Microelectronic Engineering 72 (2004) 154–159

www.elsevier.com/locate/mee

Photoelectron spectroscopy of ultrathin

yttrium oxide films on Si(1 0 0)
A. Ohta, M. Yamaoka, S. Miyazaki *

Department of Electrical Engineering, Hiroshima University Graduate School of Advanced Sciences of Matter,
Hiroshima University, Higashi-Hiroshima 739-8530, Japan

Abstract

The Y2 O3 /SiO2 /Si(1 0 0) stack structures were prepared by the thermal decomposition of a yttrium organic complex
in O2 ambient at 350 °C and subsequent O2 -anneal at 500 °C. From the analysis of O1s energy loss spectra, the energy
band gap was determined to be 6.0
0.05 eV for Y2 O3 and 8.9
0.05 eV for interfacial SiO2 . By deconvoluting the
valence band spectra into the components, valence band offsets for Y2 O3 with respect to Si(1 0 0) and interfacial SiO2
were obtained to be 3.3 and 1.3 eV, respectively, which indicates the conduction band offset of 1.58 eV between
Y2 O3 and Si(1 0 0). Total photoelectron yield spectra show an increase in the electronic defect states with post depo-
sition O2 -anneal in the temperature range 300–700 °C, which is related to the formation of interfacial SiO2 layer at such
low temperatures.
Ó 2004 Elsevier B.V. All rights reserved.

Keywords: Yttrium oxide; Energy band alignment; Photoemission; X-ray photoelectron spectroscopy; Energy loss spectrum; Valence
band spectrum

1. Introduction tivated the replacement of ultrathin SiO2 with

Continuous scaling of complementary metal-
oxide-semiconductor field-effect-transistors (CMO-
SFETs) down to sub-100 nm technology nodes
requires increasing capacitive coupling between the
gate and the Si(1 0 0) surface with keeping an al-
lowable leakage current through a gate dielectric
thinner than 1.5 nm in equivalent SiO2 thickness
(EOT) [1]. Such a mandatory requirement has mo-
* k dielectrics. In our previous work, we determined
Corresponding author. Tel.: +81-824-24-7656; fax: +81-824-
22-7038.
E-mail address: miyazaki@sxsys.hiroshima-u.ac.jp (S. Mi-
yazaki).
physically thicker insulators with higher dielectric
constants (high-k) than SiO2 and stimulated exten-
sive studies of alternative high-k dielectrics, such as
transition metal oxides, rare earth metal oxides and
their silicates and aluminates, staked dielectrics and
high-k dielectric/Si interfaces[2]. Even for physi-
cally thicker high-k gate dielectrics, the energy band
offsets for the high-k dielectric/Si interfaces as well
as electrical active defects are other curial factors to
suppress the gate leakage current through the high-
the energy band alignments between Si(1 0 0) and
Ta2 O5 [3], Al2 O3 [3], ZrO2 [4] and HfO2 [5] as pos-
sible candidates for SiO2 substitution by XPS

0167-9317/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.mee.2003.12.030
 A. Ohta et al. / Microelectronic Engineering 72 (2004) 154–159 155

measurements. Yttrium oxide (Y2 O3 ) can become
another alternative from viewpoints of a moderate
dielectric constant (15) the thermodynamic sta-
bility of Y2 O3 in contact with silicon [6]. Indeed, a
significant reduction of the gate leakage current in
comparison to the SiO2 case and a good thermal
stability against post-deposition anneal below 900
°C have been reported [7,8], and the scalability
down to EOT ¼ 1 nm has been discussed although
the electrical leakage through the Y2 O3 /Si(1 0 0)
system is still not understood quantitatively.
In this work, to gain a better understanding of
electrical properties for the Y2 O3 /Si(1 0 0) system,
we extended our research to determine the energy
band alignment between Y2 O3 and Si(1 0 0) and
characterize the chemical bonding features at the
interface by photoemission measurements. Also,
the energy distribution of electronic defect states in
the system of interest was quantified by total
electron yield spectroscopy [9,10].
2. Sample preparation
Amorphous Y2 O3 films were prepared at 350 °C
on HF-last Si(1 0 0) by thermal decomposition of
Tri(dipivaloylmethanato) yttrium [Y(DPM)3 ] va-
porized in O2 ambient under 102 Pa. After de-
position, the samples were annealed at 500 °C in
dry O2 for 1 min to eliminate residual carbon. The
interfacial oxide layer formed by O2 -anneal, was
characterized separately after removal of the top
Y2 O3 layer using a 0.1% HF solution at room
temperature.
3. Results and discussion
The changes in chemical bonding features at
Y2 O3 /Si(1 0 0) interfaces by O2 -anneal were evalu-
ated by measuring Si2p, Y3d and O1s spectra as
shown in Fig. 1. Distinct increases in the chemi-
cally shifted Si2p and O1s signals by O2 -anneal are
observed, indicating the formation of the interfa-
cial silicon oxide layer. From the ratios in the in-
tegrated intensities of the chemically shifted Si2p
to metallic Si2p of Si(1 0 0) and to the increment of
O1s signals, it is found that the SiO2 layer at the
interface is increased from 0.7 (as-deposited) to 1.6
nm by the O2 -anneal. A slight increase in Y3d
signals by O2 -anneal only results from the nor-
malization by the signals from the Si(1 0 0) sub-

(a) (b) (c)

Fig. 1. Si2p (a), Y3d (b) and O1s (c) spectra for 2.6-nm thick Y2 O3 evaporated on HF-last Si(1 0 0) before and after 500 °C annealing
in dry O2 for 1 min, where the binding energy was calibrated with the Si2p(3/2) peak from the Si(1 0 0) substrate at 99.3 eV and the
intensity for each spectrum was normalized by the Si2p(3/2) peak intensity. In (c), the deconvoluted components due to Y–O and Si–O
bonds for the annealed sample were shown with open squares and open circles, respectively.
156 A. Ohta et al. / Microelectronic Engineering 72 (2004) 154–159

strate. Notice that the Y3d spectrum for the an-
nealed sample is shifted by 0.2 eV toward the
higher binding energy side with keeping the spec-
tral shape, implying that there exist the potential
drop of 0.2 eV in the interfacial oxide layer. The
energy separation between the O1s peaks origi-
nating from Y–O bonds and interfacial Si–O
bonds implies that the valence band offset of Y2 O3
and the interfacial oxide is to be 1.3 eV including
a potential drop in the interfacial oxide if any,
being in consistence with the result from a direct
analysis of valence band spectra as described later.
From the XPS analysis after complete removal of
the Y2 O3 layer from the 500 °C annealed sample
by 0.1% HF etching, no incorporation of Y atoms
in the interfacial oxide layer is detectable as indi-
cated in Figs. 1(b) and (c). Also, one can find that
the removal of the Y2 O3 layer is accompanied with
a clear reduction in the lower binding energy side
of chemically shifted Si2p signals (Fig. 1(a)), which
indicates that the reduced signals are attributed to
the Si oxidized states bonded to less electronega-
tive Y atom(s) as the second nearest-neighbor(s).
The energy bandgap of ultrathin Y2 O3 with
different thicknesses were determined from the
onset of the energy loss signals for O1s photo-
electrons after subtracting the Si–O component
from the primary core line signals to clarify the
background level for the energy loss signals. In
each of the spectra, the onset of the energy loss
spectrum was defined by linearly extrapolating the
leading segment to the background level. As rep-
resented in Fig. 2(a), the bandgap value so deter-
mined is constant at 6.0 eV within an accuracy of
0.1 eV in the thickness range 0.9–3.8 nm and re-
mains unchanged by 500 °C O2 -anneal. From the
onset of the O1s loss spectrum for the 1.2-nm thick
interfacial SiO2 which were taken after complete
removal of Y2 O3 from the annealed sample, we
obtained the bandgap value (8.9 eV) being the
same as thermally grown pure SiO2 (Fig. 2(b)).
To evaluate the valence band offset between
Y2 O3 and Si(1 0 0) from the valence band spectra of
the samples before and after O2 -anneal, the com-
ponent of the Si(1 0 0) valence band was first sub-
tracted from the measured valence band spectra for

(a) (b)

Fig. 2. O1s energy loss spectra for Y2 O3 films with different thicknesses (a) and for the interfacial SiO2 (b). The spectrum for the
interfacial SiO2 was taken after removal of the top Y2 O3 layer from the 2.6-nm thick annealed sample. The spectrum for 2.0-nm thick
thermally grown SiO2 are shown as a reference in (b).
 A. Ohta et al. / Microelectronic Engineering 72 (2004) 154–159 157

the heterostructures by using the reference valence

band spectrum which was separately measured for
H-terminated Si(1 0 0) as demonstrated in Figs. 3
and 4, where the binding energy for each valence
band spectrum was calibrated with the Si2p(3/2)
core line peak originating from the Si(1 0 0) sub-
strate. In addition, for the annealed sample, the
valence band spectrum was taken after removal of
the top Y2 O3 layer and deconvoluted into two
components of interfacial SiO2 and Si(1 0 0) as also
shown in Fig. 4. Considering that the valence band
top of Y2 O3 is shallower than that of SiO2 , from the
energy separation between the tops of the decon-
voluted valence band spectra, the valence band
offset between Y2 O3 and Si(1 0 0) is determined to
be 3.3 eV for the as-deposited sample (Fig. 3) and
3.5 eV for the annealed one (Fig. 4) with an accu-
racy of 0.1 eV. The valence band offset between the
interfacial SiO2 and Si(1 0 0) is obtained to be 4.6
eV. The increase in the valence band offset by 0.2
eV can be interpreted in terms of the potential drop Fig. 4. Valence band spectra for the annealed sample, Y2 O3
in the interfacial SiO2 as discussed in the analysis of (2.6 nm)/SiO2 (1.6 nm)/Si(1 0 0) (a) and the sample after re-
moval of the top Y2 O3 layer by 0.1% HF etching (b). The de-
convoluted spectra for Si(1 0 0) (c), and remains corresponding
to Y2 O3 /SiO2 and interfacial SiO2 which were obtained from
the spectral subtraction of (a) ) (c) and (b) ) (c), respectively.

Y3d and O1s spectra. Considering these results and

Fig. 3. Valence band spectra for as-deposited Y2 O3 (2.6 nm)/
SiOx (0.7 nm)/Si(1 0 0) and the deconvoluted spectra for
Si(1 0 0) and remains corresponding to Y2 O3 /SiOx . In the
spectral deconvolution, the valence band spectrum separately
measured for wet-chemically prepared H-terminated Si(1 0 0)
was used with a consideration of the binding energy of Si2p
core line peak.
previously measured Y2 O3 bandgap of 6.0 eV, the
conduction band offset between Y2 O3 and Si(1 0 0)
is obtained to be 1.58 ( ¼ 1.38 + 0.2) eV as indicated
in Fig. 5. The experimentally determined energy
band alignment between Y2 O3 and Si(1 0 0) seems
to be consistent with the theoretical prediction [11]
in which, for an ideal heterojunction between
crystalline Y2 O3 and Si(1 0 0) without an interfacial
SiO2 layer, the conduction and valence band offsets
are calculated to be 2.3 and 2.6 eV, respectively.
The difference in the dipole formation between
amorphous Y2 O3 /SiO2 and c-Y2 O3 /Si(1 0 0) inter-
faces may reflect in the difference between the ex-
perimental and theoretical results.
The energy distribution of electronic defect
states in such a thin dielectric stack structure may
play an important role in electronic properties es-
pecially the leakage current. Therefore, to quantify
electronic defect states in the dielectric stack
structure, we measured total photoelectron yields
158 A. Ohta et al. / Microelectronic Engineering 72 (2004) 154–159
Fig. 5. Energy band profile for the Y2 O3 /SiO2 /Si(1 0 0) system.
from 1-nm thick Y2 O3 deposited on nþ -Si(1 0 0)
before and after O2 -anneal as a function of inci-
dent photon energy in the range 4–6 eV as shown
in Fig. 6. In this figure, the yield spectra were
Fig. 6. Total photoelectron yield spectra for 1.0-nm thick
Y2 O3 deposited nþ -Si(1 0 0) with a donor concentration of
3  1018 cm3 and after O2 -annealed at 300–700 °C. The gray
region corresponds to the yield of Si valence electrons which
was confirmed from the yield spectrum of H-terminated pþ -
Si(1 0 0) with an acceptor concentration of 1  1019 cm3 [10].
The Ev denotes the Si valence band top measured from the
vacuum level.
normalized with the yield at 5.7 eV. Since no
photoemission of valence electrons in the oxide
layers occurs for photons as low as 6 eV as can be
seen in the energy band profile of Fig. 5, filled
states distributed in oxides and at the interfaces if
any in the energy region corresponding to the Si
bandgap reflect in the yield spectrum as an integral
with respect to energy. Notice that, for photons
higher than 5.15 eV, the photoemission from the Si
valence band becomes significant as shown in
the reference yield spectrum of H-terminated
pþ -Si(1 0 0). The observed increase in the photo-
electron yield for photons below 4.8 eV with in-
creasing anneal temperature indicates that deep
defect states in the stack structure are generated
with increasing O2 -anneal temperature over 300
°C. In the case annealed at 700 °C, the yield re-
duction for photons higher than 4.8 eV implies
that some defects presumably existing in the oxide
layer rather than at the interface are eliminated.
From the 1st derivative of the yield spectrum,
the energy distribution of the filled defect state
density was crudely estimated in each case using the
same manner described in [10]. In the estimation,
Fig. 7. Energy distributions of filled state densities derived
from the yield spectra shown in Fig. 6. The vertical scale is
expressed in areal density and the horizontal axis is the energy
from the Si valence band top Ev toward the Si conduction band.
The interfacial SiO2 thickness determined from the analysis of
the Si2p spectrum is 1.0 nm for as-deposited and 300 °C an-
nealed samples, 1.8 nm for 500 °C annealed and  2.5 nm for
700 °C annealed.
 A. Ohta et al. / Microelectronic Engineering 72 (2004) 154–159
since the yield for the Si valence band can be
characterized by its power-law dependence with
respect to the energy exceed to its threshold energy
(5.15 eV in the flat band condition), the yield in the
energy region above 5.7 eV was first converted to
the density-of-states (DOS) in consideration of the
DOS curve of the Si valence band and the photo-
electron escape depth. In addition, the energy de-
pendence of ionization cross-section for localized
defect states was neglected. As indicated in Fig. 7,
by the O2 annealing at 700 °C, the midgap state
density is increase by a factor of 5 from the value of
as-deposited sample (1  1011 eV1 cm2 ). The
observed increase in defect states is presumably
attributable to the growth of the interfacial oxide
layer and presumably in part to hydrogen desorp-
tion at temperature as low as 700 °C as in the cases
of ZrO2 [4] and HfO2 [5].
4. Conclusions
The Y2 O3 /SiO2 /Si(1 0 0) stack structure with
well-defined abrupt interfaces and no detectable
incorporation Y atoms into the interfacial SiO2
layers was prepared by LPCVD using
Y[DPM]3 + O2 at 350 °C and subsequent O2 -an-
neal at 500 °C. The energy band alignment for the
stack structure has been determined from the
analyses of O1s energy loss spectra and valence
band spectra, where the conduction and valence
band offsets between Si(1 0 0) and Y2 O3 are eval-
uated to be 1.58 and 3.3 eV, respectively. From
PYS measurements, we suggested that the gener-
ation of defect states by O2 -anneal in the temper-
159
ature range 300–700 °C is related to the promotion
of interfacial oxidation.
Acknowledgements
The authors are very grateful to M. Ikeda and
H. Murakami for their contribution in performing
the experiments. Part of this work was supported
by the MIRAI project in Japan.
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