JOURNAL OF APPLIED PHYSICS 107, 024305 共2010兲

Thickness effect on the band gap and optical properties of germanium thin
films
Eunice S. M. Goh,1,a兲 T. P. Chen,1,b兲 C. Q. Sun,1 and Y. C. Liu2
1
School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798,
Singapore
2
Singapore Institute of Manufacturing Technology, Singapore 638075, Singapore
共Received 28 September 2009; accepted 12 December 2009; published online 22 January 2010兲
The band gap and optical properties 共dielectric functions and optical constants兲 of Ge thin films with
various thicknesses below 50 nm, which were synthesized with electron beam evaporation
technique, have been determined using spectroscopic ellipsometry and UV-visible
spectrophotometry. The optical properties are well described with the Forouhi–Bloomer model.
Both the band gap and optical properties show a strong dependence on the film thickness. For film
thickness smaller than ⬃10 nm, a band gap expansion is observed as compared to bulk crystalline
Ge, which is attributed to the one-dimensional quantum confinement effect. However, a band gap
reduction was observed for thickness larger than ⬃10 nm, which is explained in terms of the
amorphous effect in the Ge layers. © 2010 American Institute of Physics. 关doi:10.1063/1.3291103兴

I. INTRODUCTION and 46 nm兲, which is attributed to the influence of the Ur-

Germanium 共Ge兲 has been a popular material of study as
its properties benefit many applications. Ge was the choice
of material used in the first bipolar transistor which was in-
vented in 1949 by Bardeen, Brattain, and Shockley; hence
proving its electrical functionality.1,2 Due to its small energy
band gap 共0.66 eV兲, Ge is also popularly used in optical and
optoelectronic devices. Examples of optical and optoelec-
tronic devices that uses Ge are photodetectors,2–4 solar
cells,2,5 and waveguides.2,6 However, the challenge to design
a light source based on Ge has not been solved as Ge is
known to be a poor light emitter, but the scaling of materials
toward nanoscale, which will change its’ properties as the
motion of electrons, holes, and excitons are restricted in
three dimensions, has shed some ray of hope for Ge to emit
light. Hence, it is necessary to study the physical properties
of Ge in nanoscale. Previous studies on the optical properties
of Ge films were usually focused on the films thicker than
100 nm7–9 and also in longer wavelengths 共2 – 200 ␮m兲.10–12
In this paper, we present a study on the optical properties and
band gap of Ge thin films in nanoscale regime 共thinner than
50 nm兲, using spectroscopic ellipsometry 共SE兲8,13–15 in the
wavelength range of 350–1100 nm. The optical properties of
the Ge thin films are well described by the Forouhi–Bloomer
共FB兲 model,14,16,17 and the modeling using the FB
formula16,17 yields the energy band gap of the Ge thin films.
The values of the band gap yielded from the modeling are in
good agreement with those obtained from the measurement
of ultraviolet-visible 共UV-visible兲 spectrophotometry. The
ultra-thin Ge films 共2.6, 4.7, and 8.2 nm兲 exhibits a band gap
expansion as compared to bulk crystalline Ge, showing the
one-dimensional quantum confinement effect. However, a
band gap reduction was observed for thicker films 共15.3, 22,
a兲
Electronic mail: e070032@ntu.edu.sg.
b兲
Electronic mail: echentp@ntu.edu.sg.
bach band tails arising from the amorphous effect.
II. EXPERIMENT DETAILS
Initially, a 30 nm SiO2 layer was grown on the cleaned
surface of p-type 具100典 Si substrate using dry oxidation at
950 ° C for 1 h. A Ge layer of different thicknesses 共with
nominal values of 3, 5, 8, 15, 20, and 50 nm兲 was then
deposited on the SiO2 layer using the electron beam evapo-
ration method. To examine the amorphous degree of the Ge
thin films, Raman spectroscopic measurement was conducted
using the Renishaw 1000 Ramascope system with the 633
nm line of He–Ne laser. The actual thicknesses of the Ge thin
films were determined by the SE spectral fitting with the
surface roughness taken into account. The SiO2 layer, which
acts as a buffer layer for the deposition of the Ge layer, can
prevent the formation of SiGe alloy and also avoid possible
strains or defects occurring at the interface between the Ge
layer and the Si substrate. The SE measurements were car-
ried out using a variable angle ellipsometer 共J.A.Woollam
Inc., Model HS-190兲 in the wavelength range of 350–1100
nm 共1.13–3.54 eV兲 with a step of 5 nm. The measurements
were conducted at three different angles of incidence 共65°,
70°, and 75°兲. The absorption measurements of Ge layer de-
posited on fused silica substrate were carried out using a
UV-visible spectrophotometer 共Shimadzu UV2450兲 in the
wavelength range of 350–900 nm with a step of 5 nm. All
measurements were conducted in room temperature environ-
ment.
III. MODELING AND DISCUSSIONS
Figure 1共a兲 illustrates the five-phase model 共i.e., air/
surface-roughness layer/Ge layer/SiO2 layer/Si substrate兲
used in the SE analysis. The inclusion of surface roughness
of the Ge layer is supported by the three-dimensional atomic
force microscopic 共AFM兲 image of the Ge layer shown in
Fig. 1共b兲. The AFM measurement shows the existence of the

0021-8979/2010/107共2兲/024305/5/$30.00 107, 024305-1 © 2010 American Institute of Physics

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024305-2 Goh et al.
(a)
Ѳ incidence. Based on the two-term FB model, the optical con-
Ge layer
30nm SiO2
p-Si substrate
(b)
FIG. 1. 共Color online兲 共a兲 Five-phase model used in the SE analysis and 共b兲
AFM image of the surface roughness of the Ge layer.
surface roughness of 0.8 nm. The phase of the surface-
roughness layer is modeled by the Bruggeman effective me-
dium approximation18
␧tf−Ge − ␧i ␧void − ␧i
f+ 共1 − f兲 = 0,
␧tf−Ge + 2␧i ␧void + 2␧i
where ␧i 共=N2i , where Ni is the effective complex refractive
index of the surface-roughness layer兲 is the effective dielec-
tric function of the surface roughness layer, ␧tf−Ge is the Ge
dielectric function, f is the volume fraction of Ge in the
surface-roughness layer, and the void dielectric function ␧void
is 1.
In the SE analysis, based on the model in Fig. 1共a兲, the
ellipsometric angles 共⌿ and ⌬兲 can be expressed as functions
of the optical constants and the thickness of the Ge layer.
However, due to their complexity, these functions cannot be
displayed as analytical formulas. These functions are used in
the spectral fitting to the experimental data of ⌿ and ⌬, in
order to obtain the optical constants and thickness of the Ge
layer. In the spectral fitting, an appropriate optical dispersion
model should be used to describe the spectral dependence of
the optical constants of the Ge layer. In this work, the FB
model16,17 was used. The two-term FB model is found to be
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J. Appl. Phys. 107, 024305 共2010兲
able to yield a reasonable spectral fitting in the whole wave-
length range of the SE measurements at different angles of
stants including the refractive index 共n兲 and extinction coef-
ficient 共k兲 of the Ge layer are given by14,16,17
k共E兲 = 冉兺2
i=1
Ai
E 2 − B iE + C i
冊
共E − Eg兲2 , 共2兲
2
B 0iE + C 0i
n共E兲 = n共⬁兲 + 兺 , 共3兲
i=1 E 2 − B iE + C i
where
B 0i =
Ai
Qi
冉 B2
− i + EgBi − E2g + Ci ,
2
冊 共4兲
C 0i =
Ai
Qi
冉 B2
共E2g + Ci兲 i − 2EgCi ,
2
冊 共5兲
1
Qi = 共4Ci − B2i 兲1/2 , 共6兲
2
where Ai, Bi, and Ci 共i = 1 , 2兲 are some parameters related to
electron transition, n共⬁兲 is the refractive index when photon
energy E → ⬁, and Eg is the energy band gap of the Ge layer.
The spectral fitting was carried out by freely varying
both the parameters of the two-term FB model of the Ge
layer with the values of their counterparts, bulk crystalline
Ge used as the initial values; and also by freely varying the
thickness of the Ge layer as well, in order to minimize the
mean-square error14 for the SE measurements at the three
angles of incidence 共i.e., 65°, 70°, and 75°兲. Excellent spec-
tral fittings in the whole wavelength range of the SE mea-
surements at the three angles of incidence have been
achieved for all the samples. As an example, Fig. 2 shows
the spectral fittings for the Ge layer with nominal thickness
of 3 nm at the angles of incidence of 65°, 70°, and 75°,
respectively. The values of the parameters of the two-term
共1兲
FB model obtained from the spectral fittings for some of the
Ge layers were given in Table I. For comparison, the corre-
sponding values for bulk crystalline Ge is also shown in the
table. The thicknesses of the Ge layers with the nominal
values of 3, 5, 8, 15, 20, and 50 nm obtained from the spec-
tral fittings are 2.6, 4.7, 8.2, 15.2, 22, and 46 nm, respec-
tively. The thickness values obtained from the SE fittings are
close to the nominal values which were set for the electron-
beam evaporation based on a standard calibration procedure.
In addition, they are also in good agreement with the AFM
measurement. On the other hand, it is worthy to mention that
the volume fraction of Ge in the surface-roughness layer is
about 60%.
The most important parameter for the FB modeling is
the energy band gap of the Ge layers. As can be seen in Table
I, the band gap of the 2.6 nm Ge layer is 1.03 eV, showing a
large band gap expansion of 0.37 eV as compared to the
band gap 共0.66 eV兲 of the bulk crystalline Ge, however, the
46 nm Ge layer have a band gap of 0.33 eV, which is
024305-3 Goh et al. J. Appl. Phys. 107, 024305 共2010兲

FIG. 3. Plot of 共␣E兲1/2 vs photon energy 共E兲 for the 2.6 and 46 nm Ge
layers. The plot for bulk crystalline Ge is included for comparison.

Another important finding from Fig. 4 is the thickness

FIG. 2. Spectral fittings of ⌿ and ⌬ for the 2.6 nm Ge layer at the angles of
incidence of 65°, 70°, and 75°.
significantly smaller than the value of the bulk crystalline
Ge. The band gap values obtained from the above spectral
fittings based on the FB model are consistent with the results
from the absorption measurements of the corresponding Ge
layers deposited on fused silica substrate with the UV-visible
spectrophotometer. As examples, Fig. 3 shows the plots of
共␣E兲1/2 versus E where ␣ is the absorption coefficient ob-
tained from the absorption measurement and E is the photon
energy for the 2.6 nm and 46 nm Ge layers. The values of the
band gap obtained by extrapolating the linear portion of the
plots for all the samples are shown in Fig. 4, and they are
also compared to the values obtained from the spectral fit-
tings based on the FB model in the figure. As can be seen in
the figure, there is a good agreement between the two tech-
niques, indicating that the results from the SE study are re-
liable.
dependence of the band gap. When the film thickness is
smaller than ⬃15 nm, the band gap increases as the thick-
ness decreases, and it is even larger than the band gap of
bulk crystalline Ge when the thickness is less than ⬃10 nm,
showing a band gap expansion. However, when the thickness
is larger than ⬃10 nm, the band gap is smaller than the
value of bulk crystalline Ge. As discussed below, the thick-
ness dependence of the band gap can be explained with the
one-dimensional quantum confinement effect and the amor-
phous effect in the Ge thin films.
The very thin Ge films 共e.g., the thickness less than
⬃15 nm兲 could be considered as a one-dimensional con-
fined system. In such a two-dimensional system, elementary
excitations will experience quantum confinement resulting in
finite motion in the confinement direction 共i.e., the thickness
direction兲 and infinite motion in other two directions.19 It has
been well known that as the confining dimension decreases,
typically in nanoscale, the energy spectrum turns to discrete
and thus the band gap of a semiconductor becomes size de-
pendent. For one-dimensional confinement, the quantization
energies increase when the size along the confinement direc-
tion 共i.e., the film thickness in the present case兲 decreases, as
described by19–21

TABLE I. Values of parameters Ai, Bi, Ci 共i = 1 , 2兲, n共⬁兲, and Eg of the FB model of some Ge layers obtained
from the spectral fittings. The values of bulk crystalline Ge are included for comparison.

FB modeling

Dominant effect Size Ai Bi Ci n共⬁兲 Eg

Bulk 0.0140 7.4019 13.6767 2.4738 0.66

0.0686 8.6418 18.7880
Amorphous effect 46 nm 0.3432 3.3081 3.1303 2.3007 0.33
0.3172 5.8803 10.1510
22 nm 0.0964 2.7755 2.2746 2.1714 0.40
0.6566 4.6818 7.6074
One-dimensional quantum 4.7 nm 0.1082 3.8072 4.8970 2.2328 0.80
confinement effect 0.1077 6.2906 11.2363
2.6 nm 0.2859 4.1000 4.8841 2.4302 1.03
0.0529 7.1618 13.2426

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024305-4 Goh et al.
FIG. 4. Band gaps of the Ge layers with various thicknesses obtained from
either the FB modeling or the extrapolation of plot 共␣E兲1/2 vs E. The solid
curve is used for guiding the eyes only.
ប2
⌬Eg ⬃ , 共7兲
2ma2
where a is the thickness of the layer and m is the effective
carrier mass. Equation 共7兲 can generally explain the band gap
expansion with reduction of film thickness, but it cannot
quantitatively describe the result shown in Fig. 4 because the
amorphous effect also affects the band gap significantly as
discussed below.
Figure 5 shows the Raman spectra of the Ge layers with
different thicknesses. A broad Raman band at around
⬃270 cm−1 is observed for all samples, and the situation is
similar to that of amorphous Ge films.22,23 It is been reported
that scattering of local transverse optical phonons leads to a
broad Raman band at around 275 cm−1.22,23 The result of the
Raman measurement indicates that all the Ge layers under
study are amorphous or at least present a high degree of
structural disorder. The situation is expected as the substrate
temperature was maintained below 50 ° C during the Ge
evaporation and there was no postevaporation annealing
关note that the temperature required for the transition from
amorphous to crystalline is ⬃200– 300 ° C 共Ref. 7兲兴. In an
amorphous or structurally disordered film, the imperfection
in the film causes the bands of localized states to get
FIG. 5. Raman spectra of Ge layers with various thicknesses. A broad peak
at ⬃270 cm−1 can be observed for all the samples under study.
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J. Appl. Phys. 107, 024305 共2010兲
FIG. 6. Refractive index 共n兲 and extinction coefficient 共k兲 of the 2.6 and 46
nm Ge layers. The n and k of bulk crystalline Ge 共Ref. 25兲 is included for
comparison.
broaden, and a band gap reduction may occur due to the
Urbach edge.9,24 The band gap reduction shown in Fig. 4
indicates that the amorphous effect is dominant for film
thickness larger than ⬃10 nm. However, for film thickness
smaller than ⬃10 nm, the one-dimensional quantum con-
finement effect is dominant, and thus the band gap increases
when the film thickness is reduced.
On the other hand, the optical constants 共n and k兲 of the
Ge layers can be calculated with Eqs. 共2兲–共6兲 by using the
values of the parameters of the FB model given in Table I,
and for a clear presentation, only the results for the thinnest
layer 共2.6 nm兲 and the thickest layer 共46 nm兲 are shown in
Fig. 6. The real part 共=n2-k2兲 and imaginary part 共=2nk兲 of
the complex dielectric functions of the Ge layers can be ob-
tained also, and the results are shown in Fig. 7. For compari-
son, the optical constants and dielectric function of bulk
crystalline Ge are also included in Figs. 6 and 7,
respectively.25 The broadened structures in the dielectric
function spectra observed in Fig. 7 are due to the amorphous
or disorder structures presented in the Ge layers. It is worth
mentioning that as can be seen in Fig. 6, the dielectric func-
tion of the 2.6 nm Ge layer is much lower than that of the
bulk crystalline Ge. This phenomenon could be related to the
quantum size effect as a large band gap expansion has been
observed as a result of the quantum confinement in the 2.6
nm Ge layer. It has been well established that the static di-
electric constant decreases as the size of quantum confined
physical systems is of nanometric range14,26 although the de-
tailed mechanism is still not fully understood. The reduction
in dielectric constant has been attributed to the opening of
the gap which should lower the polarizability27 or the break-
024305-5 Goh et al. J. Appl. Phys. 107, 024305 共2010兲

band gap expansion is observed, however, for thickness

larger than ⬃10 nm, the amorphous effect is dominant, lead-
ing to a reduction in the band gap.

ACKNOWLEDGMENTS
Financial support from the National Research Founda-
tion of Singapore under Project No. NRF-G-CRP 2007-01 is
acknowledged.
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