Park Et Al-2013-Physica Status Solidi (A)

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Phys. Status Solidi A 210, No. 2, 267275 (2013) / DOI 10.1002/pssa.201228555
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applications and materials science
Structural and optical properties of

phase-change amorphous and crystalline
Ge1 xTex (0 < x < 1) thin films
Jun-Woo Park1, Misun Song2, Seokhyun Yoon2, Hyungkwang Lim3, Doo Seok Jeong3, Byung-ki Cheong3,
,1
and Hosun Lee*
1
Department of Applied Physics, Kyung Hee University, 446-701 Yong-In, South Korea
Department of Physics, Ewha Womans University, 120-750 Seoul, South Korea
3
Electronic Materials Center, Korea Institute of Science and Technology, 136-791 Seoul, South Korea
2
Received 17 August 2012, revised 25 September 2012, accepted 1 October 2012

Published online 23 October 2012
Keywords germanium telluride, joint density of states, Raman spectroscopy, spectroscopic ellipsometry
author: e-mail hlee@khu.ac.kr, Phone: 82 31 201 2412, Fax: 82 31 204 8122
Ec
Ed
a-GeTe
Ea
Eb
Ge1 xTex thin films were grown using thermal coevaporation

deposition. The dielectric functions and the phonon modes
of amorphous (a-) and crystalline (c-) Ge1 xTex films were
measured using spectroscopic ellipsometry and Raman spectroscopy in order to investigate electronic and vibrational
properties of these alloys. Using the second derivative spectra
of the dielectric functions of a-Ge1 xTex alloys and the
standard critical point (SCP) model, we obtained optical
transition energies for the a-Ge1 xTex alloys. The optical
transition energies were not only consistent with the density
of states (DOS) reported in the literature, but also provided
more detailed structures for the joint density of states (JDOS)
of a-Ge1 xTex.
d /dE (arb. units)
* Corresponding
3
4
5
Photon Energy (eV)
The second derivative spectra of d2e(E)/dE2 for amorphous

GeTe. The transition energies were estimated using SCP model
(short arrows) and were compared to those of photoemission
spectroscopy from literature (long arrows).
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1 Introduction Recently, GeTe has received renewed

attention as a promising phase-change memory material
for high temperature use, such as in automobiles, due to
its higher crystallization temperature than conventional
Ge2Sb2Te5 (GST) [13]. Alloying four-fold coordinated
Ge with two-fold coordinated Te renders amorphous
chalcogenides with high thermal stability via the formation
of covalent bond network structures. It has been shown,
however, that the resulting GeTe alloys have crystallization
kinetics that hardly vary monotonously with Ge content but
exhibit rather complex composition dependence behavior.
Specifically the crystallization temperature and crystallization rate reach a minimum and maximum, respectively,
with equiatomic GeTe. Therefore, a detailed study of the
physical characteristics of GeTe alloys, specifically the

atomic and electronic structures of the amorphous and
crystalline phases, was deemed necessary to gain a better
understanding of the observed behavior as well as to insure
proper applications of these materials.
Regarding atomic structure, investigation of vibrational
modes can reveal information about the local atomic
structures of Ge1 xTex alloys. Several groups have investigated the phonon modes of a-GeTe and c-GeTe [49].
In particular, Andrikopoulos et al. [4, 5] and Mazzarello
et al. [9] studied in detail the phonon modes of a-GeTe
and Gourvest et al. [6] studied those of Ge-rich Ge1 xTex.
Additionally, De Bastiani et al. [7] investigated the effect of
ion-implantation on the phonon modes of GeTe thin films.
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J.-W. Park et al.: Properties of phase-change amorphous and crystalline Ge1 xTex thin films
However, the phonon modes of Te-rich Ge1 xTex alloy thin

films have not yet been reported. The presence of GeGe
homopolar bonds has been controversial for crystalline
GeTe. For example, Maeda and Wakagi observed GeGe
bonds only for a-GeTe and Kolobov et al. found about 10%
GeGe bonds even for c-GeTe using X-ray absorption fine
structure spectroscopy [10, 11].
Understanding the electronic properties of the amorphous phase of Ge1 xTex alloys may lead to a comprehensive understanding of the amorphous phase of stoichiometric
GeTe thin films. The electronic structure of the valence
band for amorphous GeTe has been studied using ultraviolet photoemission spectroscopy (UPS) 12]. However,
few groups have studied the electronic structure of the
conduction band of a-Ge1 xTex alloys. Hosokawa et al.
investigated the density of states (DOS) of both the valence
and conduction bands of a-GeTe and a-GeSe using UPS
and inverse photoemission spectroscopy (IPES) [12]. The
electronic structures of a-Ge1 xTex alloys, e.g., dielectric
functions and optical gap energies, have not been investigated as a function of Te composition. Dielectric function is
a multiplication of oscillator strength and the joint density
of states (JDOS) [13], and JDOS is a convolution of the
DOS of both the valence and conduction bands. Therefore,
dielectric function can provide detailed information about
the structures of both the valence and conduction bands.
However, the dielectric functions of a-Ge1 xTex alloys have
not previously been investigated.
In this work, Raman spectroscopy was used to
characterize the phonon modes of as-grown and annealed
Ge1 xTex thin films prepared by a thermal co-evaporation
technique. Spectroscopic ellipsometry was also employed to
measure the dielectric functions and to estimate the optical
(band) gap energies of amorphous (crystalline) Ge1 xTex
thin films from absorption coefficients as a function of Te
composition. Finally, we discussed the optical properties of
amorphous Ge1 xTex alloys such as the dielectric functions
and the optical transition energies.
2 Experiments We grew 120 nm-thick Ge1 xTex
(x 0.273, 0.533, 0.667) thin films on SiO2 (300 nm)/Si
substrates or 5 nm-thick ZnS(SiO2)-coated quartz using
thermal coevaporation of Ge and Te; each film was denoted,
respectively, as GeTe, GeTe, and GeTe hereafter. Film
composition was estimated using an electron probe microanalyzer with an error of 0.002. The as-grown amorphous
films were annealed in an Ar gas flow for 10 min for
crystallization. The annealing temperatures were 125 and
350 8C for both the GeTe and GeTe films, and 125, 250, and
400 8C for the GeTe films; crystallization was complete at
350 8C for the GeTe and GeTe films, and at 400 8C for the
GeTe films. XRD was used to verify structural characteristics
of the annealed films. GeTe4 films (denoted as GeTe
hereafter), grown at RT, were annealed at 350 8C for 5 or
10 min. The composition was determined to be Ge0.187Te0.813.
The dielectric functions and phonon modes of Ge1 xTex
films were measured using spectroscopic ellipsometry and
Raman spectroscopy, respectively. Ellipsometric angles

(C, D) were measured at various angles of incidence at
room temperature and Raman spectra of Ge1 xTex were
obtained at an excitation wavelength of 488 nm with the
lowest possible laser power (0.1 mW) to prevent laserinduced annealing. Note that the compositions of GeTe,
GeTe, GeTe, and GeTe were roughly, Ge2Te, GeTe,
GeTe2, and GeTe4, respectively.
3 Results and discussion
3.1 X-ray diffraction Figure 1 shows XRD spectra of
the crystalline phases of GeTe, GeTe, and GeTe thin films
grown on SiO2/Si substrates. In Fig. 1, R denotes the
rhombohedral (RH) phase of GeTe, Ge denotes the facecentered-cubic (FCC) phase of Ge grains, Te denotes the
hexagonal (HEX) phase of Te grains, and GeTe4 denotes the
cubic phase of GeTe4 grains. The (202), (220), (042) peaks of
RH GeTe were present for all Te compositions. The XRD
spectrum of GeTe was very similar to that of GeTe
except for the presence of additional FCC (111) and (220) Ge
phase peaks. The XRD spectrum of GeTe film was very
different from those of GeTe and GeTe, and had cubic
GeTe4 peaks of (310), (222), (332), and (500), RH GeTe
peaks of (202), (220), (104), and (042), and HEX Te peaks
of (112) and (200). Therefore, it follows that the GeTe
thin film consisted of a single RH phase, the GeTe thin
film had a main RH phase of GeTe with Ge precipitates,
but the GeTe thin film had a predominant GeTe4 phase
coexisting with RH-GeTe and HEX-Te. The XRD
data suggest that precipitation of Ge phases for GeTe,
and Te and GeTe4 phases for GeTe thin films occurred
after crystallization. It appears that the GeTe4 phase is
thermodynamically much more stable than the GeTe and Te
phases. It should be noted that no sharp peak was detectable
in the XRD spectra of Ge1 xTex thin films annealed at
intermediate temperatures as well as as-grown ones, which
(2 2 2 )G T 4
(3 1 0 )G T 4
(1 1 2 )T e
(1 0 4 )R
(5 0 0 )G T 4
(3 3 2 )G T 4
(2 0 0 )T e
Intensity (arb. units)
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G eTe
(2 0 2 )R
(0 2 1 )R
(2 2 0 )R
(0 4 2 )R
(1 1 1 )G e
G eTe
(2 2 0 )G e
Ge Te
20
30
40
2 (deg.)
50
Figure 1 (online color at: www.pss-a.com) X-ray diffraction

spectra of GeTe, GeTe, and GeTe crystalline thin films grown
on SiO2/Si substrates.
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Phys. Status Solidi A 210, No. 2 (2013)
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suggests that all of the intermediate temperature-annealed

films basically consisted of amorphous phases with no longrange order. Raoux et al. reported the XRD spectra of 50-nmthick Ge1 xTex thin films on SiO2/Si substrates grown by
sputtering deposition [14], and Gourvest et al. [6] reported
XRD data that included an a-GeTe (101) peak for GeTe and
GeTe films, and a-GeTe (003) and c-Ge (111) peaks for
GeTe films, where a-GeTe stands for the RH phase of
GeTe. These XRD results are similar to our results for GeTe
and GeTe.
3.2 Raman spectroscopy Figure 2 shows Raman
spectra of Ge1 xTex thin films grown on ZnS(SiO2)-coated
quartz measured at RT. Quartz substrates were used to
eliminate Raman peaks associated with the Si substrate, and
5 nm-thick ZnS(SiO2) coatings were added to facilitate
better adhesion with the crystallized Ge1 xTex thin films.
XRD spectra of the Ge1 xTex thin films grown on
100
(a) A B
200
C
300
D E
500
400
F
+
Ge Te(X)
+
Ge Te(R2)
+
Ge Te(R1)
+
Ge Te(A)
(b)
GeTe(X)
GeTe(R1)
GeTe(A)
(c)
100
GeTe (X)
+
GeTe (R1)
+
GeTe (A)
200
300
400
-1
Raman Shift (cm )
500
Figure 2 (online color at: www.pss-a.com) Raman spectra of (a)

GeTe, (b) GeTe, and (c) GeTe thin films grown on quartz substrate, where the phonon spectra of amorphous, intermediate, and
crystalline phases are shown. A, R1, R2, and X denote amorphous,
125, 250 8C, and crystalline thin films, respectively.
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ZnS(SiO2)-coated quartz were very similar to those in

Fig. 1. Very sharp, but random, peaks near 330, 430, and
470 cm1 in the Raman spectra of GeTe thin films were
attributed to cosmic rays. The phonon modes are denoted as
A (80 cm1), A1(95 cm1), B(119 cm1), B0(120 cm1),
B1(125 cm1), B2(138 cm1), B3(151152 cm1), B4(158 cm1),
C(170 cm1), D(280 cm1), D1(300 cm1), E(330 cm1),
F(380 cm1), and G(465 cm1) in increasing order of wave
number. The measured phonon modes were assigned as
shown in Table 1 [49]. Note that the phonon modes of
a-Ge1 xTex were interpreted using either the GeTe4 nGen
(n 0, 1, 2, 3, 4) tetrahedral model of Andrikopoulos et al.
[4, 5], or the defective octahedral model of Mazzarello et al.
[9] A, C, and D modes were observed for all a-Ge1 xTex and
c-Ge1 xTex films. B mode was observed with GeTe
and GeTe films. Mode C (GeTe mode) was very sharp
for all phases and compositions. E, F, and G modes were
marginally observed and thus could be overtones or
multi-phonons of lower wave-number phonons. Raman
data also showed the phonon mode from the Te phase of
GeTe thin films. Strikingly, the phonon spectra of the
amorphous and crystalline phases were very similar for
GeTe thin films except for some peak shifts in the A mode,
seemingly consistent with a fast phase transition between
the amorphous and crystalline phases with an equiatomic
composition.
The phonon peaks of amorphous and crystalline thin
films of GeTe (GeTe4) were also examined. Figure 3
shows the (a) XRD and (b) Raman spectra of a- and
c-GeTe films. According to the XRD data, the as-grown
thin film was amorphous, but after annealing the film for
5 min, it was composed mainly of simple cubic c-GeTe4 with
a minor phase of c-GeTe. After 10 min annealing, the c-GeTe
phase disappeared and c-Te phase precipitation in addition
to the c-GeTe4 phase was observed. Since the Raman spectra
of amorphous and 5 min-annealed GeTe4 were similar, we
suspect that the GeTe was not completely crystalline after
5 min of annealing. The Raman spectra of GeTe (GeTe4)
films were very similar to those of GeTe films (GeTe2) for
both the amorphous and crystalline states. Using information
from the literature, all of the Raman peaks were identified
as follows.
(i) The A1 (95 cm1) mode almost overlapped the A
(80 cm1) mode for c-GeTe, but was very sharp for
c-GeTe, and disappeared for GeTe thin films. This
phonon mode has not been reported for Ge, Te, or GeTe
crystalline films in the literature. We assigned this
mode to Ge-Te in c-GeTe [6].
(ii) The broad B mode observed for GeTe and GeTe was
attributed to an overlap of corner-sharing GeTe4 nGen
(111 cm1, n 0) and GeTe4 nGen (127 cm1, n 1, 2,
B1 in this work), as reported in the literature [5]. The
B1 (125 cm1) and B2 (138 cm1) modes were found
for the amorphous and crystalline phases, respectively,
for GeTe and GeTe films and were distinctively
sharp. The frequency of the B1 (125 cm1) mode red 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Table 1 The measured phonon modes of Ge1 xTex thin films.

Raman shift (cm1)
literature values
corresponding bonds
phase
80
95
119
A
A1
B
88a,b,c
GeTe (bending mode)a,b,c

GeTe
a- and c-Ge1 xTex

c-GeTe
a- and c-Ge1 xTex
120
125
B0
B1
127a,b,c
138
150152
B2
B3
140.7d
162a,b
158
170
220
280
300
B4
C
C1
D
D1
157e
182a,b
218a,b
275a,b,f,g
300g
overlap of 111a,b,c
and 127a,b,c
GeTe (corner sharing GeTe4 nGen, n 1,2)b,
defective octahedrac
TeTe
GeTe (edge sharing GeTe4 n Gen, n 0)b,
defective octahedrac
TeTe
GeTe (edge sharing GeTe4 n Gen, n 1,2)b
GeTe (antisymmetric stretching)b
GeGef,g
GeGeg
c-GeTe4
a-Ge1 xTex
c-Te
a- and c-Ge1 xTex
a-Te
a- and c-Ge1 xTex
a- and c-Ge1 xTex
a- and c-Ge1 xTex
c-Ge
a
Andrikopoulos et al., Ref. [5]; bAndrikopoulos et al., Ref. [4]; cMazzarello et al., Ref. [9]; dPine and Dresselhaus, Ref. [15]; eBrodsky et al., Ref. [16]; fCoppari
et al., Ref. [17]; gGourvest et al. Ref. [6].
shifted and became B0 (120 cm1) after crystallization.

Thus, the B0 mode was attributed to the phonon mode
from the c-GeTe4 phase. The B2 (138 cm1) mode
appeared only for crystalline GeTe and GeTe
thin film and was identified as TeTe mode in c-Te
grains [6, 15]. Notably, the B3 mode (150152 cm1)
was found in the amorphous or crystalline phases of all
Te compositions and was identified as the GeTe mode
Te(110)
(510)
(a) GeTe4
(500)
(332)
(220)
10 min annealing
(222)
(721)
(600)
GeTe(012)
5 min annealing
(511)
20
30
(b)
B0
As-grown
40
50
2 (deg.)
B1 B4
GeTe(110)
60
B2
A
C
E 10 min annealing
5 min annealing
As-grown
100
200
300
400
-1
Raman Shift (cm )
500
Figure 3 (online color at: www.pss-a.com) (a) XRD and (b) Raman
spectra of amorphous and crystalline GeTe (GeTe4) films.
in edge-sharing GeTe4 nGen (n 0) tetrahedra [4, 5].

Note that B4 mode (158 cm1) was attributed to TeTe
modes in the a-Te phase, which should exist in greater
quantities with Te-rich films [16].
(iii) Investigating the phonon modes of a- and c-Ge1 xTex
thin films in Fig. 2, new phonon modes, not previously
reported in the literature, were identified such as A1
(95 cm1), B0 (120 cm1), and B4 (158 cm1), as shown
in Table 1. The phonon modes of A1 (95 cm1),
B0 (120 cm1), and B4 (158 cm1) were assigned to
c-GeTe, c-GeTe4, and a-Te phases, respectively.
All of the GeTe, GeTe, and GeTe thin films had
phonon mode D (280 cm1), which was identified as GeGe
mode. Because of the lack of crystalline Ge peaks in
the XRD spectra of GeTe and GeTe thin films, this mode
may not be related to precipitation of Ge crystals. In fact,
the D1 (300 cm1) mode appearing only in the case of the
crystallized GeTe thin film can be ascribed to the GeGe
mode in the c-Ge phase [6]. It then follows that the common
D mode may result from otherwise existing homopolar
GeGe bonds. Similar batches of GeTe, GeTe, and GeTe
thin films were investigated using the extended X-ray
absorption fine structure (EXAFS) of Choi et al. [18], and
GeGe as well as TeTe homopolar bonds were observed
for both a-GeTe and c-GeTe in agreement with the
Raman spectra of Fig. 2. Choi et al. attributed the origin of
non-negligible amount of GeGe homopolar bonds to a
substantial amount of Ge-vacancies [18]. It is surprising
that an abundance of GeGe bonds were present (as
indicated by the significant intensities of the D mode) in
all Ge1 xTex (x 0.667) thin films, including Ge-deficient
films, regardless of the bonding environments being
either tetrahedrally coordinated in amorphous GeTe or
octahedrally coordinated in crystalline GeTe. In Fig. 3(b),
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A
R1
R2 40
X
40
20
20
0
1
60
2
3
4
5
Photon Energy (eV)
(b) GeTe
0
6
A
R1 60
X
40
2
40
1
20
20
0
-20
40
3
4
5
Photon Energy (eV)
(c) GeTe+
0
6
A
R1
X 40
20
2
3.3 Spectroscopic ellipsometry The dielectric

functions of Ge1 xTex thin films were estimated via
multi-layer model analysis of the ellipsometric angles. We
assumed four phases: surface roughness, Ge1 xTex, SiO2,
and Si substrate. Furthermore, the parametric optical
constant (POC) model was used as the model dielectric
function of Ge1 xTex thin films [20].
Figure 4 shows the dielectric functions (e e1 ie2)
of Ge1 xTex films (a) GeTe, (b) GeTe, and (c) GeTe
grown on SiO2/Si substrates. The dielectric functions of the
a-Ge1 xTex films did not discernibly change after annealing
at the given intermediate temperatures. After complete
crystallization, the dielectric functions changed appreciably
from those of a-Ge1 xTex, with the degrees of changes
apparently increasing in the order of GeTe, GeTe, and
GeTe. The amplitude of the imaginary dielectric functions
increased substantially in the photon energy range of visible
light between 1 and 3 eV after crystallization, giving rise
to the large optical contrast needed for optical memory
applications. Note that the complex refractive index, n ik,
is the square root of e (e1 ie2).
The optical band gap energies of the amorphous and
crystalline phases can be estimated using the absorption
coefficient (a) and a linear extrapolation method as shown
in Fig. 5. The absorption coefficient can be estimated as
a 4pk/l. The optical
(band) gap energy is given by

aEn C E Eg , where n 1/2 for the optical (band)
gap of amorphous (indirect gap and crystalline) semiconductors and n 2 for direct gap semiconductors with a
crystalline phase [21]. The optical gap energies of the
amorphous (crystalline) phase were 0.74 (0.72), 0.75 (0.73),
0.89 (0.59) eV, respectively, for GeTe, GeTe, and GeTe
films. The indirect band gap energy of the crystalline phases
decreased with increasing metallic Te content. The 20 meV
decrease in the optical gap energy after crystallization of
GeTe and GeTe was the smallest observed.
In comparison, Park et al. reported a larger decrease in
energy of 190 meV for GeTe because they estimated the
optical gap energies of 0.80 and 0.61 eV for amorphous and
crystalline GeTe films, respectively [22]. This discrepancy
may arise from the fact that the linear extrapolation method
may be significantly affected by subgap states. Note that the
amorphous Ge1 xTex films were homogeneous, whereas
the crystalline GeTe (GeTe) films had a major GeTe
(GeTe4) phase with Ge (GeTe and Te) precipitates. There-
(a) Ge+Te
the D mode was absent for both amorphous and

crystalline GeTe (i.e., Ge0.187Te0.813). Uemura et al. also
observed that the D mode was absent for a-Ge1 xTex
(0.80 x 0.84) using Raman spectroscopy [19]. We
presume that the presence of unexpected GeGe homopolar
bonds as structural defects may be the result of the
highly non-equilibrium nature of the co-evaporation
process employed in the present study and may play a nonnegligible role in determining the physical properties of
GeTe thin films although this proposition has yet to be
investigated.
271
20
0
-20
2
3
4
5
Photon Energy (eV)
0
6
Figure 4 (online color at: www.pss-a.com) Dielectric function

spectra of (a) GeTe, (b) GeTe, and (c) GeTe thin films grown
on SiO2/Si substrates. The dielectric functions of as-grown (A)
and intermediately annealed (R1, R2) films are almost identical
and are not discernable from each other. X means a fully crystalline
film.
fore, the band gap energies of crystalline GeTe and GeTe

films were actually averaged gap energies.
In this work, the GeTe4 phase was found in crystalline
GeTe and GeTe films. There are few reports of the
optical characteristics of GeTe4 crystals. Jiang et al. grew
GeTe4 thin films using pulsed laser deposition and
investigated the structural, optical, and electrical properties
of the amorphous and crystalline phases [23]. Our work
shows that the physical characteristics of GeTe as well as
GeTe films include a GeTe4 major phase as well as minor
GeTe and Te phases. For example, the B0 phonon mode arose
from the c-GeTe4 phase.
Next, the optical properties of amorphous Ge1 xTex
alloys are discussed in detail. Amorphous Ge1 xTex alloys
are a single phase, whereas crystalline films are composed of
several phases such as GeTe, Ge, Te, and GeTe4.
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A B B1 B4C
1000
(E)
0.5
(eV/cm)
0.5
1500
500
0.5
1.0
1.5
2.0
Photon Energy (eV)
2.5
Raman Intensity (arb. units)
(a) Ge+Te
0.5
++
GeTe
GeTe
GeTe
+
Ge Te
100
(b) GeTe
1500
B3
200
300
400
-1
Wavenumber (cm )
500
Figure 6 (online color at: www.pss-a.com) Raman spectra of

amorphous GexTe1 x alloys as a function of Te composition.
1000
500
20
0.5
1.0
1.5
2.0
Photon Energy (eV)
2.5
15
(c) GeTe
12
0.5
8
5
1000
-5
500
0.5
0.5
(eV/cm)
16
10
1500
(E)
Ge Te
GeTe
+
GeTe
++
GeTe
(E)
0.5
(eV/cm)
C1
1.0
1.5
2.0
Photon Energy (eV)
2.5
Figure 5 (online color at: www.pss-a.com) (aE)1/2 C(E Eg)

spectra of amorphous and crystalline (a) GeTe, (b) GeTe, and
(c) GeTe thin films grown on SiO2/Si substrate.
Figure 6 shows the phonon modes of a-Ge1 xTex as a

function of Te composition. Mode A of a-Ge1 xTex was
fixed at 81 cm1 for GeTe, GeTe, and GeTe and was blueshifted to 84 cm1 for GeTe. As the Te composition was
increased, the intensity of the B4 mode increased because
it arose from the a-Te phase. The D mode, which arose
from GeGe homopolar bonds, disappeared for GeTe
thin films. The various phonon modes for amorphous and
crystalline GeTe as well as GeTe have been assigned by
several groups [5, 9]. In this work, phonon modes of Te-rich
GeTe films such as GeTe (i.e., Ge0.333Te0.667) and GeTe
(i.e., Ge0.187Te0.813) were also examined. We found that
most of the phonon modes could be explained in terms of the
GeTeGe4 n (n 0,1,2,3, and 4) tetrahedral model developed by Andrikopoulos et al. [4, 5]. Figure 7 shows the plot
of the real and imaginary parts of the amorphous dielectric
functions of Ge1 xTex films. The dielectric functions of
Ge1 xTex thin films depended on the Te composition.
2
3
4
5
Photon Energy (eV)
0
6
Figure 7 (online color at: www.pss-a.com) Dielectric function

spectra (e e1 ie2) of amorphous GexTe1 x thin films grown on
SiO2/Si substrate.
However, the dielectric functions of GeTe and GeTe

(Group I) were very similar and those of GeTe and GeTe
(Group II) are also very similar. Therefore, the effect of
GeGe homopolar bonds on the dielectric functions are
negligible in Group I whereas the effect of TeTe homopolar
bonds on the dielectric functions are similar for Group II.
In Group I, the number of GeGe homopolar bonds is
much larger for GeTe than for GeTe. In Group II, the
number of TeTe homopolar bonds is much larger for
GeTe than for GeTe. Detailed calculations on the
electronic structure of a-Ge1 xTex alloys are necessary to
understand the optical properties of a-Ge1 xTex alloys. The
similarity of the phonon modes for Group I and Group II is
also found in the phonon spectra of a-Ge1 xTex in Fig. 6.
Judging from the intensity of the B4 mode, a-GeTe films
contain TeTe homopolar bonds while Te-rich films such
as a-GeTe and GeTe films have a much larger number
of TeTe bonds. Andrikopoulos et al. [5] modeled the
Ge1 xTex alloys as composed of various GeTeGe4 n
(n 0,1,2,3, and 4) tetrahedra and estimated the fraction of
GeTeGe4 n (n 0,1,2,3,and 4) tetrahedra in amorphous
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where CP is described by the amplitude A, the threshold

energy Eth, the broadening G, and the excitonic phase angle
F. The exponent n takes the values of 1/2 for onedimensional (1D), 0 [logarithmic, i.e., lnE Eth iG ] for
2D, and 1/2 for 3D CPs. Discrete excitons are represented
by n 1, and the excitonic phase angle F represents a
coupling between the discrete exciton states and continuum
band states or a mixture between two CPs. To remove the
background contribution, the second derivative of the
dielectric function is fit with respect to energy (d2e/dE2)
using the SCP model. The SCP model is a generalization of
the Lorentzian oscillator and has been successfully applied
to polymers as well as semiconductors [26]. Using the
SCP model, we obtained the accurate values of the optical
transition energy of amorphous thin films as well as the CP
energy of crystalline thin films [25].
The imaginary part of the dielectric function, originating
from either crystalline or amorphous semiconductors, is a
multiplication of oscillator strength and the JDOS. The
oscillator strength is a square of the optical transition matrix
element [13]. The CP energy is determined from the JDOS,
which is given by
Z
2
dS
;
(2)
rcv E 3
8p
jrk Ec Ev jEc Ev E
where rcv(E) is the JDOS, and Ec and Ev are the valence and
conduction band energies as a function of k, respectively.
JDOS is a convolution of the DOS of both valence and
conduction bands, and can be expressed, whether crystalline
www.pss-a.com
rv E0 rc E E0 dE0 ;
(3)
1
where rv(E) and rc(E) are the DOSs in the valence and
conduction bands, respectively [27, 28]. The DOS can have
a structure at a particular energy, such as an extremum or a
shoulder, which originates from symmetric points in the
Brillouin zone, where the CPs are located. The separation of
energy between a structure in rv(E) and in rc(E) is the same
as the CP energy, which is determined from the second
derivative of the dielectric functions. Note that the critical
lines such as the L line in the Ge semiconductor can
manifest as a structure in JDOS spectra, whereas they do not
have any structure in DOS spectra.
Figure 8 shows the second derivative spectra of the
dielectric functions, e e1 ie2 (n ik)2 of the a-Ge1 xTex alloys of Fig. 7. Figure 9 shows the second derivative
spectra of the dielectric functions for (a) a-GeTe and (b)
c-GeTe. We also designate the transition energies of a-GeTe
and c-GeTe with short arrows as compared with those from
the literature with long arrows [12]. Figure 10 shows the
optical gap (Eg) and transition energies of a-Ge1 xTex as
a function of Te composition. In Fig. 10, we denote the
optical gap, i.e., the lowest gap energy, as Eg (0.8 eV), and
other transition energies as Ea (1.3 eV), Eb (2.1 eV), Ec
(3.0 eV), and Ed (5.3 eV) in the order of increasing
transition energy.
The lowest gap energy Eg increased from 0.74 to 0.95 eV
with increasing Te composition. Similar to the dielectric
functions in Fig. 7, the optical gap energies of GeTe
and GeTe were similar at approximately 0.75 eV, whereas
those of GeTe and GeTe were at approximately 0.9 eV in
Fig. 10. Note that the optical gap energy of a-Ge varies from
0.7 to 0.9 eV depending on growth condition and material
density [29], and that of a-Te is about 1.0 eV [30]. Therefore,
literature suggests that the optical gap energy will increase as
the Te composition increases as is shown in Fig. 10. Similar
++
a-GeTe
(1)
rcv E
Z1
a-GeTe
a-GeTe
eE C AeiF E Eth iG n ;
or amorphous, as
d /dE (arb. units)
Ge1 xTex thin films using the random bonding model

of Philip [24], neglecting TeTe bonds for Ge1 xTex
(0 < x < 0.67). However, our Raman data shows that TeTe
bonds are not negligible for a-GeTe and a-GeTe.
Information on the critical point (CP) energy is basic to
understanding the electronic band structures of crystalline
semiconductors. A CP is the symmetry point in the E(k)
band diagram where the slopes of Ec(k) and Ev(k) are
parallel [13]. The electronic band structures of semiconductors are important for understanding their optical and
electronic properties. Using standard critical point (SCP)
model analysis of dielectric function spectra, the CP
energies can be experimentally determined and compared
to other experimental probes such as photoemission
spectroscopy or theoretical band structure calculations.
In the case of amorphous semiconductors, the concept of
electronic band structure cannot be applied because the
wave vector k is not well-defined by disorder. However,
the SCP model can still be applied as a phenomenological
model even though the band picture is not rigorously
applicable.
The SCP model assumes simple parabolic dispersion
relations for the valence and conduction bands of semiconductors. The SCP lineshape equation is given by [25]
a-Ge Te
2
3
4
Photon Energy (eV)
Figure 8 (online color at: www.pss-a.com) The second derivative

spectra of d2e(E)/dE2 for amorphous GexTe1 x. The arrows designate the optical transition energies estimated using the SCP model.
solidi
status
physica
pss
274
Ec
Ed
3
4
5
Photon Energy (eV)
d /dE (arb. units)
(b) c-GeTe
3
4
5
Photon Energy (eV)

spectra of d2e(E)/dE2 for (a) amorphous and (b) crystalline GeTe. We
designated the transitions energies using short arrows (black) as
compared with those estimated from the DOS data from Ref. [12]
using long arrows (green).
optical studies of a-Ge1 xTex (x 0, 0.4, 0.5, 0.6) films,

previously reported by other groups [31, 32], did not find any
composition dependence with refractive index (n 4) and
band gap energy (Eg 0.8 eV).
In Fig. 10, the transition energies of (Eg, Ea, Eb, Ec, Ed)
were compared to those of a-GeTe measured using UPS
and IPES as reported by Hosokawa et al. [12], and our
estimated transitions (Eg, Ec, and Ed) energies were
consistent with their results. Furthermore, our work provided
more transitions energies such as Ea and Eb as shown in
Figs. 9 and 10. The overall energy resolution from Hosokawa
et al. was about 0.5 eV, which is much larger than the 0.02 eV
Optical Gap Energy (eV)
6
5
Ed
a-Ge1-xTex
4
Ec
Eb
Ea
1
0
0.2
Eg
0.4
0.6
0.8
Te Composition, x
Figure 10 (online color at: www.pss-a.com) Plot of the optical gap

and transition energies of amorphous GexTe1 x alloys estimated
by linear extrapolation of (aE)0.5 and SCP analysis. Open symbols
are quoted from Ref. [12].
Ge Te
(x 1/10)
R2
R1
of our work. In Fig. 10, all of the transition energies appear to

increase continuously with increasing Te composition. Note
that the Eb transition was split into the two transitions for
GeTe (i.e., Ge0.187Te0.813). In Fig. 9 (b), SCP curve-fitting
to the second derivative of the dielectric function for c-GeTe
provided 1.11, 1.62, 2.36, 3.66, 4.10, and 4.30 eV, whereas
Ref. [12] gave only 2.0, 4.2, and 5.4 eV. Considering the
poorer resolution of Ref. [12], our dielectric function data
provides more accurate CP energies.
It has been argued that the electronic structures of
amorphous semiconductors such as GaAs and Si are very
similar to the corresponding crystalline semiconductors
because the short-range order is almost the same for both
semiconductor types [33, 34]. Only medium range and longrange order substantially differentiates the electronic structures
of amorphous and crystalline semiconductors. Since the wave
vector k is not conserved in amorphous semiconductors
by disorder, the lineshapes of the dielectric functions
associated with the transitions energies are broader than
those associated with CPs in the corresponding crystalline
semiconductors. For example, the dielectric functions of
amorphous GaAs and Si were modeled using the model
dielectric functions which were similar to those of the
corresponding crystalline semiconductors [35, 36]. This
work shows that the dielectric functions of chalcogenide
glasses can be modeled using the SCP model. Note that short
range order changes with tetrahedral (a-GeTe) to octahedral
(c-GeTe) coordination [22].
Note that we did not observe crystalline XRD peaks for
Ge1 xTex thin films annealed at intermediate temperatures
in Fig. 1. Compared to the amorphous phase (i.e., as-grown
phase) films, phonon modes, and dielectric function spectra
showed little change with intermediate annealing temperatures as shown in Figs. 2 and 4. However, the second
derivative of the dielectric function spectra showed a very
large change in amplitudes with an intermediate temperature
of 250 8C for GeTe as shown in Fig. 11, although very small
changes in amplitude for GeTe and GeTe were found with
intermediate temperature (not shown here). This suggests
that there was a significant configurational change of atomic
d /dE (arb. units)
d /dE (arb. units)
(a) a-GeTe
Ea
Eb
2
3
Photon Energy (eV)

spectra of d2e(E)/dE2 for GeTe thin film with increasing annealing
temperature. A, R1, R2, and X denote amorphous, 125, 250 8C,
and crystalline thin films, respectively.
www.pss-a.com
Original
Paper
bondings in GeTe films annealed with an intermediate

temperature compared to as-grown film, although they had
an amorphous phase and did not show any long-range order
of a crystalline phase.
4 Conclusions Amorphous Ge1 xTex thin films were
grown and then annealed for crystallization. The dielectric
functions and the phonon modes of Ge1 xTex films were
measured using spectroscopic ellipsometry and Raman
spectroscopy, respectively. The XRD and Raman data
suggested precipitation of a Ge phase in the major GeTe
phase for GeTe films, whereas GeTe4 was the major phase
with minor GeTe and Te phases for GeTe and GeTe thin
films. Raman data also showed the phonon mode from the
Ge, Te, and GeTe4 phases as well as from the GeTe phase.
The phonon mode at 280 cm1 (D mode) arising from GeGe
bonds in amorphous Ge1 xTex (x 0.067) was found
even for the corresponding crystalline thin films possibly
due to Ge vacancies arising from non-equilibrium growth.
In addition to the reported phonon modes [5, 6], we
observed A1 (95 cm1), B0 (120 cm1), B2 (125 cm1), and
B4 (158 cm1) modes, which were attributed to c-GeTe,
c-GeTe4, c-Te, and a-Te phases, respectively. The optical
gap energy was estimated using linear extrapolation of
absorption coefficients derived from the dielectric functions.
The optical gap energy of a-Ge1 xTex films increased
continuously with increasing Te composition, whereas the
indirect gap energy of c-Ge1 xTex films decreased. Using
the second derivative spectra of the dielectric functions of
a-Ge1 xTex alloys and the SCP model, optical transition
energies of a-Ge1 xTex alloys were obtained. The optical
transition energies were not only consistent with the
photoemission spectra of Ref. [12], but also provided more
detailed and accurate electronic structure information for
a-Ge1 xTex alloys.
Acknowledgements The work at KHU was supported by
National Research Foundation Grant No. 2012039969 and the
work at KIST was supported by a grant from the Fundamental R&D
Program for Core Technology of Materials, Ministry of Knowledge
Economy, Republic of Korea.
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Phys. Status Solidi A 210, No. 2, 267275 (2013) / DOI 10.1002/pssa.201228555

applications and materials science

Structural and optical properties of

Received 17 August 2012, revised 25 September 2012, accepted 1 October 2012

Ge1 xTex thin films were grown using thermal coevaporation

d /dE (arb. units)

The second derivative spectra of d2e(E)/dE2 for amorphous

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction Recently, GeTe has received renewed

physical characteristics of GeTe alloys, specifically the

However, the phonon modes of Te-rich Ge1 xTex alloy thin

Raman spectroscopy, respectively. Ellipsometric angles

Intensity (arb. units)

Figure 1 (online color at: www.pss-a.com) X-ray diffraction

suggests that all of the intermediate temperature-annealed

Intensity (arb. units)

Intensity (arb. units)

Figure 2 (online color at: www.pss-a.com) Raman spectra of (a)

ZnS(SiO2)-coated quartz were very similar to those in

Table 1 The measured phonon modes of Ge1 xTex thin films.

GeTe (bending mode)a,b,c

a- and c-Ge1 xTex

shifted and became B0 (120 cm1) after crystallization.

Intensity (arb. units)

Intensity (arb. units)

in edge-sharing GeTe4 nGen (n 0) tetrahedra [4, 5].

3.3 Spectroscopic ellipsometry The dielectric

the D mode was absent for both amorphous and

Figure 4 (online color at: www.pss-a.com) Dielectric function

fore, the band gap energies of crystalline GeTe and GeTe

Raman Intensity (arb. units)

Figure 6 (online color at: www.pss-a.com) Raman spectra of

Figure 5 (online color at: www.pss-a.com) (aE)1/2 C(E Eg)

Figure 6 shows the phonon modes of a-Ge1 xTex as a

Figure 7 (online color at: www.pss-a.com) Dielectric function

However, the dielectric functions of GeTe and GeTe

where CP is described by the amplitude A, the threshold

d /dE (arb. units)

Ge1 xTex thin films using the random bonding model

Figure 8 (online color at: www.pss-a.com) The second derivative

d /dE (arb. units)

Figure 9 (online color at: www.pss-a.com) The second derivative

optical studies of a-Ge1 xTex (x 0, 0.4, 0.5, 0.6) films,

Optical Gap Energy (eV)

Figure 10 (online color at: www.pss-a.com) Plot of the optical gap

of our work. In Fig. 10, all of the transition energies appear to

d /dE (arb. units)

d /dE (arb. units)

Figure 11 (online color at: www.pss-a.com) The second derivative

bondings in GeTe films annealed with an intermediate

[5] K. S. Andrikopoulos, S. N. Yannopoulos, G. A. Voyiatzis,

2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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