243 2002, Insiiiuie of Seniconducior Fhysics, Naiional Acadeny of Sciences of Ukraine

Seniconducior Fhysics, Quaniun Elecironics & Opioelecironics. 2002. . 5, N 3. F. 243-246.

PACS: 71.15H, 71.25T, 64.3O, 71.45
Total energy, equation of states and bulk modulus
of Si and Ge
A.R. Jivani, P.N. Gajjar and A.R. Jani
Deparineni of Fhysics, Sardar Faiel Universiiy, allabh idyanagar-388 120, Gujarai, India
Abstract. A model olenlial desciiLing eleclion-ion inleiaclion is iesenled loi inliinsic semiconduc-
lois Si and Ge. Tle iesenl model olenlial is single aiameliic, conlinuous in r-sace and weaIei
willin coie and CoulomLic oulside lle coie. Tle aiamelei ol lle olenlial is deleimined using lle
equiliLiium condilion al zeio iessuie. Tle lolal eneigy, equalion ol slales and LulI modulus ol Si and
Ge aie calculaled using liglei oidei eiluiLalion lleoiy Lased on seudoolenlial loimalism wlicl
includes covalenl coiieclion leim. umeiical iesulls ol lolal eneigy and LulI modulus oLlained loi lle
Si and Ge aie in good agieemenls will exeiimenlal dala and lound sueiioi llan ollei sucl lleoielical
lindings. Tle iedicled equalion ol slales ol Si and Ge aie also excellenl.
Keywords: seudoolenlial mellod, semiconduclois, Linding eneigy, equalion ol slales, LulI
modulus
Paei ieceived O8.O4.O2; acceled loi uLlicalion 1O.12.O2.
1. Introduction
Tle second oidei eiluiLalion lleoiy Lased on lle
seudoolenlial loimalism las Leen alied lo simle mel-
als and lleii Linaiy alloys, glasses and comounds will
many successlul examles [1-5]. Howevei, lle second oi-
dei eiluiLalion lleoiy lailed loi covalenl ciyslals Le-
cause ol covalenl Londing claiaclei ol llese ciyslals.
Tlese dillicullies weie iemoved will lle exlension ol lle
eiluiLalion lleoiy in leims ol lle seudoolenlial Ly
laIing inlo accounl liglei oidei leims coiiesonding lo
lle covalenl Londing ellecl [6-8]. Tle liealmenl ol cova-
lenl ciyslals is dillicull nol Lecause ol comlex sliucluie
ol llese ciyslals Lul mainly due lo lle deleiminalion ol
lle model olenlial. Soma [9] used llis liglei oidei ei-
luiLalion lleoiy lo calculale lolal eneigy and LulI modu-
lus ol !V semiconduclois emloying Aslcioll [1O] emly
coie model olenlial. !n addilion lo lle usual olenlial
aiamelei R
c
, an adjuslaLle addilional aiamelei R
c
was
used Ly Soma lo ensuie minimum eneigy condilion in lle
liisl oidei eiluiLalion eneigy [9]. He las also ieoiled
lle iesulls using lle Heine-ALaienIov [11] model olen-
lial. !n all sucl ieoiled alicalions [9, 12], eole lave
woiIed will lisloiical model olenlials liIe lle Aslcioll
and Heine-ALaienIov model olenlials. Heie, in lle
iesenl aei, we exlended lle alicalions ol oui single
aiameliic model olenlial [13] lo invesligale lolal en-
eigy, equalion ol slales and LulI modulus ol Si and Ge
inliinsic semiconduclois using lle exlended eiluiLalion
lleoiy.
Tle analylical loim ol oui model olenlial in r-sace
[13] is

'

<
1
1
]
1

, R r
r
Ze
R r
R
r
R
r
R
Ze
r W
c
c
c
c c
2
2
2
2
2
3
2
) (
(1)
wleie Z is valency ol lle ion, e is lle eleclionic claige
and R
c
lle model olenlial aiamelei. Tle olenlial a-
iamelei R
c
is deleimined Ly using zeio iessuie condi-
lion. Tle momenlum-sace ieiesenlalion ol llis model
olenlial is given Ly
.
R
R
R
R
R
A
W
c
c
c
c
c
b
1
1
]
1

+
2 3
2
) (q
) (q sin
q
1
2
) (q sin
G
12
(q)
(2)
Wleie is lle alomic volume and q is lle wave vecloi.
2. Computational method
Ioi a covalenl ciyslal will lle diamond sliucluie, Lased
on lle liglei oidei eiluiLalion lleoiy, lle lolal eneigy
ei eleclion ol lle ciyslal [6, 8] is given Ly
E = E
i
+ E
O
+ E
1
+ E
2
+ E
cov
(3)
!n equalion (3), E
i
is eleclioslalic eneigy ol oinl ions
immeised in lle uniloim gas ol valence eleclions, called
lle Madelung eneigy, wlicl is given Ly
244 SQO, 5,3), 2002
A.R. Jivani et al.: Total energy, equation of states and bulk modulus od Si and Ge
s
i
r

E
3
5
, (4)
wleie i
s
is lle aveiage inleieleclionic dislance. Tle Lwald
conslanl () loi covalenl ciyslals is 1.67O85.
!n equalion (3), E
O
is lle sum ol lle Iinelic, exclange
and coiielalion eneigies ol lle valence eleclion and is
given Ly
( )
1
]
1

) ( ln 031 0 115 0
916 0 21 2
2
0 s
s
s
r . .
r
.
r
.
Z E
(5)
E
1
is lle liisl oidei eiluiLalion eneigy ol lle valence
eleclion due lo lle seudoolenlial and is given Ly
1
1
]
1

(q)
G
4
lim
2
2 2
0 q
1 b
ZW
e Z
E
(6)
Ioi iesenl seudoolenlial, lle value ol lle elec-
lion-ion inleiaclion is
10
9
2 2 2
1
c
R e Z
E (7)
Tle second oidei leim E
2
in equalion (3) can Le wiil-
len as
) q ( ) q ( ) q ( ) q (
q
'
2
S W E
s

, (8)
weie lle summalion excludes q = O and is caiiied oul
loi 2OO6 ieciiocal veclois. !n aLove equalion, sliucluie
lacloi ol lle diamond lallice is given Ly
), q cos( ) q (
q
Q q,

S
(9)
wleie Q is lle ieciiocal vecloi and = (a/4, a/4, a/4) is
a lall ol lle vecloi in lle Lody diagonal diieclion sea-
ialing lle lwo inleienelialing ICC lallices ol lallice
conslanl `a`.
!n equalion (8), lle seudoolenlial scieened Ly lle
eleclion gas is
) q (
) q (
) q (

b
S
W
W
(1O)
Tle scieening lacloi (q) loi a liee eleclion gas is
[ ] (q) (q) 1
G
8
1 (q)
2
2
f
e
(11)
leie f(q) is lle local-lield coiieclion and ?(q) is eiluiLa-
lion claiacleiislics wlicl is given Ly
1
1
]
1

+
X
X
X
X
.
k
Z

F
1
1
ln
2
1
5 0
4
3
(q)
2
2
, (12)
wleie
F
k
X
2
q
and k
F
is lle Ieimi wave vecloi.
Tle covalenl Lond coiieclion (E
cov
) coiiesonding
lo lle lliid and louill-oidei leims lo lle lolal eneigy is
given Ly

,
_

4
2
2
2
cov
) 111 (
4
) (
s F
W
a
E n E

1
]
1

,
_

+
2
2
2
) 111 ( ) 220 (
2
s s
W W
a

, (13)
wleie lle valence eleclion densily ol slales ei alom al
lle Ieimi suilace n(E
F
) = Z(2E
F
/3)
1
. !n equalion (13),

S
(111) and
S
(22O) aie lle scieened seudoolenlial
Iouiiei comonenls al ieciiocal oinls (111) and (22O).
Tle equalion ol slales and LulI modulus aie oLlained
liom

d
dE
P (14)
and
2
2

d
E d
B (15)
!n lle iesenl calculalions, lo deleimine R
c
, lle ies-
suie less llan 1O
3
ILai is laIen as equal lo zeio. Ioi lle
incoioialion ol exclange and coiielalion ellecls lo lle
dielecliic lunclion (q), we adoled seven aioxima-
lions, ioosed Ly Hailiee (H) [14], HuLLaid and Slam
(HB) [15,16], modilied HuLLaid Slam (HS) [15-17],
Kleinman (K) [18], Kleinman and Iangiell (KI) [18,
19], Vaslislla and Singwi (VS) [2O] and Tayloi (T) [21].
3. Results and discussion
TaLles 1 and 2 slow lle lolal eneigy ei eleclion ol semi-
conduclois oLlained Ly using equalions (3-13) alongwill
exeiimenlal and ollei sucl ieoiled values [9, 12]. !l is
lound liom llese laLles llal lle ellecl ol exclange and
coiielalion is cleaily dislinguislaLle. Tle inclusion ol
exclange and coiielalion lunclion suiesses lle value
ol lolal eneigy ol Si and Ge llan llose oLlained Ly lle
slalic H dielecliic lunclion (willoul exclange and coiie-
lalion). Tlus, deciease in lolal eneigy due lo inclusion ol
lle exclange coiielalion lo lle dielecliic lunclion lavois
lle colesion ol semiconduclois. !l is also iedicled llal
lle Tayloi`s f(q) gives minimum eneigy loi Loll Si and
Ge.
Iiguies 1 and 2 slow lle iessuie-volume ielalions
loi Si and Ge alongwill lle exeiimenlal dala [12]. Tle
iesenl linding ol equalion ol slales will vaiious f(q) is
loi Si and Ge al dilleienl volume aie willin lle value
oLlained Ly inclusion ol H and T local lield coiieclion lo
lle dielecliic lunclion. Hence, lo avoid lle comlicalion
in lle liguies, equalion ol slales oLlained due lo H and T
aie lolled. Al 9 comiession lle ellecl ol exclange
and coiielalion lunclion ol T will iesecl lo H is 25
loi Si and 28 loi Ge. Oui equalion ol slales loi Si and
A.R. Jivani et al.: Total energy, equation of states and bulk modulus od Si and Ge
245 SQO, 5,3), 2002
Ge aie comaied will lle exeiimenlal dala ieoiled Ly
Biidgman, Vaidya el al (Ly islon-cylindei mellod) and
Senoo (Ly X-iay dilliaclion mellod)[12]. Tle excellenl
agieemenl loi equalion ol slales ol Si and Ge is concluded
in lle iesenl sludy.
Tle iesenlly invesligaled LulI modulus (B)

ol semi-
conduclois is laLulaled in TaLles 3 and 4 alongwill ollei
sucl lleoielical and oLseived dala [6, 9]. Tle values in lle
aienllesis slow lle eicenlile devialion liom lle exeii-
menlal dala. Iiom laLles 3 and 4, il is noliced llal lle devia-
lion ol oui iesull liom oLseived values is 1.64 lo 18.25
loi Si and 2.14 lo 33.79 loi Ge. Tle iesulls due lo
olleis [6, 9] include lle devialion ianging liom 14.72 lo
31.59 loi Si and O.94 lo 25.73 loi Ge liom lle oL-
seived values. Iiom TaLles 1 lo 4, we conclude llal llougl
lle calculaled values ol lolal eneigy and LulI modulus ol
Si and Ge scallei in a Lil wide iange aiound lle oLseived
values, iesenl lindings aie moie imioved iesulls as com-
aied lo ieviously ieoiled ollei sucl lleoielical val-
ues [6, 9, 12]. Tlus, lle iesenl sludy conliims lle liuil-
lulness ol oui model olenlial in iedicling eleclionic
ioeilies ol semiconduclois. Tlis also iovides Lellei
sel ol lleoielical iesulls on lolal eneigy, equalion ol slales
and LulI modulus loi inliinsic semiconduclois Si and Ge
loi luillei comaiison eillei will lleoielical oi exeii-
menlal iesulls.
Acknowledgements
Tle woiI is suoiled undei lle secial assislance io-
giamme al lle level ol Deailmenlal ieseaicl suoil Ly
lle \niveisily Gianls Commission, ew Delli, !D!A.
Tle aulloi (PG) acInowledges lle lacililies availed al
lle ALdul Salam !nleinalional cenlei loi Tleoielical
Plysics, !TAIY, duiing lle couise ol lle woiI.
Fig. 1. Tle iessuie-volume ielalions ol Si Fig. 2. Tle iessuie-volume ielalions ol Ge
Table 1. Total energy - per electron of Si (in Rydberg units) Table 2. Total energy - per electron of Ge (in Rydberg units)
0
0
f (q) Piesenl Olleis OLseived
[9] [9] [12] [9]
H 1.9413 1.9758
HB 2.O458 1.9758 1.9882
HS 2.O44O 1.9734 1.9859
K 2.O898 1.9965 2.OO78 1.98O
KI 2.O89O 1.9965 2.OO41
VS 2.1237 2.OOO3 2.O1O5
T 2.1463
f (q) Piesenl Olleis OLseived
[9] [9] [12] [9]
H 1.8617 1.96O
HB 1.96O8 1.9418 1.9663
HS 1.9605 1.9404 1.9647
K 2.0010 1.9654 1.9874 1.978
KI 2.0037 1.9635 1.9852
VS 2.0397 1.9736 1.9933
T 2.0597
246 SQO, 5,3), 2002
A.R. Jivani et al.: Total energy, equation of states and bulk modulus od Si and Ge
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12
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2
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f(q) Piesenl Olleis OLseived
[6] [9] [9] [9]
H 1.1565 (18.25) O.833
(14.83)
HB 1.O315 (5.47) O.775 O.852 O.8O1
(2O.76) (12.88) (18.1)
HS 1.OO41 (2.67) O.729 O.834 O.78O
(25.46) (14.72) (2O.24)
K O.994O (1.64) O.81O O.754 0.978
(17.18) (22.9O)
KI O.9369 (4.2O) O.774 O.717
(2O.86) (26.69)
VS O.9176 (6.17) O.723 O.669
(26.O7) (31.59)
T O.8625 (11.81)
f(q) Piesenl Olleis OLseived
[6] [9] [9] [9]
H 1.0035 (33.79) 0.757
(0.94)
HB 0.8810 (17.17) 0.680 0.728 0.685
(9.33) (2.93) (8.67)
HS 0.8554 (14.06) 0.654 0.717 0.662
(12.8) (4.40) (11.73)
K 0.8455 (12.74) 0.704 0.646 0.750
(6.13) (13.87)
KI 0.7924 ( 5.65) 0.661 0.603
(11.87) (19.60)
VS 0.7661 ( 2.14) 0.615 0.557
(18.00) (25.73)
T 0.7218 ( 3.76)