Appl. Phys.
A 67, 317322 (1998)
Resonant Raman studies of surface composition and structural
ordering in laser-irradiated Hg1xCdx Te
M. Scepanovic, M. Jevtic
Institute of Physics, Pregrevica 118, 11000 Belgrade, Yugoslavia
Received: 14 July 1997/Accepted: 10 October 1997
Abstract. Resonant Raman scattering has been used to study
the effects of high-power laser annealing on Hg1x Cdx Te for
x = 0.165 and x = 0.18. The annealing was performed in air
with a Nd:YAG laser tuned to the first harmonic. A pulse du-
ration of 72 ns and irradiation energy densities of 270 and
400 mJ/cm2 were used. Information on both the structural or-
dering and the alloy composition in irradiated Hg1x Cdx Te
was obtained by resonance Raman spectroscopy with laser
photon energies of between 2.41 and 2.54 eV. The presented
Raman spectra from annealed samples indicate structural dis-
order and a decrease in the degree of alloying as a result
of Hg outdiffusion and segregation caused by laser-induced
nonequilibrium melting and solidification. Moreover, a shift
of the maximum resonant enhancement for the TO2 , LO2 , A,
and LO1 &TO1 modes in the case of a Hg0.82 Cd0.18 Te sam-
ple, annealed by 400 mJ/cm2 laser pulse, to higher photon
energy points to an increase in the composition from x = 0.18
to x 0.3.
PACS: 42.55P; 81.40Z
Mercury cadmium telluride (Hg1x Cdx Te) has high potential
for the fabrication of thermal imagers, but is a defect semi-
conductor. Namely, the electronic properties of Hg1x Cdx Te
are controlled by lattice defects rather than by external im-
purities. On the other hand, rapid thermal processing of
semiconductors has become very attractive because of the
theoretical research into nonequilibrium processes as well
as selective applications in semiconductor technology. Ac-
cording to the high partial pressure, the mercury losses ob-
served under conventional or pulsed thermal annealing tech-
niques influence the structural defects and compositional
changes which lead to the change in the electrical proper-
ties of Hg1x Cdx Te. Therefore, the study of the structural and
compositional changes in laser-irradiated Hg1x Cdx Te is of
theoretical and practical interest, in order to optimize the con-
ditions of Hg1x Cdx Te laser processing.
Raman scattering is a powerful tool for studying the vi-
brational and electronic properties of semiconductors. Since
Applied Physics A
Materials
Science & Processing
Springer-Verlag 1998
phonon frequencies are sensitive to the interatomic forces and
the ion masses, phonon Raman scattering is an effective probe
of local structural order. In addition, the intensities of Ra-
man lines are sensitive to the details of the electronic band
structure of the semiconductors, which reflects alloy compo-
sition [1]. Thus the Raman effect is sensitive to both alloy
composition and structural order. The resonant Raman scat-
tering with photon energies between 2.35 and 2.7 eV has been
used to study both the alloy composition and the local struc-
tural order in Hg1x Cdx Te for x values near 0.25, depending
on the growth conditions [1].
In order to investigate the structural and compositional
changes at the Hg1x Cdx Te surface irradiated by Nd:YAG
laser pulses with energies appropriate for laser annealing, res-
onance Raman scattering experiments before and after the
irradiation were performed. The results presented in this pa-
per show resonant behavior of the HgTe-like TO2 and LO2 ,
clustering, and CdTe-like LO1 &TO1 modes for as-grown and
annealed samples. They are discussed and analyzed on the
basis of our earlier numerical analyses of laser annealing of
Hg1x Cdx Te [2, 3].
1 Experimental details
In this study we used Hg1x Cdx Te samples, with composition
x = 0.165 and x = 0.18, prepared by the solid-state recrys-
tallisation (SSR) technique. Single-crystal wafers were cut
and subjected to a mechanical polishing and chemical etch-
ing in a Br/methanol solution (0.5% by volume). After that,
the samples were rinsed in methanol for 1 h to remove all
traces of bromine.
The Raman measurements were performed in a stan-
dard facility equipped with a Jobin Yvon U1000 double
monochromator. The Raman experiments were carried out
in the backscattering geometry from the h111i surface with
the samples cooled to 10 K. The samples were excited with
various lines of an Ar+ laser, which is close to the E 1 gap
resonance for the present alloy composition [1]. The prob-
ing depth 1/(2), where denotes the absorption coefficient,
318
amounts to 13 nm [4]. 150-m slits were used, giving an
instrumental resolution of 0.8 cm1 . The total incident laser
power for all lines was about 190 mW (5%).
The laser annealing was performed with a Nd:YAG laser,
tuned to the first harmonic ( = 1.06 m), with a pulse
duration of 72 ns. The beam diameters were 6 mm and
3 mm for irradiation energy densities of 270 mJ/cm2 and
400 mJ/cm2 , respectively. The wafers were partially exposed
to the laser beam. The irradiation was performed at room
temperature in air, as the first step in the investigation of the
atmosphere influence on the effects of laser irradiation.
2 Experimental results
Figure 1 displays a sequence of Raman spectra from
Hg0.835 Cd0.165 Te before and after the pulsed-laser anneal-
ing. The pulse wavelength and duration were kept constant,
whereas the pulse energy and spot size were varied.
In order to extract individual peak heights and widths in
the presence of a significant peak overlap, the experimental
Raman spectra were fitted by a sum of Lorentzian peaks. In
Fig. 1 the experimental points are denoted by (), thick solid
curves represent fitted spectra, and thin solid lines represent
individual peaks.
Hg1x Cdx Te is a two-mode system with two sets of Bril-
louin zone center optical phonons: (a) the CdTe-like TO1
and LO1 phonons, and (b) the HgTe-like TO2 and LO2
Fig. 1ac. Raman spectra () of Hg0.835 Cd0.165 Te sample at 10 K obtained
by 514.5 nm line of an Ar+ laser beam from: as-grown area (a), area an-
nealed by laser pulse with energy of 270 mJ/cm2 (b), and 400 mJ/cm2 (c).
Thick solid line presents the fitting curve obtained as a sum of individual
Lorentzian peaks (thin solid lines). The observed features are denoted in the
upper part of the figure
phonons [5]. For a low value of x the features originating
from the CdTe-like TO1 and LO1 phonons are too close to
be resolved and the broad feature at this position has been
denoted by LO1 &TO1 [5].
In addition to the well-known transverse and longitudinal
optical phonons of the HgTe-like and CdTe-like vibrations,
plasmons and multiphonon contributions, the Raman spectra
of Hg1x Cdx Te exhibit two more features, so-called cluster
and surface modes. The cluster mode (labeled A) is associ-
ated with a vibration of the Te3HgCd tetrahedral combi-
nation [6]. The surface mode (labeled S_) indicates the qual-
ity of the surface, but its origin is not clearly understood [6].
Figures 1b,c show the appearance of two new modes
related to TeO2 [7] after the annealing. These features at
128 cm1 and 145 cm1 are labeled as A1 and E, respec-
tively. Their appearance may be due to an excess of tellurium
oxidized in air. This excess remained after the outdiffusion
of Hg atoms from HgTe that built Hg1x Cdx Te solid solu-
tion with CdTe. Very intensive Hg outdiffusion is caused by
temperature increase and surface layers melting due to laser
irradiation [2, 3]. In this way, the modes A1 and E can be used
as indicators of the Hg outdiffusion.
2.1 Frequencies of Raman modes
It is obvious from Fig. 1a that the Raman spectrum from the
as-grown surface is dominated by the CdTe-like LO1 &TO1 ,
Fig. 2ac. The frequency positions of TO2 , LO2 and LO1 &TO1 modes in
Hg1x Cdx Te, for x = 0.165 () and x = 0.18 (4), measured at different
distances from the sample center before and after the annealing by laser
pulses with energies of 270 mJ/cm2 and 400 mJ/cm2

HgTe-like LO2 , and TO2 phonon modes at 156.5 cm1 ,
141.5 cm1 , and 120 cm1 , respectively, and by the clus-
ter mode (A) and surface mode (S_) at 135 cm1 and
132 cm1 , respectively [7]. Figures 1b,c show slightly
shifted LO2 , TO2 , and LO1 &TO1 phonon modes, and strongly
suppressed cluster and vanishing S_ modes, after the anneal-
ing. Figure 2 presents the frequency positions of TO 2 , LO2 ,
and LO1 &TO1 Raman modes in Hg1x Cdx Te for x = 0.165
and x = 0.18, before and after laser annealing with two dif-
ferent energies, and at different distances from the sample
center. It can be seen that the positions of modes for non-
treated areas for both samples are within an experimental
error of 0.8 cm1 . There is no significant change in the pos-
ition of the LO1 &TO1 mode after the annealing, i.e., its shift
is within the experimental error. On the other side, the fre-
quencies of LO2 and TO2 modes for both samples decrease
after the annealing. The reduction exceeds the experimental
error, which is particularly obvious for LO2 mode.
2.2 Mode broadening with laser annealing
Full widths at half maximum (linewidths) of the LO1 &TO1
mode before and after the annealing versus the position
across 7-mm-wide samples of Hg1x Cdx Te, for x = 0.165
and x = 0.18, are shown in Fig. 3. Note that the left parts of
the sample surfaces were irradiated by Nd:YAG laser pulses
with an energy of 270 mJ/cm2 whereas the right ones were
Fig. 3a,b. Full width at half maximum (linewidth) of the LO1 &TO1
mode at the as-grown and annealed surfaces of Hg0.835 Cd0.165 Te (a) and
Hg0.82 Cd0.18 Te (b)
319
irradiated by pulses with an energy of 400 mJ/cm2 . An in-
crease in the mode width after the annealing is obvious. The
broadening of the LO1 &TO1, feature for most points is larger
for the higher annealing energy. Only the linewidth for the
area at the edge of the Hg0.835 Cd0.165 Te sample irradiated by
270 mJ/cm2 energy is in the range of those for the areas irra-
diated by 400 mJ/cm2 energy.
2.3 Resonant Raman study of compositional changes
Resonant Raman scattering with photon energies of between
2.41 and 2.54 eV has been used to study the alloy composition
change in Hg1x Cdx Te (x = 0.18) caused by laser anneal-
ing. In Fig. 4, we show the Raman spectra obtained at 10 K
from as-grown Hg0.82 Cd0.18 Te sample for three wavelengths
of the incident Ar+ laser beam. The HgTe-like TO2 and LO2 ,
clustering and CdTe-like LO1 &TO1 modes are clearly visible
in the Raman spectra obtained for all wavelengths. However,
a surface mode at 131 cm1 , labeled as S_, is distinct only
in Fig. 4c for a wavelength of 514.5 nm. An additional feature
at 111 cm1 , denoted by P1 , is observed in the spectrum
for a wavelength of 496.5 nm. This feature is characteris-
tic of HgTe and Hg-rich Hg1x Cdx Te but its origin is not
well understood [8]. It may arise from the acoustic mode of
HgTe type activating by structural disordering of the HgCdTe
lattice [9].
Fig. 4ac. Raman spectra () from as-grown Hg0.82 Cd0.18 Te sample at
10 K at various wavelengths of an Ar+ laser beam: 488 nm (a), 496.5 nm
(b), 514.5 nm (c). The solid line presents the fitting curve obtained as a sum
of individual Lorentzian peaks. The observed features are denoted in the
upper part of the figure
320
Fig. 5ac. Raman spectra () from annealed Hg0.82 Cd0.18 Te sample at 10 K
at various wavelengths of an Ar+ laser beam: 488 nm (a), 496.5 nm (b),
514.5 nm (c). The solid line presents the fitting curve obtained as a sum of
individual Lorentzian peaks. The observed features are denoted in the upper
part of the figure
Figure 5 shows Raman spectra from an area of
a Hg0.82 Cd0.18 Te sample annealed by two 72-ns Nd:YAG
laser pulses with an energy density of about 400 mJ/cm2 .
Besides TO2 , LO2 , cluster, and LO1 &TO1 modes charac-
teristic of as-grown Hg1x Cdx Te, the features originating
from tetragonal TeO2 [7], created at the sample surface under
the laser annealing conditions, are clearly visible. For all
photon energies they are at frequencies of 128 cm1 and
145 cm1 .
Strong wavelength-dependent effects are evident in the
spectra in Figs. 4 and 5. Integrated Raman intensities (peak
areas) of the TO2 , LO2 , cluster, and LO1 &TO1 modes were
obtained by the fitting procedure mentioned. Their dependen-
cies on the laser photon energy before and after the annealing
are shown in Fig. 6.
Figure 6a shows that the integrated Raman intensities for all
four phonon modes decrease as the energy increases from 2.41
to 2.54 eV. This could be expected as the LO2, A, and LO1 &TO1
modes are resonantly enhanced near the E 1 electronic transition
of Hg1x Cdx Te [10]. The amount of E 1 at 10 K was estimated
from the E 1 compositional dependence [4] for x = 0.18 and its
temperature dependence [11] extrapolated to 10 K. The pos-
ition of E 1 = 2.38 eV is denoted by the arrow in Fig. 6a. Note
that the resonance of the TO2 mode has a very distinct shape
and indicates that an even stronger resonance may occur at the
E 1 + 1 edge at about 3 eV [10].
Fig. 6a,b. Integrated intensities of the four Raman modes (TO2 ( ), A (),
LO2 (N) and LO1 &TO1 ()) as a function of the exciting laser photon
energy for as-grown (a) and annealed (b) sample. Arrows in figures a
and b indicate estimated position of the E 1 optical feature for x = 0.18 and
x = 0.3, respectively
The integrated Raman intensities of the relevant modes
after annealing as a function of laser photon energy are shown
in Fig. 6b. All four phonon modes show maximum intensities
at a photon energy of about 2.5 eV. The arrow in Fig. 6b indi-
cates the position of E 1 = 2.473 eV, estimated for x = 0.3 at
10 K.
2.4 Disorder-induced effects on Raman spectra
The intensity of the Raman modes gives information about
crystallinity, which may be reduced in crystals damaged by
laser irradiation or other means. The strengths and frequen-
cies of the Raman phonon bands can also determine the de-
gree of alloying in a ternary material such as Hg1x Cdx Te.
The ratio of the LO2 to the TO2 mode intensity ver-
sus position across the Hg0.835 Cd0.165 Te and Hg0.82 Cd0.18 Te
samples is presented in Figs. 7a,b, respectively. This ratio
increases drastically after the annealing, in addition to a de-
crease in strength of both modes. As we can see in Fig. 7a,
the I(LO2 )/I(TO2 ) ratio for Hg0.835 Cd0.165 Te is greater for
a higher laser annealing energy for most points. Only at the
edge of the sample does this ratio have a similar value for
both applied laser-annealing energies. On the contrary, the
I(LO2 )/I(TO2 ) ratio for Hg0.82 Cd0.18 Te (Fig. 7b) is smaller
for the higher pulse energy.

Fig. 7a,b. Ratio of the LO2 to the TO2 mode intensity vs distance from the
sample center before and after the annealing of Hg1x Cdx Te for x = 0.165
(a) and x = 0.18 (b)
In addition, the Raman spectra obtained by using the
496.5 nm laser line before (Fig. 4b) and after (Fig. 5b) the an-
nealing show the influence of irradiation on the P1 mode at
111 cm1 . The annealing causes an enhancement in the in-
tensity of this mode as well as a great increase in the P1 to
TO2 mode intensity ratio I(P1 )/I(TO2 ).
3 Discussion
The annealing of Hg1x Cdx Te in air by high-energy pulses
from a Nd:YAG laser causes the following effects on Raman
spectra: (i) the appearance of new Raman features at about
128 and 145 cm1 , ascribed to tetragonal TeO2 created at the
sample surface; (ii) strong suppression of the cluster mode
and vanishing of the surface mode; (iii) a reduction in fre-
quencies of the TO2 and the LO2 modes; (iv) broadening of
the LO1 &TO1 mode; (v) a shift in the maximum resonant
enhancement for the TO2 , LO2 , A, and LO1 &TO1 modes to
higher photon energy; (vi) a significant increase in the ratios
of the LO2 to TO2 mode intensity I(LO2 )/I(TO2 ) and the P1
to TO2 mode intensity I(P1 )/I(TO2 ).
The appearance of features related to TeO2 may be the re-
sult of an excess of tellurium oxidized in air [7]. This excess
remained after the intensive outdiffusion of Hg atoms caused
by the temperature increase and the melting of the surface
layers due to laser irradiation.
The suppression of the cluster mode and the vanishing of
the surface mode could be a consequence of changes in local
321
structural order and surface inhomogeneities induced by the
rapid quench during the laser annealing process. Under these
conditions the intensity of the cluster mode may be trans-
ferred to the LO2 mode [10].
The reduction in the frequency of the LO2 mode, may
be a consequence of enhancement in the composition of
Hg1x Cdx Te caused by Hg outdiffusion during laser irradi-
ation. The broadening of the TO2 mode and its shift to the TO
mode frequencies of pure HgTe, which is at about 118 cm1
at 10 K [8], may be caused by a segregation process during
solidification of the surface layers after laser irradiation [3].
The softening of the LO2 and TO2 modes may also refer to
a lower degree of alloying after nonequilibrium melting and
solidification induced by laser irradiation.
The broadening of the LO1 &TO1 mode may be a con-
sequence of the surface disorder and inhomogeneities and
the concentration gradient near the surface. This gradient
is caused by an outdiffusion and segregation process in-
duced by melting and solidification under laser annealing
conditions. Hg-concentration changes due to irradiation are
determined by numerical simulation of mercury diffusion
in Hg1x Cdx Te, which includes the existence of Hg out-
diffusion and segregation during and after the laser irradi-
ation [2, 3]. The results of this numerical calculation of Hg-
concentration profiles in Hg0.82 Cd0.18 Te after irradiation by
pulses with two different laser energies are presented in
Fig. 8. The shaded area in Fig. 8 refers to the probing depth
of light for Raman measurement (of about 13 nm). The aver-
age Hg concentrations in the surface layer (up to the depth
of 40 nm) for both applied pulse energies are similar and
correspond to a composition of about 0.3(0.025). However,
the Hg concentration slopes in this layer (except for the first
7 nm) are opposite to each other. A difference in concentra-
tion profiles for the two applied annealing energies may be
caused by great segregation during solidification after irradi-
ation by higher laser energy [3]. More intensive segregation
may correspond to the much higher maximum temperature at
the sample surface for higher pulse energy. Namely, the max-
imum temperature for laser energy of 270 mJ/cm2 is about
714 C, compared to 810 C for 400 mJ/cm2 .
Fig. 8. Calculated Hg-concentration profiles in Hg0.82 Cd0.18 Te after the an-
nealing by laser pulses with energy of 270 mJ/cm2 (broken curve) and
400 mJ/cm2 (solid curve). Shaded area refers to penetration depth of Ra-
man scattering
322
The observed shift (Fig. 6) of the maximum resonant en-
hancement for the TO2, LO2 , A, and LO1 &TO1 modes of
the annealed sample to a higher photon energy corresponds
to an increase in composition from x = 0.18 to x 0.3. This
is in good agreement with average values of x, predicted
by numerical calculation of the Hg concentration changes in
Hg1x Cdx Te caused by laser annealing under the same condi-
tions (presented in Fig. 8). A somewhat higher Hg concentra-
tion at the sample surface than the one that corresponds to the
composition of x 0.3 could be a consequence of the men-
tioned segregation process for that laser annealing energy.
A drastic increase in the LO2 to the TO2 mode inten-
sity ratio after the annealing (presented in Fig. 7) points to
the crystalline imperfections induced by laser irradiation. The
defect-induced LO phonon scattering increases as a result of
the increasing number of defects, which mediate this scatter-
ing mechanism [12]. Only for large defect concentrations is
this increase in defect concentration offset by the broadening
of the resonance in scattering efficiency. This also leads to
a decrease in the LO scattering strength in heavily damaged
material [12]. As can be seen in Fig. 7a, the I(LO2 )/I(TO2 )
ratio at the edge of the Hg0.835 Cd0.165 Te sample annealed by
the laser pulse energy of 270 mJ/cm2 has a larger value than
that in the central part of the sample. This increase can be
explained by the imperfections that may be induced by the
mechanical defects at the edges of the sample. The behav-
ior of the I(LO2 )/I(TO2 ) ratio for the Hg0.82 Cd0.18 Te sample
with increasing laser annealing energy deviates from the ex-
pected one. It may be a consequence of a better crystallinity
of that sample after the irradiation by higher laser energy, or
different conditions for transfer of the intensity of the cluster
mode to the LO2 mode.
Regarding the nature of P1 mode [9], the I(P1 )/I(TO2 )
ratio could be used as a quantitative measure of the relative
degree of alloying in the Hg1x Cdx Te lattice produced dur-
ing annealing. An increase in the ratio after laser irradiation
points to the lower degree of alloying caused by Hg outdiffu-
sion and segregation.
4 Conclusions
The results presented in this paper confirm that the reso-
nant Raman scattering is a powerful technique for study-
ing the structural ordering and alloy composition changes in
Hg1x Cdx Te induced by high-power laser irradiation. The
appearance of the features related to TeO2 points to the Hg
outdiffusion since it produces an excess of Te at the annealed
surface. Great suppression of the cluster and surface modes,
increases in the LO1 &TO1 mode width, and the LO2 to TO2
mode intensity ratio after the annealing indicate structural
disorder as a consequence of laser-induced nonequilibrium
melting and solidification. On the other hand, the decrease in
LO2 and TO2 mode frequencies and the increase in the P1 to
TO2 mode intensity ratio may be an indicator of a decrease in
the degree of alloying caused by irradiation-induced outdiffu-
sion and segregation-like processes. These results confirm the
main assumptions used in theoretical model for investigation
of the effects of laser irradiation on Hg1x Cdx Te. The best
indicator of the compositional changes is the observed shift
in the maximum resonant enhancement for the TO2 , LO2 , A,
and LO1 &TO1 modes in Raman spectra from the annealed
sample. The higher photon energy corresponds to an increase
in composition from x = 0.18 to x 0.3 as a result of the Hg
outdiffusion. This is in good agreement with the calculated
Hg-concentration profile obtained from numerical simulation
under the same conditions.
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