ARTICLE IN PRESS

Physica B 340342 (2003) 116120

Transition metal impurities in 3C-SiC and 2H-SiC

L.V.C. Assalia,*, W.V.M. Machadoa, J.F. Justob
a

Instituto de F!sica, Universidade de Sao

* Paulo, CP 66318, CEP 05315-970, Sao
* Paulo, SP, Brazil
b
Escola Polit!ecnica, Universidade de Sao
* Paulo, CP 61548, 05424-970, Sao
* Paulo, SP, Brazil

Abstract
The electronic and structural properties of 3d transition metal (TM) impurities in 3C-SiC and 2H-SiC have been
investigated by ab initio calculations. The stability, spin states, formation and transition energies of isolated Ti, V, and
Cr impurities in several charge states were computed. Our results were compared to available experimental data.
r 2003 Elsevier B.V. All rights reserved.
PACS: 61.72.Ww; 71.55.
i; 71.55.Cn
Keywords: Silicon carbide; Transition metals; LAPW methods

1. Introduction
Titanium, vanadium, and chromium are common impurities in SiC. Experiments indicate that
Ti is stable in a Si site [1], but while it is electrically
active in 4H-SiC, it is inactive in 3C-SiC [2].
Although the local structure for a substitutional Ti
impurity is essentially the same in either hexagonal
or cubic material, the electronic activity results
from the differences in the materials band gap (eg ).
Deep level transient spectroscopy experiments on
Ti in 4H-SiC show that Ti introduces gap levels
near the conduction band bottom [3]. Since eg is
considerably smaller in 3C-SiC (2:42 eV) than in
4H-SiC (3:27 eV), the Ti-related energy levels
would be pinned in the conduction band for the
3C-SiC, and therefore, they would be undetectable. On the other hand, V and Cr generate active
centers in all polytypes [2].
*Corresponding author. Tel.: +55-11-3091-7041.
E-mail address: lassali@if.usp.br (L.V.C. Assali).

Here, we carried out a theoretical investigation

on the properties of isolated Ti, V, and Cr
impurities in 3C-SiC and 2H-SiC. The calculations
were performed within the framework of the
density functional theory [4] and the Perdew
BurkeErnzerhof approximation [5], using the
full-potential linearized augmented planewave
(FP-LAPW) method, implemented in the WIEN97
package [6]. We considered 54- and 56-atom
reference supercells for the 3C and 2H polytypes,
respectively. The convergence in total energy was
achieved using 5:8=R (maximum length of the
( is the smallest
plane waves), where R 0:64 A
radius which denes the atomic spheres. The
Brillouin zone was sampled by a unique point in
the irreducible zone [7]. Self-consistent interactions
were performed until convergence on both the
total energy (10
4 eV per unit cell) and total
charge in the atomic spheres (10
5 electronic
charges per atom) were achieved. The atomic
positions were relaxed until the forces were smaller
(
than 0:02 eV=A:

0921-4526/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2003.09.008

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L.V.C. Assali et al. / Physica B 340342 (2003) 116120

117

2. Results
We rst investigated the stability of neutral
titanium impurities in cubic silicon carbide. Considering the case of neutral Ti impurity, which is
isoelectronic with Si and C host atoms, in Si or C
substitutional sites; both centers have a closed shell
conguration, being stable in Td symmetry. However, the bonding is considerably different. This
becomes clear when inspecting Fig. 1, which shows
the contour plot of the total electronic charge
density in the 1 1 0 plane containing the impurity;
while there is a rebonding of the vacancy dangling
bonds for substitutional Ti in a Si site, Ti0Si in
Fig. 1a, this is not observed for a substitutional Ti
in a C site, Ti0C in Fig. 1b. By computing formation
energies of isolated interstitial and substitutional
Ti impurities, following the procedure presented in
Ref. [8], substitutional Ti at a Si site is the most
stable conguration [9], which is consistent with
experimental ndings [1]. The formation energies
for other Ti congurations are at least 6:1 eV
higher than the energy of this conguration.
Therefore, here we will focus our investigation
only on the properties of Ti, V, and Cr present in
the Si sublattice (TMSi ) in both 3C-SiC and 2HSiC materials.
Fig. 2 displays the KohnSham energy eigenvalues representing the 3d-related impurity levels for
the neutral substitutional Ti, V and Cr in 3C-SiC
and 2H-SiC. In 3C-SiC, the 3d-related energy
levels are split into an e plus a t2 representation,
while in 2H-SiC, due to the C3 symmetry, the t2
levels split into an e plus an a level. The valence
band tops (ev ) in 3C and 2H polytypes were
aligned in the gure, without any valence band
offset. This could be justied by experimental data
in which a small valence band offset is found
between 4H- and 6H-SiC (0:17 eV) [10] and by
theoretical investigations which computed a small
valence band offset between 2H and 3C-SiC
(0:13 eV) [11].
The substitutional Ti on a Si site in 3C-SiC introduces no energy levels in the band gap (Fig. 2a).
The neutral center shows a closed shell conguration, leading to an effective spin S 0: This center
has a Td point symmetry, where the four nearest
neighbors undergo an outward relaxation of 7%

Fig. 1. Contour plot of the total electronic charge density in

the 1 1 0 plane for (a) Ti0Si and (b) Ti0C : The line separation is
( 3:
0:1 e=A

(with relation to the theoretical crystalline intera( The Ti-related energy

tomic distance of 1:90 A).
levels are unoccupied resonant levels in the
conduction band, where the e level lies below the
t2 level. Therefore, when a Ti atom replaces a Si
atom, it undergoes a pd hybridization, binding to
the four nearest neighbor carbon atoms (Fig. 1a).
Furthermore, the Ti impurity reconstructs the
vacancy dangling bonds, affecting only slightly

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L.V.C. Assali et al. / Physica B 340342 (2003) 116120

118

0
3C-SiC:TMSi

Ti

2H-SiC:TMSi
Cr

t2
e

Ti

t2
(15)

e
t2

Cr

a
e
e

CB

a
e
e
a
e

(41)

(50)

(29)

(33)

(52)

e
VB

t2

t2
(a)

(b)

(c)

e
a
(d)

(e)

(f)

e
e
a
a

Fig. 2. KohnSham energy eigenvalues representing the 3d-related impurity levels in the gap region for the neutral substitutional Ti, V
and Cr, in the Si site, in 3C-SiC, (a)(c), and 2H-SiC, (d)(f). The valence band top of 3C and 2H were aligned. The lled circles
indicate the number of electrons in the last occupied gap level, the m and k arrows represent the up and down spins, and the numbers in
( in the e energy level.
parenthesis give the d-character percentage of charge (inside the TM spheres with atomic sphere radius of 0:79 A)
VB and CB symbols represent the valence and conduction bands, respectively.

the crystalline band structure. By comparing the Ti

related energy levels in 3C and 2H-SiC (Figs. 2a
and d), we nd that the non-bonding level with erepresentation lies essentially at the same position
with relation to ev : However, this unoccupied level
lies inside the band gap in the 2H polytype and has
a higher d-character when compared to the
respective level in the 3C polytype. This center
has a C3 point symmetry, with the four nearestneighbors undergoing outward relaxation of about
6%.
The gure also presents the 3d-related energy
levels for neutral substitutional V and Cr in 3C
and 2H polytypes. In both materials, the V
impurity introduces a partially occupied em level
in the center of the gap (Figs. 2b and e). The Cr
impurity introduces a fully occupied em level in the
lower half part of the gap (Figs. 2c and f). The
energy level ordering shows that the V center
presents a low spin conguration S 12 while
the Cr center presents a high spin conguration
S 1: As a result of the electronic conguration
for V, an 2 E ground state, one would expect a
symmetry lowering for the center. However, our
calculations show that distortions are very small

and the center remains essentially in a Td

symmetry. In terms of the structural relaxation,
we nd that for both the V and Cr centers, the four
nearest neighbors undergo outward relaxation of
about 3% in both 3C and 2H polytypes.
Table 1 presents the symmetry, total spin S;
formation energies (DEf )1 and transition energies
(Et ), in relation to ev ; for TMSi in 3C-SiC and 2HSiC in different charge states. Available electron
paramagnetic resonance (EPR) measurements for
V0 and V
in 4H and 6H polytypes assign spins
S 12 and 1, respectively [12]. EPR measurements
on 6H and 4H polytypes [12,13] for Cr ; Cr0 ; and
Cr
assign spins S 12; 1 and 32; respectively. All
these results are consistent with our results in 3C
and 2H polytypes. On the other hand, EPR
measurement for the Cr2
in 6H nds a spin S
2 [14]. While our result for this center in 2H is
consistent with such data, the center in 3C gives a
spin S 0: From the Ti0 to the Cr0 impurities in
1
The calculation of formation energies of the defects
considered the chemical potentials of silicon, diamond, silicon
carbide, and TM carbides (TM Ti; V; and Cr) in the
respective stable crystalline congurations.

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119

Table 1
Results for TMSi in 3C-SiC and 2H-SiC in different charge states
3C-SiC

Ti0
Ti

V
V0
V

Cr
Cr0
Cr

Cr2

2H-SiC

Sym.

DEf (eV)

Td

0.0

Td
Td
Td
Td
Td
C3v
C3v

0
1
2

1
1
2

1
3
2

2:2 eF
3.6
5:2
eF
6.0eF
6.5
8.6
eF
11.0
2eF

Et (eV)

1:40=
1:60=

0.5(0/+)
2:10=

2:4
=
2

Sym.

DEf (eV)

C3
C3
C3
C3
C3
C3
C3
C3
C3

0.0
2:7
eF

0:7 eF
0.7
2:5
eF

0:5 eF
0.0
2.2
eF
4.5
2eF

1
2

0
1
2

1
1
2

1
3
2

Et (eV)
2:70=

1.4(0/+)
1:80=

0:50=
2:20=

2:3
=
2

The table presents the symmetry, total spin S; formation energies (DEf with relation to the Ti0 center in each polytype), and transition
energies (Et ) with relation to ev : The reference formation energies of Ti0 are 4:3 eV and 2.8 eV in 3C-SiC and 2H-SiC, respectively. The
theoretical approximations and numerical truncations lead to an estimated error of E0:2 eV in the calculated transition energies. eF is
the Fermi energy.

3C-SiC, the crystal symmetry is kept (Td ), while

for Cr
there is a symmetry lowering to C3v : This
behavior results from the symmetry of the last
occupied level, which has a non-bonding character
(e state) from Ti0 to the Cr0 but an anti-bonding
character (a1 state) for Cr
; resulting in a high spin
conguration for Cr
: For the Cr2
; the C3v
distortion is very large, driving the center to a
closed shell conguration (e4 state).
Table 1 also presents the transition energies for
the centers. Since the Ti0 center in the 3C-SiC
presents no energy levels in the band gap (Fig. 2a),
the acceptor transition energy of this center could
not be computed. However, the absence of this
acceptor transition for Ti in 3C-SiC is consistent
with experimental data. While acceptor transition
energy levels for Ti impurity in hexagonal polytypes, ev 3:13 eV in 4H [2] and ev 2:90 eV in
6H [14], have been observed, no Ti transition level
has been measured in the cubic polytype [2]. These
results for the 0=
transition should be compared to our value of ev 2:7 eV in 2H-SiC.
However, we should compare those transition
energies with caution due to the different lattice
structures of cubic and hexagonal SiC. While there
is only one non-equivalent Si sublattice in 2H-SiC,
there are two and three non-equivalent Si sublattices in 4H-SiC and 6H-SiC, respectively. As a
result, experimentalists nd multiple TM-related
transition energies.

We nd that the vanadium center (VSi ) is

amphoteric in both 3C and 2H polytypes, which
is consistent with experimental data in several
polytypes [12,15,16]. For the 0= transition, our
value of ev 1:4 eV in both 3C and 2H-SiC should
be compared to the experimental values of ev
1:7 eV in 3C-SiC and ev 1:6 eV in 6H-SiC [13].
For the 0=
transition, our values (Table 1)
should be compared to experimental data values of
ev +(2.12:3 eV in 4H-SiC [15,16] and ev 2:4 eV
in 6H-SiC [17]. For the chromium center (CrSi ),
we nd three transitions in 2H-SiC. These results
are consistent with experimental ndings in
4H-SiC [17,18].

3. Conclusion
In summary, we performed a theoretical investigation of isolated Ti, V, and Cr impurities in
hexagonal and cubic silicon carbide. We nd that
substitutional impurities (in the Si sublattice) are
energetically more favorable than the interstitial
ones. Our results for spin in several charge states
and transition energies for substitutional TM are
fully consistent with available experimental data.
The chemical trends of neutral 3d-transition
metals in SiC follow the typical trends of
TM-related centers in semiconductors [19,20]. As
the 3d-level is lled, there is a deepening of the

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L.V.C. Assali et al. / Physica B 340342 (2003) 116120

non-bonding e state with increasing impurity

atomic number Z: The exchange splitting of this
e level goes from 0:0 eV in Ti to 1:9 eV in Cr. The
t2 bonding level, which lies in the valence band, is
only slightly inuenced by variations in Z: On the
other hand, the t2 anti-bonding level is more
strongly affected by Z changes. On going from V
to Cr, the exchange splitting is such that it drives
the TM center from a low to a high spin
conguration, if distortions can be neglected.

Acknowledgements
The authors acknowledge support from FAPESP and CNPq. The calculations were performed
at the LCCA-CCE of the Universidade de S*ao
Paulo.

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