.613 1.533
1.587
121.9
117.8
0.759 0.734
0.757
0.628
0.65
0.651
17.3
11.4
14
49  6 52.4
52.3
a

( 3)

a B

E oh

( 3)
a(B 8)

B0 B

=a

( 8)
V1 (B 3)=V0
V2 (B 8)=V0

V %
B0 B

Pt

Pseudo
4.731
102
3.239
1.593
122
0.727
0.648
10.9
58.5

BeS e

Expt. Present Pseudo

5.139 5.137
5.037
9.235
92.2
82.2
92.2
3.524
3.421
1.587
1.55
1.578
97.8
94.7
0.716 0.733
0.759
0.632 0.658
0.659
11.7
10.2
13.2
56  5 45.7
42.7
d

BeT e

Expt. Present P
5.627 5.638
7.793
66.8
60.5
3.858
1.615 1.561
72.3
0.714 0.742
0.633 0.668
11.3
10
35  5 34.7

Referen e 2.
Referen e 3.
Referen e 4.
d Referen e 1.

a
b

In Figs.2(a) to 2( ), the al ulated P -V urves are ompared with the experimental

data points. >From the gures it an be seen that there is a good agreement between
the experimental and the al ulated P -V relation.
The stru tural transition pressures (Pt ) were al ulated at whi h the enthalpies for
the two stru tures be ome equal. The al ulated Pt for the B 3 to B 8 phase for BeS e
is 45.7 GPa whi h is slightly lower than the experimental value of 56  5 GPa . For
BeT e, Pt is al ulated to be 34.7 GPa and is in good agreement with the experimental
value of 35 5 GPa . For BeS , the al ulated value of Pt , 52.4 GPa , is in agreement
with the pseudopotential result of 52.3 GPa [? and 58 GPa [? and is slightly lower
than the value of 69 GPa suggested by the experimental trends [?. The transition
volume and the volume redu tion are also given in Table I whi h agree very well with
the experimental and the pseudopotential results.
The self onsistent s alar relativisti band stru tures were obtained in the B 3 and
B 8 phases at ambient as well as in the high pressure region. Figs.3(a) to 3( ) show
the band stru tures of BeS , BeS e and BeT e along the high symmetry dire tions in
the B 3 phase at equilibrium volume. The overall band prole for these ompounds are
same and are in agreement with the earlier results [?, ?, ?. The lowest band arises predominantly from the hal ogen valen e s state and the upper valen e bands arise from
the hal ogen valen e p states with the top o urring at the -point. The ondu tion
band arises from the Be 2s states with the minimum energy o urring at X -point. The

5
al ulated value of indire t band gap ( -X ) for these ompounds are given in Table II
along with the experimental and the pseudopotential results. When ompared to the
experimental values, the band gap values are underestimated by 30-50%. This error
arises due to the usage of LDA, whi h is known to underestimate the zero pressure
band gap. However, they are in good agreement with the pseudopotential results whi h
uses the same type of approximation.
Table II. Energy band gap (Eg ) ( -X ) in the B 3 phase in eV .

Eg

present work Pseudoa Expt.b

BeS
3.78
2.75
> 5.5
BeSe
3.12
2.4
4 - 4.5
BeTe
2.17
1.18
2.7

a
b

Referen e 3.
Referen e 7.

Figs. 4(a) to 4( ) show the band stru ture of BeS , BeS e and BeT e in the B 8
phase at stru tural transition. From the gure it an be seen that both BeS e and
BeT e are metalli . Metallisation is due to the indire t band gap losing at
and K
by the hal ogen p and the Be- s bands. However, we should keep in mind the fa t
that LDA underestimates the bandgap. Even after the stru tural transition, BeS still
remains semi ondu ting with gap o urring between and K points. Upon further
ompression, the band gap de reases leading to band overlap metallization at a high
pressure of about 100 GPa . The variation of band gap for BeS and BeS e as a fun tion
of redu ed volume in the B 8 phase are given in Table III. BeT e remains metalli in
the B 8 phase even at the equilibrium volume of the B 3 phase. So far, no experimental
work has been done on the insulator-metal transition for these ompounds. Perhaps the
smaller value of the band gap of BeT e be the reason for it's metalli nature in B 8 phase
at the equilibrium volume of B 3 phase. Further opti al or ele tri al measurements are
required to onrm our results.
Table III. Variation of Eg with redu ed volume (V =V0 ) in the B 8 Phase.

6
Eg

V =V0
BeS

1.0
0.9
0.8
0.7
0.6
0.535
4.

(eV )

BeS e

1.347 0.0
1.333 0.340
1.251 0.299
0.979 0.190
0.612 0.0
0.0
0.0

BeT e

0.0
0.0
0.0
0.0
0.0
0.0

Con lusions

The stru tural and ele troni properties of BeS , BeS e and BeT e in the B 3 and B 8
phases were al ulated using the T B -LM T O method. The al ulated latti e parameters, bulk modulus and the P -V relation were found to be in good agreement with the
experimental and the pseudopotential results. The al ulated E oh is onsistent with the
B0 values. From the energy-volume relations we nd that these ompounds are stable
in the B3 phase at ambient onditions and undergo a stru tural transition to the B8
phase at high pressures. The al ulated values of transition pressures, transition volume and volume ollapse are in good agreement with the experimental values and the
pseudopotential results. At ambient onditions, the ompounds are indire t band gap
semi ondu tors with gap o urring between and X points. When ompared to the
experimental values, the bandgap values are underestimated by 20-30%, whi h is due
to LDA. In the B 8 phase, at the transition pressure, as the ation size in reases from
S to T e the metalli ity in reases in that BeS is semi ondu ting, BeS e is semimetalli
and BeT e is metalli . In the B 8 phase, BeS is an indire t band gap semi ondu tor
with gap o urring between and K points. No experimental study on the band gap
value in the high pressure phase has so far been reported. From our al ulations we
nd that there is a possibility for these ompounds to be ome metalli at high pressures.

7
A knowledgments

One of the authors (G:P ) wishes to thank the University of Warwi k, Coventry, England
for the nan ial support.

Figure Captions

1. Variation of total energy as fun tion of relative volume,

phases of a) BeS , b) BeS e and ) BeT e.
2. Plot of relative volume
BeT e.
3. Band stru ture of a)
volume.
4. Band stru ture of a)
transition.

V =V0

BeS

for the B 3 and B 8

as a fun tion of pressure for a) BeS , b)

, b)BeS e and )

BeS

V =V0

, b)

BeS e

BeT e

and )

in the

BeT e

in the

BeS e

and )

3 phase at equilibrium

8 phase at stru tural

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