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IOP PUBLISHING SEMICONDUCTOR SCIENCE AND TECHNOLOGY
Semicond. Sci. Technol. 25 (2010) 095010 (8pp) doi:10.1088/0268-1242/25/9/095010

Raman scattering study of vibrational

modes and hole concentration in
GaxMn1−x Sb
M R Islam1,4 , M M Hasan1 , N Chen2 , M Fukuzawa3 and M Yamada3
1
Department of Electrical and Electronic Engineering, Khulna University of Engineering and
Technology, Khulna-9203, Bangladesh
2
Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of
Sciences, Beijing 100083, People’s Republic of China
3
Department of Electronics, Kyoto Institute of Technology, Kyoto 606-8585, Japan
E-mail: islambit@yahoo.com/mri@eee.kuet.ac.bd

Received 14 April 2010, in final form 19 July 2010

Published 23 August 2010
Online at stacks.iop.org/SST/25/095010

Abstract
The Raman scattering study of vibrational modes and hole concentration in a ferromagnetic
semiconductor Ga1−x Mnx Sb grown by Mn ion implantation, deposition and post-annealing has
been presented. The experiments are performed both in implanted and unimplanted regions
before and after etching the samples. The Raman spectra measured from the unimplanted
region show only GaSb-like phonon modes. On the other hand, the spectra measured from the
implanted region show additional phonon modes approximately at 115, 152, 269, 437 and
659 cm−1 . The experimental results demonstrate that the extra modes are associated with
surface defects, crystal disorder and blackish layer that is formed due to Mn ion implantation,
deposition and annealing processes. Furthermore, we have determined the hole concentration
as a function of laser probing position by modeling the Raman spectra using coupled mode
theory. The contributions of GaSb-like phonon modes and coupled LO-phonon plasmon mode
are taken into consideration in the model. The hole-concentration-dependent CLOPM is
resolved in the spectra measured from the implanted and nearby implanted regions. The hole
concentrations determined by Raman scattering are found to be in good agreement with those
measured by the electrochemical capacitance–voltage technique.

1. Introduction temperature of less than 300 K, as reported so far [5, 6]. On

In recent years, research interest has been highly concentrated
on investigating and fabricating new semiconductor materials
for the development of spintronic technology [1–4].
Diluted magnetic semiconductors (DMSs) are promising
materials for new class spintronic devices as they can
integrate semiconducting properties with magnetic properties.
Compared with II–VI semiconductor-based DMSs, III–V
semiconductor-based DMSs possess greater advantages,
because doping control is far more difficult in II–VI
compounds than in III–V compounds. In most of the
III–V semiconductor-based DMSs (GaMnAs, InMnAs), the
ferromagnetic phase transition occurs at a maximum Curie
4 Author to whom any correspondence should be addressed.
the other hand, Ga1−x Mnx Sb is an attractive III–V-based DMS
for fabricating spintronic devices due to its room-temperature
ferromagnetic properties [7–9].
For the last few years, the structural and room-
temperature ferromagnetic properties of Ga1−x Mnx Sb have
been investigated by an x-ray diffraction, vibrating sample
magnetometer [7, 8]. The structural properties of this material
grown by digitally doped Mn are also analyzed theoretically
and experimentally using a cross-sectional scanning tunneling
microscope [9]. In our recent study [10], Raman spectroscopic
determination of Mn composition and strain has been reported
in Ga1−x Mnx Sb prepared by liquid-phase epitaxy. However,
due to lower Mn concentration (x < 4%) in the samples, we
were unable to understand vibrational properties in detail.

0268-1242/10/095010+08$30.00 1 © 2010 IOP Publishing Ltd Printed in the UK & the USA
Semicond. Sci. Technol. 25 (2010) 095010
Further, the magnetic properties of Ga1−x Mnx Sb arise from
the S = 5/2 Mn spin system [8]. It is well established that the
maximum Curie temperature of DMSs depends on the hole
density [6–9] which is correlated with the incorporation of
Mn atoms into the GaSb matrix. Therefore, it is immensely
important to characterize hole density in DMS Ga1−x Mnx Sb
for understanding its ferromagnetic as well as electronic
properties.
Measurement of hole concentration is difficult in DMS
by standard magneto-transport techniques (Hall measurement)
due to the anomalous Hall effect [11–13]. In addition,
Hall measurements are not applicable to magnetically di-
luted samples that are insulating [11]. Although the elec-
trochemical capacitance–voltage (ECC-V) technique is used
to measure hole concentration in DMS, it is destructive in
nature. Moreover, results of the ECC-V technique depend
on the selection of solvents suitable for the sample under
study. On the other hand, there is a strong correlation be-
tween the coupled plasmon-LO-phonon mode (CPLOM) and
the hole density in the Raman spectra measured from DMSs
[12–14]. This leads us to determine hole density nondestruc-
tively by modeling the phonon line shapes using coupled mode
theory. Although few Raman scattering studies have been per-
formed on GaAs, GaSb, GaMnAs and GaN [8–13, 19, 20],
to the best of authors’ knowledge, nobody has performed the
Raman scattering study of the vibrational modes and hole den-
sity in Ga1−x Mnx Sb.
The Ga1−x Mnx Sb samples studied here were prepared
with higher Mn composition (x ∼ 10%) by Mn ion
implantation, deposition and post-annealing. Some
preliminary Raman results have been reported in our recent
studies [15, 16]. In this paper, the Raman scattering
study of the vibrational modes and hole density has been
presented in detail. To understand the optical phonon modes
clearly, the samples were measured from both the implanted
and unimplanted regions before and after etching. By
correlating the Raman spectra measured from the implanted
and unimplanted regions, some additional phonon modes are
identified. From the experimental observations, the origin
of these modes is discussed in detail. Furthermore, the
hole concentration as a function of laser probing position is
evaluated analyzing the Raman line shape using coupled mode
theory. The Raman results are found to be in good agreement
with those measured independently by the ECC-V technique.
2. Experimental procedure
The zinc blende Ga1−x Mnx Sb single crystals were prepared by
a low-energy ion-beam deposition (LEIBD) system [8]. There
are magnetic analyzers in the LEIBD system, with which the
manganese can be purified to be as pure as an isotope. First,
the manganese ions with an energy of 1 keV were implanted
at 200 ◦ C into a small region of an unintentionally doped
p-type (1 1 1)-oriented GaSb wafer at the depth of about
100 nm. Then, the manganese ions with an energy of 100 eV
were deposited on the surface of the wafer, which formed a thin
layer of about 5 nm thickness. After the Mn-ion implantation
and deposition, the wafers were annealed at 400 ◦ C in an
2
M R Islam et al
argon ambience for 30 min. The purpose of deposition is to
increase the Mn concentration in the samples. A portion of the
sample surface was found to be blackish after annealing. To
clean the sample surface, it was etched using diluted H3 PO4
for 15 min. The crystalline structure and room-temperature
magnetic properties of the samples were studied [8] using the
x-ray diffraction and vibrating sample magnetometer. Energy
dispersive x-ray was used to evaluate the Mn concentration.
The maximum Mn concentration was found to be x ∼ 0.09 at
the surface of the sample. The hole density profile along the
thickness of the sample was measured by the ECC-V technique
and found to be 1 × 1021 cm−3 at the surface and drops abruptly
to 1 × 1019 cm−3 within a depth of 70 nm. After that the
hole density drops flatly to about 9 × 1017 cm−3 at the depth
of 4 μm.
Raman experiments were performed at room temperature
in the backscattering configuration employing the 514.5 nm
line of an argon-ion laser. The laser beam was focused, and
then the scattered light was collected with a 20× objective
lens. In order to eliminate elastic diffusion, a suitable notch
filter was used. The slit width was reduced to about 100 μm to
prevent background noise. The laser power was low enough
to prevent the local heating of the sample. The scattered light
was dispersed with a Renishaw-2000 model spectrometer and
detected with a cooled CCD detector.
3. Experimental results and discussion
The first-order Raman scattering from a semiconductor
typically shows longitudinal and transverse optical (LO and
TO) phonon modes [17]. But, depending upon the crystal
orientation and experimental geometry, one of them may
be optically forbidden. It is found that some compound
semiconductors (InGaAs, InGaSb and AlGaSb) show two-
mode behavior in the first-order Raman scattering where
LO and TO phonon modes are found corresponding to
binary end materials [18]. The appearance and frequency
position of these phonons depend on the crystal orientation
and composition. Similarly to compound semiconductor
Ga1−x Inx As, Ga1−x Mnx Sb may show GaSb- and MnSb-like
LO and TO phonon modes in the first-order Raman scattering.
3.1. Raman spectra before etching
Figure 1 shows some of the Raman spectra recorded from
inside and outside of the implanted regions before etching the
sample. The experimental schematics are shown in the inset of
figure 1 where the filled white circles indicated by the letters a
to f are laser probing points. The spectra indicated by the letters
a, b and f, and c to e are from outside, close to the implanted and
inside the implanted regions of the sample, respectively. The
spectrum indicated by a shows phonon modes only at 235.6
and 226 cm−1 , which are identified as GaSb-like LO and TO
modes, respectively [19]. Besides the GaSb-like LO and TO
modes, some additional modes are observed at about 116 and
152 cm−1 in the spectra indicated by b, c, e and f. It is found in
figure 1 that the intensity of the phonon modes changes when
the laser beam is probed at different measurement points. It
Semicond. Sci. Technol. 25 (2010) 095010
Figure 1. Room-temperature Raman spectra measured from the
Ga1−x Mnx Sb sample before etching. The inset shows sample
overview and experimental schematic where filled white circles
indicate measurement points. The spectra designated by the letters
a, b, c, d, e and f are obtained from the corresponding points shown
in the inset.
should be mentioned here that some portion of the sample
surface was blackish due to annealing. Consequently, the
intensity of phonons changes drastically in the blackish region
due to suppression of the Raman signal. Almost complete
suppression of the Raman signal is found in the spectrum
indicated by d, because it was measured from a more blackish
region. The GaSb-like LO phonon is also found to be screened
in the spectra due to free carrier plasma, which coupled with
the LO phonon via their macroscopic electric fields. In our
sample, the free carriers are holes which originate from the
acceptor Mn. Figure 2 shows the Raman spectra in the higher
frequency range where the spectra are truncated from the top
to observe the weak phonon modes. Several spectra from the
blackish and the clean regions are shown in figure 2 to confirm
the reproducibility of the weak phonon modes. The spectra
measured from the clean region show weak phonon modes at
269 and 437 cm−1 . On the other hand, the spectra measured
from the blackish region show a strong phonon mode at
659 cm−1 .
The 437 cm−1 mode is found to be broad in the spectra
and can be assigned to a disorder-activated mode. The phonon
dispersion may experience disorder due to the implantation of
Mn atoms in the GaSb matrix resulting in the appearance of the
disorder-activated mode. The existence of the disorder phonon
mode was also found in the Raman spectra measured from GaN
3
M R Islam et al
Figure 2. Comparison of the Raman spectra measured from
blackish and clean regions of the sample. Several spectra from these
regions are presented to confirm the reproducibility of the phonon
modes.
layers implanted with Mn, Ar, P, C, Mg and Ca ions [20]. As
seen in figure 2, the 659 cm−1 mode completely disappeared
from the spectra measured from the clean region. This
indicates that the appearance of this phonon mode is connected
with the blackish layer. It is thought that manganese oxide
may form on the surface of the sample due to annealing. In a
previous study [21], the phonon mode observed in the Raman
spectra at 660 cm−1 was assigned to Mn3 O4 -like phonon
modes. Therefore, the phonon mode observed at 659 cm−1
is assumed to be related to manganese oxide vibration.
The origin of the phonon modes observed at 116, 152 and
269 cm−1 will be discussed below.
3.2. Raman spectra after etching
The origin of the phonon modes observed at 116 and 152 cm−1
is not so clear. It is anticipated that these modes are associated
with Mn ion implantation with higher energy. It was reported
[22] that the Raman spectra measured from GaN doped with
Mg show a low-frequency phonon mode (132 cm−1 ) and are
assigned to the local vibrational mode (LVM) of Mg in the
GaN matrix. As the concentration of Mn ions in our samples
is quite high, the local vibrations of Mn in the GaSb matrix
may be assumed. The frequency position of local vibration
of Mn in the GaSb matrix is determined within the simple
mass defect approximation [22] and found to be 245 cm−1 ,
which does not agree with the experimentally observed 116
and 152 cm−1 phonon modes. To understand the origin of
these modes, Raman experiments are further performed after
etching the sample in the same schematic shown in the inset of
figure 1. The Raman spectra obtained from the etched sample
are shown in figure 3. It is clearly observed that the 116 and
152 cm−1 phonon modes almost disappeared in the spectra
measured from the etched sample. We therefore conclude that
these modes are associated with surface defects formed by the
Mn ion implantation and deposition processes.
Semicond. Sci. Technol. 25 (2010) 095010
Figure 3. Room-temperature Raman spectra measured after etching
the Ga1−x Mnx Sb sample. The spectra indicated by the letters a, b, c,
d, e and f are from the same measurement points as shown in the
inset of figure 1.
3.3. Additional phonon modes
3.3.1. Phonon mode at 269 cm−1 . Raman spectra measured
from Ga1−x Mnx Sb should show GaSb- and MnSb-like phonon
modes. To the best of our knowledge, the frequency positions
of MnSb-like phonon modes are unknown. In order to
interpolate unknown phonon modes in ternary compound
semiconductors, the reduced-mass model was used [23].
Figure 4 shows the plots of TO and LO phonons of GaSb,
√  2
AlSb and InSb crystals in dependence of 1/ μ, where μ is
the reduced mass of Ga, Al and In atoms. The frequency
positions of MnSb-like TO and LO phonons are interpolated
from the simple fits as shown in figure 4 and found to be
approximately at 253.2 and 266.4 cm−1 , respectively. Since
the interpolated MnSb-like mode (266.4 cm−1 ) shows good
agreement with the phonon peak experimentally observed at
269 cm−1 , the peak appeared in the spectra at 269 cm−1 may
be assigned to the MnSb-like LO mode, but we are not certain
at this stage.
3.3.2. Coupled-LO phonon plasmon mode. In a polar
semiconductor, an LO phonon and the plasmon formed by
free carriers interact via their macroscopic electric fields
[13]. Depending on the carrier concentration in Ga1−x Mnx Sb
crystal, the frequency position of CLOPM varies from the
GaSb-like LO mode to the TO mode. The Mn atoms may
diffuse from the implanted region due to its high diffusivity.
As a result, CLOPM can be found in the spectra measured
from the implanted region as well as close to the implanted
4
M R Islam et al
Figure 4. The circles and squares represent LO and TO phonon
frequencies,
√ respectively, for GaSb, AlSb and InSb in dependence of
1/ μ. The LO and TO phonon frequencies for MnSb can be
obtained from the interpolation technique.
region. In our case, the CLOPM is convoluted with LOGaSb
and TOGaSb modes in the form of a broad structure. In order
to decompose the convoluted phonon modes, the line shapes
of the spectra are modeled using coupled mode theory. The
results obtained from the coupled mode theory are discussed
in the next section.
4. Determination of the hole density in Ga1−x Mnx Sb
Two Raman active CPLOMs ω+ and ω− are observed in n-type
semiconductors due to the coupling between LO phonon and
electron plasmon [24]. On the other hand, only one CPLOM
is observed (ω+ or ω−) in p-type semiconductors due to a
strong hole plasmon damping, moving from the LO to the TO
frequency depending on the hole concentration [11–13, 19].
According to the coupled mode theory, the frequencies of two
CPLOMs are given [13] by
  2 2  12 
ω±2
= 12 ωLo + ωp2 ± ωLo + ωp2 − 4ωp2 ωTO2
, (1)
where ωLo and ωTo are the LO and TO phonon frequencies,
respectively. ωp is the hole plasma frequency which can be
defined by
ωp2 = 4πpe2 /ε∝ m∗h , (2)
where p, ε∝ and m∗h arethe hole concentration, optical
dielectric constant and the effective mass of the free hole,
respectively. The calculated ω± frequencies of the CPLOM
as a function of hole concentration are shown in figure 5
for Ga1−x Mnx Sb crystal. The material parameters used in
this calculation are listed in table 1. It can be seen from
figure 5 that upper mode frequency of ω+ approximately
coincides with LO phonon at low hole concentration and the
lower mode frequency ω− coincides with TO phonon at high
hole concentration. The ω+ and ω− modes are screened in
Raman spectra at high and low hole concentrations. The hole
concentration-dependent shift in CLOPM leads to determining
the carrier concentration by modeling the Raman line shapes
using coupled mode theory. According to the formulations
Semicond. Sci. Technol. 25 (2010) 095010 M R Islam et al

Figure 6. Peak frequency variation of CPLOM evaluated with

Figure 5. The predicted frequencies of the coupled modes (ω+ and various hole concentrations using equation (3).
ω−) and the plasmon mode ωp as a function of carrier densities.
ωLo and ωTo are the GaSb-like LO and TO phonon frequencies.
ωp2
Table 1. GaSb material parameters taken from [19, 29]. 4π χf c = −ε∞ , (9)
ω(ω + ip )
Parameters Value where χph , χf c , γ and p are the ionic susceptibility, the
free carrier susceptibility, the phonon damping constant and
LO-phonon optical frequency, ωLO 235.6 cm−1
TO-phonon optical frequency, ωTO 226 cm−1 the plasmon damping constant, respectively. In equation (3),
High-frequency dielectric constant, ε∞ 14.4 g1 and g3 arise due to the modulation of the first-order
Faust–Henry coefficient, C −0.23 Raman susceptibility, respectively, by the atomic displacement
∗
Average hole effective mass, mh 0.34 m and by the macroscopic electric field associated with the
Static dielectric constant, ε0 15.7 coupled mode. g2 is the cross-correlation term between the
Barrier height, ϕ 0.724 eV
Lattice constant, a 6.09 A◦
atomic displacement and the macroscopic electric field. Using
equation (3), the peak frequency of the CPLOM in function
of hole density is evaluated. The results are shown in
derived by Katayama and Murase [13], the line shape of the figure 6. The peak frequency varies from 235.2 to 227.0 cm−1
CPLOM can be given by for the variation of the hole density from 2.18 × 1018 cm−3 to
1.10 × 1020 cm−3 . This indicates that the peak frequency of
g T = g1 + g2 + g3 , (3) the CPLOM shifted from LOGaSb to TOGaSb depending on the
hole density.
4
Obviously, the Raman spectra under study cannot
C 2 ωTo
g1 =  2  h̄[n(ω) + 1] be modeled solely by the CPLOM band. Two further
ωLo − ωTo2
contributions corresponding to the line shape of GaSb-like
 2 
× Im[(4π )2 χph (ε∞ + 4π χf c ) ε∞ ε , (4) phonons are taken into account in the first-order Raman
spectrum by the following formulation derived by Campbell
2
2CωTo and Fauchet [25]:
g2 =   h̄[n(ω) + 1] × Im[(4π )2 χph /ε∞ ε], (5)
2
ωLo− ωTo
2
|C(0, q )|2 d q
I (ω) = A , (10)
and [ω − ω( q )]2 + (b )2
g3 = h̄[n(ω) + 1]Im[−4π /ε], (6) where ω(q) is the phonon dispersion function of the
corresponding bulk material and C(0, q) is the phonon
where C is the Faust–Henry coefficient [11] and n(ω) is the confinement function and b is the half-width half-maximum
Bose–Einstein factor. The total dielectric function ε for the of the phonon line in the bulk crystal. The C(0, q) can be
phonon and the free charge system is given [13] by given by
  2
ε = ε∞ + 4π χph + 4π χf c , (7) |C(0, q )|2 = exp −q 2 dav
2
4a . (11)
The wave vector q is expressed in unit of 2π/a, dav is the
ω2 − ω2 average diameter of the microcrystal and a is the lattice
4π χph = ε∞ 2 Lo 2 To , (8)
ωTo − ω − iωγ constant. The average phonon dispersion in the bulk is

5
Semicond. Sci. Technol. 25 (2010) 095010 M R Islam et al

(f )

Figure 8. Hole concentration profile measured from implanted

(e) (filled circles) and unimplanted (filled triangles) by ECC-V as a
function of sample thickness. At the penetration depth of 21 μm,
the hole concentration was found to be 1.49 × 1020 cm−3 in the
implanted region.

ω(q) = ω0 − ω sin(q/4),ω0 is the GaSb-like LO or TO

phonon frequency and ω is the shift in GaSb-like LO or
TO branches. With the combination of equations (3) and
(10), the Raman line shapes shown in figure 3 are analyzed
(d) taking into account plasmon damping constant p , phonon
damping constant γ and plasma frequency ωp as the main
fitting parameters. The effect of other adjustable parameters
( ω, dav and b ) on the phonon line shapes is found to be
not so significant. The parameters are adjusted until the best
possible agreement between the calculated and the measured
spectrum is achieved. The results are summarized in figure 7 in
which open circles and solid lines, respectively, correspond to
(c) the measured and calculated spectra. The dotted lines indicate
the individual phonon mode decomposed from the spectra.
Only GaSb-like phonon modes are found in the spectrum a
measured from the unimplanted region. Since this region
is away from the implanted region, the hole concentration
in this region is lower. So, only GaSb-like phonon modes
are observed due to damping of CPLOM in this region. In
contrast, the CPLOM appeared along with GaSb-like phonon
(b) modes in the spectra measured inside the implanted region as
well as close to the implanted region due to the higher hole
concentration. It was shown [26] that the diffusivity of the Mn
atom is very high. Therefore, the results obtained from close
to the implanted regions were caused by the diffusion of Mn
atoms from the implanted region. The peak frequency of the
CPLOM indicates that the hole concentration in the implanted
region is not homogeneous.
(a) In order to determine the hole concentration, the value of
ωp is determined from the best fit condition of the experimental
spectra. Using equations (3) and (10), the hole concentration
is determined corresponding to each probing position. The
results are listed in table 2. To compare the Raman
results, the hole concentration is also measured independently
Figure 7. Line shape analysis of the Raman spectra shown in along the thickness of the sample by the ECC-V technique.
figure 3. The open circles and solid lines correspond to measured Figure 8 shows the ECC-V results where the maximum
and calculated spectra, respectively. The dotted lines indicate the hole density is found near the surface of the sample (∼1 ×
individual phonon mode decomposed by line shape modeling with 1021 cm−3 ), and it drops abruptly (∼1 × 1019 cm−3 ) within a
the combination of equations (3) and (10).
6
Semicond. Sci. Technol. 25 (2010) 095010
Table 2. Comparison between Raman and ECC-V results. The letters a, b and f, and c to e indicate the laser probing position in the
unimplanted, close to the implanted, and in the implanted regions, respectively. The hole concentration p, optical mobility μop , depletion
width dL , phonon damping constant γ , hole–plasmon damping constant p , and peak frequency of the coupled mode ωR are evaluated by
modeling the Raman spectra using coupled mode theory.
Laser probing Raman result ECC-V result μop
position p (cm−3 ) p (cm−3 ) (cm2 V−1 s−1 )
a 7.82 × 1017 3.59 × 1017 54.56
b 1.34 × 1020 – 24.60
c 1.46 × 1020 1.49 × 1020 23.94
d 1.60 × 1020 22.75 27.98
e 1.30 × 1020 23.73 31.05
f 1.10 × 1020 – 24.80
depth of 70 nm. The hole density is found to be almost constant
(3.5 × 1017 cm−3 ) in the unimplanted region in figure 8. Since
the ECC-V results are as a function of depth along the sample
thickness, it is required to determine the penetration depth for
the probing laser beam (λ = 514.5 nm) to compare the Raman
results with the ECC-V results. Due to the unavailability of
the absorption coefficient for GaMnSb, the penetration depth is
determined to be approximately 0.21 μm using the absorption
coefficient of GaSb material. This can be assumed because
the sample studied here was Ga rich. Corresponding to the
penetration depth 0.21 μm, the hole density is evaluated from
figure 8 and found to be 1.49 × 1020 cm−3 and 3.59 ×
1017 cm−3 , in the implanted and unimplanted regions,
respectively. As seen in table 2, the ECC-V results are found
to be in good agreement with the results obtained from the
Raman line shape analysis by coupled mode theory. We have
also calculated depletion width, dL , and optical mobility, μop ,
using dL = (ε0 ϕ/2π e2 p)1/2 and μop = e/m∗h p . The results
are also listed in table 2 and found to be strongly dependent
on the hole concentration.
It is well established that the shift in optical phonons
in Raman scattering can be induced by the composition as
well as by the strain in ternary compound semiconductors
[27]. In our recent study [10], composition-dependent as well
as strain-induced shift was found in GaSb-like LO phonon
measured from Ga1−x Mnx Sb/GaSb layers prepared by liquid-
phase epitaxy. However, the coupled mode did not appear in
the spectra which may be due to the lower Mn concentration in
the samples. The Mn composition-dependent shift in optical
phonons was also found [11, 28] in Ga1−x Mnx As prepared by
molecular beam epitaxy and Mn ions implantation, deposition
and post-annealing. In this study, we did not find remarkable
shift in optical phonons as a function of probing position. The
causes behind this are not clear. However, our previous results
[10] indicate that the shift in optical phonons is smaller in
strained Ga1−x Mnx Sb compared to unstrained Ga1−x Mnx Sb.
Since the Ga1−x Mnx Sb layer was formed due to the Mn ion
implantation and deposition processes, the existence of strain
can be considered in the samples under investigation. It can
be conceived that with the combined influence of strain and
coupled mode, the GaSb-like phonon peaks may not show a
significant shift in the measured spectra. Since GaSb-like LO
and TO phonon positions are found to be almost constant as a
function of probing position, the parameters used in this study
correspond to GaSb material.
7
M R Islam et al
dL (A◦ ) γ (cm−1 ) p (cm−1 ) ωR (cm−1 )
399.6 3.6 500 235.60
30.50 5.2 1100 226.84
29.30 5.8 1140 226.77
7.0 1200 226.20
5.8 1150 226.90
33.70 5.0 1100 227.00
5. Conclusion
The vibronic properties and carrier concentration of
ferromagnetic semiconductor Ga1−x Mnx Sb grown by Mn ion
implantation, deposition and post-annealing have been studied
using Raman spectroscopy. To understand vibrational modes
in the Raman spectra, the samples are measured from both
implanted and unimplanted regions before and after etching.
By correlating the Raman spectra obtained from different
measurement conditions, GaSb-like LO and TO phonons are
found approximately at 235.6 and 226 cm−1 in the spectra
measured from the implanted and unimplanted regions. In
addition to GaSb-like phonons, some extra structures are found
approximately at 115, 152, 269, 437 and 659 cm−1 in the
spectra obtained from the implanted region. The 115 and
152 cm−1 modes, and 437 cm−1 mode are found to be
associated, respectively, with surface defects and crystal
disorder caused by Mn ion implantation and deposition
processes. The origin of the 269 cm−1 mode is not so clear.
However, the frequency position of the MnSb-like LO mode
(266.4 cm−1 ) determined by the reduced-mass model is found
to be close to the experimentally observed 269 cm−1 mode.
It is confirmed that the 659 cm−1 mode appeared due to the
blackish layer that is formed on the sample surface from the
annealing process. This mode is assigned to Mn3 O4 -like
phonon modes. Furthermore, the existence of CLOPM is
found in the spectra measured from the implanted and close to
the implanted regions.
We have also evaluated the hole concentration by
modeling the Raman line shape using coupled mode theory.
The typical hole concentration evaluated to be 7.82 ×
1017 , 1.6 × 1020 and 1.1 × 1020 in the unimplanted,
implanted and close to the implanted regions of the
sample, respectively. The experimental results demonstrated
inhomogeneous distribution of hole concentration in the
implanted region. The Raman results evaluated corresponding
to the penetration depth for the probing laser beam are found
to be in good agreement with the ECC-V results.
References
[1] Roukes M L 2001 Nature 411 747
[2] Ohno H, Munekata H, Molnar S and Chang L L 1991 J. Appl.
Phys. 69 6103
[3] Datta S and Das B 1990 Appl. Phys. Lett. 56 665
Semicond. Sci. Technol. 25 (2010) 095010 M R Islam et al

[4] Park Y D, Jonker B T, Bennet B R, Itzkos G, Furis M, (Dhaka, Bangladesh, 20–22 December) vol 2 p 816 IEEE
Kioseoglou G and Petrou A 2000 Appl. Phys. Lett. 77 3989 Catalog No. CFP0868A-PRT
[5] Matsukura F, Ohno H, Shen A and Sugawara Y 1998 Phys. [17] Abstreiter G, Cardona M and Pinczuk A 1984 Light Scattering
Rev B 57 R2037 in Solids IV ed M Cardona and G Guntherodt (Berlin:
[6] Hayashi T, Tanaka M, Nishinaga T and Shimada H 1997 Springer)
J. Appl. Phys. 81 4865 [18] Islam M R, Verma P, Yamada M, Tatsumi M and Kinoshita K
[7] Chen X, Na M, Cheon M, Wang S, Luo H and McCombe B D 2002 Japan. J. Appl. Phys. 41 991
2002 Appl. Phys. Lett. 81 511 [19] Maslar J E, Hurst W S and Wang C A 2008 J. Appl. Phys.
[8] Chen N F, Zhang F Q, Yang J L, Liu Z K, Yang S Y, Chai C L, 103 013502 (11 pp)
Wang Z G, Hu W R and Lin L Y 2003 Chin. Sci. Bull. [20] Limmer W, Riteter W, Sauer R, Mensching B, Liu C
46 516 and Rauscchenbach B 1998 Appl. Phys. Lett. 72 2589
[9] Boishin G I, Sullivan J M and Whitman L J 2005 Phys. Rev. B [21] Nam K W and Kim K B 2006 J. Electrochem. Soc.
71 193307 (4 pp) 153 A81
[10] Islam M R, Chen N F and Yamada M 2008 Cryst. Res. [22] Hoffmann A, Kaschner A and Thomsen C 2003 Phys. Status
Technol. 43 1091 Solidi (c) 0 1783
[11] Seong M J, Chun S H, Cheong H M, Samarth N [23] Verma P, Oe K, Yamada M, Harima H, Herms M and Irmer G
and Mascarenhas A 2002 Phys. Rev. B 2001 Appl. Phys. 89 1657
66 033202 (4 pp) [24] Katayama S and Murase K 1977 J. Phys. Soc. Japan.
[12] Limmer W, Glunk M, Mascheck S, Koeder A, Klarer D, 42 886
Schoch W, Thonke K, Sauer R and Waag A 2002 Phys. Rev. [25] Campbell I H and Fauchet P M 1986 Solid State Commun.
B 66 205209 (6 pp) 58 739
[13] Fukasawa R and Perkowitz S 1994 Phys. Rev. B 50 14119 [26] Yu K M, Walukiewicz W, Wojtowicz T, Kuryliszyn I, Liu X,
[14] Masek J, Kudrnovsky J and Maca F 2003 Phys. Rev. B Sasaki Y and Furdyna J K 2002 Phys. Rev. B
67 153203 (4 pages) 65 201303 (4 pp)
[15] Hasan M M, Islam M R, Chen N F and Yamada M 2008 Proc. [27] Islam M R, Verma P, Yamada M, Kodama S, Hanaue Y
5th Int. Conf. on Electrical and Computer Engineering and Kinoshita K 2002 Mater. Sci. Eng. B 91-92 66
(Dhaka, Bangladesh, 20–22 December) vol 2 p 821 IEEE [28] Islam M R, chen N F and Yamada M 2004 Proc. Int. Conf. on
Catalog No CFP0868A-PRT 13th SIMC (Beijing, China, 20–25 September) p 185 IEEE
[16] Hasan M M, Islam M R, Chen N F and Yamada M 2008 Proc. Catalog No. 04CH37383
5th Int. Conf. on Electrical and Computer Engineering [29] People R and Sputz S K 1990 Phys. Rev. B 41 8431