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Abstract. Resonant Raman scattering has been used to study phonon frequencies are sensitive to the interatomic forces and
the effects of high-power laser annealing on Hg1x Cdx Te for the ion masses, phonon Raman scattering is an effective probe
x = 0.165 and x = 0.18. The annealing was performed in air of local structural order. In addition, the intensities of Ra-
with a Nd:YAG laser tuned to the first harmonic. A pulse du- man lines are sensitive to the details of the electronic band
ration of 72 ns and irradiation energy densities of 270 and structure of the semiconductors, which reflects alloy compo-
400 mJ/cm2 were used. Information on both the structural or- sition [1]. Thus the Raman effect is sensitive to both alloy
dering and the alloy composition in irradiated Hg1x Cdx Te composition and structural order. The resonant Raman scat-
was obtained by resonance Raman spectroscopy with laser tering with photon energies between 2.35 and 2.7 eV has been
photon energies of between 2.41 and 2.54 eV. The presented used to study both the alloy composition and the local struc-
Raman spectra from annealed samples indicate structural dis- tural order in Hg1x Cdx Te for x values near 0.25, depending
order and a decrease in the degree of alloying as a result on the growth conditions [1].
of Hg outdiffusion and segregation caused by laser-induced In order to investigate the structural and compositional
nonequilibrium melting and solidification. Moreover, a shift changes at the Hg1x Cdx Te surface irradiated by Nd:YAG
of the maximum resonant enhancement for the TO2 , LO2 , A, laser pulses with energies appropriate for laser annealing, res-
and LO1 &TO1 modes in the case of a Hg0.82 Cd0.18 Te sam- onance Raman scattering experiments before and after the
ple, annealed by 400 mJ/cm2 laser pulse, to higher photon irradiation were performed. The results presented in this pa-
energy points to an increase in the composition from x = 0.18 per show resonant behavior of the HgTe-like TO2 and LO2 ,
to x 0.3. clustering, and CdTe-like LO1 &TO1 modes for as-grown and
annealed samples. They are discussed and analyzed on the
PACS: 42.55P; 81.40Z basis of our earlier numerical analyses of laser annealing of
Hg1x Cdx Te [2, 3].
amounts to 13 nm [4]. 150-m slits were used, giving an phonons [5]. For a low value of x the features originating
instrumental resolution of 0.8 cm1 . The total incident laser from the CdTe-like TO1 and LO1 phonons are too close to
power for all lines was about 190 mW (5%). be resolved and the broad feature at this position has been
The laser annealing was performed with a Nd:YAG laser, denoted by LO1 &TO1 [5].
tuned to the first harmonic ( = 1.06 m), with a pulse In addition to the well-known transverse and longitudinal
duration of 72 ns. The beam diameters were 6 mm and optical phonons of the HgTe-like and CdTe-like vibrations,
3 mm for irradiation energy densities of 270 mJ/cm2 and plasmons and multiphonon contributions, the Raman spectra
400 mJ/cm2 , respectively. The wafers were partially exposed of Hg1x Cdx Te exhibit two more features, so-called cluster
to the laser beam. The irradiation was performed at room and surface modes. The cluster mode (labeled A) is associ-
temperature in air, as the first step in the investigation of the ated with a vibration of the Te3HgCd tetrahedral combi-
atmosphere influence on the effects of laser irradiation. 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
2 Experimental results related to TeO2 [7] after the annealing. These features at
128 cm1 and 145 cm1 are labeled as A1 and E, respec-
Figure 1 displays a sequence of Raman spectra from tively. Their appearance may be due to an excess of tellurium
Hg0.835 Cd0.165 Te before and after the pulsed-laser anneal- oxidized in air. This excess remained after the outdiffusion
ing. The pulse wavelength and duration were kept constant, of Hg atoms from HgTe that built Hg1x Cdx Te solid solu-
whereas the pulse energy and spot size were varied. tion with CdTe. Very intensive Hg outdiffusion is caused by
In order to extract individual peak heights and widths in temperature increase and surface layers melting due to laser
the presence of a significant peak overlap, the experimental irradiation [2, 3]. In this way, the modes A1 and E can be used
Raman spectra were fitted by a sum of Lorentzian peaks. In as indicators of the Hg outdiffusion.
Fig. 1 the experimental points are denoted by (), thick solid
curves represent fitted spectra, and thin solid lines represent
individual peaks. 2.1 Frequencies of Raman modes
Hg1x Cdx Te is a two-mode system with two sets of Bril-
louin zone center optical phonons: (a) the CdTe-like TO1 It is obvious from Fig. 1a that the Raman spectrum from the
and LO1 phonons, and (b) the HgTe-like TO2 and LO2 as-grown surface is dominated by the CdTe-like LO1 &TO1 ,
HgTe-like LO2 , and TO2 phonon modes at 156.5 cm1 , irradiated by pulses with an energy of 400 mJ/cm2 . An in-
141.5 cm1 , and 120 cm1 , respectively, and by the clus- crease in the mode width after the annealing is obvious. The
ter mode (A) and surface mode (S_) at 135 cm1 and broadening of the LO1 &TO1, feature for most points is larger
132 cm1 , respectively [7]. Figures 1b,c show slightly for the higher annealing energy. Only the linewidth for the
shifted LO2 , TO2 , and LO1 &TO1 phonon modes, and strongly area at the edge of the Hg0.835 Cd0.165 Te sample irradiated by
suppressed cluster and vanishing S_ modes, after the anneal- 270 mJ/cm2 energy is in the range of those for the areas irra-
ing. Figure 2 presents the frequency positions of TO 2 , LO2 , diated by 400 mJ/cm2 energy.
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- 2.3 Resonant Raman study of compositional changes
ferent energies, and at different distances from the sample
center. It can be seen that the positions of modes for non- Resonant Raman scattering with photon energies of between
treated areas for both samples are within an experimental 2.41 and 2.54 eV has been used to study the alloy composition
error of 0.8 cm1 . There is no significant change in the pos- change in Hg1x Cdx Te (x = 0.18) caused by laser anneal-
ition of the LO1 &TO1 mode after the annealing, i.e., its shift ing. In Fig. 4, we show the Raman spectra obtained at 10 K
is within the experimental error. On the other side, the fre- from as-grown Hg0.82 Cd0.18 Te sample for three wavelengths
quencies of LO2 and TO2 modes for both samples decrease of the incident Ar+ laser beam. The HgTe-like TO2 and LO2 ,
after the annealing. The reduction exceeds the experimental clustering and CdTe-like LO1 &TO1 modes are clearly visible
error, which is particularly obvious for LO2 mode. 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
2.2 Mode broadening with laser annealing at 111 cm1 , denoted by P1 , is observed in the spectrum
for a wavelength of 496.5 nm. This feature is characteris-
Full widths at half maximum (linewidths) of the LO1 &TO1 tic of HgTe and Hg-rich Hg1x Cdx Te but its origin is not
mode before and after the annealing versus the position well understood [8]. It may arise from the acoustic mode of
across 7-mm-wide samples of Hg1x Cdx Te, for x = 0.165 HgTe type activating by structural disordering of the HgCdTe
and x = 0.18, are shown in Fig. 3. Note that the left parts of lattice [9].
the sample surfaces were irradiated by Nd:YAG laser pulses
with an energy of 270 mJ/cm2 whereas the right ones were
Fig. 5ac. Raman spectra () from annealed Hg0.82 Cd0.18 Te sample at 10 K Fig. 6a,b. Integrated intensities of the four Raman modes (TO2 ( ), A (),
at various wavelengths of an Ar+ laser beam: 488 nm (a), 496.5 nm (b), LO2 (N) and LO1 &TO1 ()) as a function of the exciting laser photon
514.5 nm (c). The solid line presents the fitting curve obtained as a sum of energy for as-grown (a) and annealed (b) sample. Arrows in figures a
individual Lorentzian peaks. The observed features are denoted in the upper and b indicate estimated position of the E 1 optical feature for x = 0.18 and
part of the figure x = 0.3, respectively
Figure 5 shows Raman spectra from an area of The integrated Raman intensities of the relevant modes
a Hg0.82 Cd0.18 Te sample annealed by two 72-ns Nd:YAG after annealing as a function of laser photon energy are shown
laser pulses with an energy density of about 400 mJ/cm2 . in Fig. 6b. All four phonon modes show maximum intensities
Besides TO2 , LO2 , cluster, and LO1 &TO1 modes charac- at a photon energy of about 2.5 eV. The arrow in Fig. 6b indi-
teristic of as-grown Hg1x Cdx Te, the features originating cates the position of E 1 = 2.473 eV, estimated for x = 0.3 at
from tetragonal TeO2 [7], created at the sample surface under 10 K.
the laser annealing conditions, are clearly visible. For all
photon energies they are at frequencies of 128 cm1 and
145 cm1 . 2.4 Disorder-induced effects on Raman spectra
Strong wavelength-dependent effects are evident in the
spectra in Figs. 4 and 5. Integrated Raman intensities (peak The intensity of the Raman modes gives information about
areas) of the TO2 , LO2 , cluster, and LO1 &TO1 modes were crystallinity, which may be reduced in crystals damaged by
obtained by the fitting procedure mentioned. Their dependen- laser irradiation or other means. The strengths and frequen-
cies on the laser photon energy before and after the annealing cies of the Raman phonon bands can also determine the de-
are shown in Fig. 6. gree of alloying in a ternary material such as Hg1x Cdx Te.
Figure 6a shows that the integrated Raman intensities for all The ratio of the LO2 to the TO2 mode intensity ver-
four phonon modes decrease as the energy increases from 2.41 sus position across the Hg0.835 Cd0.165 Te and Hg0.82 Cd0.18 Te
to 2.54 eV. This could be expected as the LO2, A, and LO1 &TO1 samples is presented in Figs. 7a,b, respectively. This ratio
modes are resonantly enhanced near the E 1 electronic transition increases drastically after the annealing, in addition to a de-
of Hg1x Cdx Te [10]. The amount of E 1 at 10 K was estimated crease in strength of both modes. As we can see in Fig. 7a,
from the E 1 compositional dependence [4] for x = 0.18 and its the I(LO2 )/I(TO2 ) ratio for Hg0.835 Cd0.165 Te is greater for
temperature dependence [11] extrapolated to 10 K. The pos- a higher laser annealing energy for most points. Only at the
ition of E 1 = 2.38 eV is denoted by the arrow in Fig. 6a. Note edge of the sample does this ratio have a similar value for
that the resonance of the TO2 mode has a very distinct shape both applied laser-annealing energies. On the contrary, the
and indicates that an even stronger resonance may occur at the I(LO2 )/I(TO2 ) ratio for Hg0.82 Cd0.18 Te (Fig. 7b) is smaller
E 1 + 1 edge at about 3 eV [10]. for the higher pulse energy.
321
3 Discussion
The observed shift (Fig. 6) of the maximum resonant en- ing the structural ordering and alloy composition changes in
hancement for the TO2, LO2 , A, and LO1 &TO1 modes of Hg1x Cdx Te induced by high-power laser irradiation. The
the annealed sample to a higher photon energy corresponds appearance of the features related to TeO2 points to the Hg
to an increase in composition from x = 0.18 to x 0.3. This outdiffusion since it produces an excess of Te at the annealed
is in good agreement with average values of x, predicted surface. Great suppression of the cluster and surface modes,
by numerical calculation of the Hg concentration changes in increases in the LO1 &TO1 mode width, and the LO2 to TO2
Hg1x Cdx Te caused by laser annealing under the same condi- mode intensity ratio after the annealing indicate structural
tions (presented in Fig. 8). A somewhat higher Hg concentra- disorder as a consequence of laser-induced nonequilibrium
tion at the sample surface than the one that corresponds to the melting and solidification. On the other hand, the decrease in
composition of x 0.3 could be a consequence of the men- LO2 and TO2 mode frequencies and the increase in the P1 to
tioned segregation process for that laser annealing energy. TO2 mode intensity ratio may be an indicator of a decrease in
A drastic increase in the LO2 to the TO2 mode inten- the degree of alloying caused by irradiation-induced outdiffu-
sity ratio after the annealing (presented in Fig. 7) points to sion and segregation-like processes. These results confirm the
the crystalline imperfections induced by laser irradiation. The main assumptions used in theoretical model for investigation
defect-induced LO phonon scattering increases as a result of of the effects of laser irradiation on Hg1x Cdx Te. The best
the increasing number of defects, which mediate this scatter- indicator of the compositional changes is the observed shift
ing mechanism [12]. Only for large defect concentrations is in the maximum resonant enhancement for the TO2 , LO2 , A,
this increase in defect concentration offset by the broadening and LO1 &TO1 modes in Raman spectra from the annealed
of the resonance in scattering efficiency. This also leads to sample. The higher photon energy corresponds to an increase
a decrease in the LO scattering strength in heavily damaged in composition from x = 0.18 to x 0.3 as a result of the Hg
material [12]. As can be seen in Fig. 7a, the I(LO2 )/I(TO2 ) outdiffusion. This is in good agreement with the calculated
ratio at the edge of the Hg0.835 Cd0.165 Te sample annealed by Hg-concentration profile obtained from numerical simulation
the laser pulse energy of 270 mJ/cm2 has a larger value than under the same conditions.
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- References
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- 1. A. Compaan, R.C. Bowman, Jr., D.E. Cooper: Appl. Phys. Lett. 56,
pected one. It may be a consequence of a better crystallinity 1055 (1990)
of that sample after the irradiation by higher laser energy, or 2. M.M. Jevtic, M.J. Scepanovic: Appl. Phys. A 53, 332 (1991)
different conditions for transfer of the intensity of the cluster 3. M. Scepanovic, M. Jevtic: Phys. Stat. Sol. (a) 147, 379 (1995)
4. L. Vina, C. Umbach, M. Cardona, L. Vodopyanov: Phys. Rev. B 29,
mode to the LO2 mode.
6752 (1984)
Regarding the nature of P1 mode [9], the I(P1 )/I(TO2 ) 5. P.M. Amirtharaj, K.K. Tiong, P. Parayanthal, F.H. Pollak, J.K. Furdyna:
ratio could be used as a quantitative measure of the relative J. Vac. Sci. Technol. A 3, 226 (1985)
degree of alloying in the Hg1x Cdx Te lattice produced dur- 6. P.M. Amirtharaj, N.K. Dhar, J. Baars, H. Seelewind: Semicond. Sci.
ing annealing. An increase in the ratio after laser irradiation Technol. 5, S68 (1990)
7. M. Scepanovic, M. Jevtic: Phys. Stat. Sol. (a) 157, 515 (1996)
points to the lower degree of alloying caused by Hg outdiffu- 8. M.L. Bansal, A. Ingale, A.P. Roy: Phys. Rev. B 43, 7020 (1991)
sion and segregation. 9. Biao Li, J.H. Chu, H.J. Ye, S.P. Guo, W. Jiang, D.Y. Tang: Appl. Phys.
Lett. 68, 3272 (1996)
10. A. Compaan, R.C. Bowman, Jr., D.E. Cooper: Semicond. Sci. Technol.
4 Conclusions 5, S73 (1990)
11. A. Ksendzov, F.H. Pollak, J.A. Wilson, V.A. Cotton: J. Appl. Phys. 66,
5528 (1989)
The results presented in this paper confirm that the reso- 12. J. Wagner, P. Koidl, K.H. Bachem, C. Uzan-Saguy, R. Kalish, M. Bur-
nant Raman scattering is a powerful technique for study- der: J. Appl. Phys. 73, 2739 (1993)