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Thin-film growth of (110) rutile TiO2 on (100) Ge substrate by pulsed laser deposition

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2016 Jpn. J. Appl. Phys. 55 06GG06
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REGULAR PAPER

Japanese Journal of Applied Physics 55, 06GG06 (2016)

http://doi.org/10.7567/JJAP.55.06GG06

Thin-lm growth of (110) rutile TiO2 on (100) Ge substrate by pulsed laser deposition
Yoshihisa Suzuki1,2, Takahiro Nagata2,3*, Yoshiyuki Yamashita2, Toshihide Nabatame2,
Atsushi Ogura1, and Toyohiro Chikyow2
1

Graduate School of Science and Technology, Meiji University, Kawasaki 214-8571, Japan
WPI-MANA, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, Japan
3
JST, PRESTO, Kawaguchi, Saitama 332-0012, Japan
2

*E-mail: NAGATA.Takahiro@nims.go.jp
Received November 30, 2015; revised December 28, 2015; accepted January 3, 2016; published online April 26, 2016
The deposition conditions of (100) rutile TiO2 grown on p-type (100) Ge substrates by pulsed laser deposition (PLD) were optimized to improve the
electrical properties of the TiO2/Ge structure. Increasing the substrate temperature (Tsub) enhanced the grain growth, the surface roughness of the
lm, and Ge diffusion into the TiO2 layer. The growth rate, which was controlled by the laser density in PLD (Ld ), affected the Ge diffusion. Ld of
0.35 J/cm2 (0.37 nm/min) enhanced the Ge diffusion and improved the crystallinity and surface roughness at a temperature of 450 C, at which
GeOx undergoes decomposition and desorption. However, the Ge diffusion into TiO2 degraded the electrical properties. By using the optimized
conditions (Ld = 0.7 J/cm2 and Tsub = 420 C) with postannealing, the TiO2/Ge structure showed an improvement in the leakage current of 3 orders
of magnitude and the capacitancevoltage property characteristics indicated the formation of a pn junction.
2016 The Japan Society of Applied Physics

1.

Introduction

In recent years, SiO2=Si metaloxidesemiconductor (MOS)

devices have been facing the crucial issue of the scaling limit
due to the leakage current and mobility.1) In order to achieve
further progress in MOS devices, a high-mobility semiconductor and a high-dielectric-constant (high-k) material are
essential. Ge is a candidate next-generation channel material
to enhance MOS gate structures. Ge has higher electron and
hole mobilities than Si.2,3) However, there is an issue of
interface states because of the formation of GeOx, which has
a low dielectric constant and is thermodynamically unstable4,5) and water-soluble.6) To overcome this issue, many
experiments have been performed to investigate the eects
of GeN passivation,79) Si passivation,10) and direct HfO2
formation on Ge. However, there have been no denitive
solutions regarding the interface structure and dielectric
constant. We have proposed the direct growth of rutile-type
TiO2 on Ge(100). Rutile-type TiO2 has a higher dielectric
constant ([110] = 86)1113) and a lower formation energy of
the oxide (TiO2; G = 887.6 kJ=mol) than those of Ge
(GeO2; G = 518.5 kJ=mol),1416) which enable further
equivalent oxide thickness (EOT) scaling and make it
possible to suppress the formation of GeOx. We have
demonstrated the epitaxial growth of (110) rutile TiO2 on a
(100) Ge substrate at a substrate temperature of 450 C,
which is generally the growth temperature of anatase TiO2
by pulsed laser deposition (PLD).17) However, there are still
issues of the poor leakage current property and surface
roughness of the TiO2 layer. Furthermore, Ge diusion,
which enhances the crystallinity but reduces the dielectric
constant, was conrmed. In this work, to overcome these
issues and determine the eect of Ge diusion, we optimized
the substrate temperature and deposition rate by controlling
the laser energy density in the PLD process.
2.

Experimental procedure

P-type Ge(100) was used as substrates. The substrates were

cleaned in organic solvents and rinsed with deionized water
then subjected to UVozone cleaning before loading into a
growth chamber. TiO2 lms were deposited by PLD with a

KrF excimer laser ( = 248 nm). Before the TiO2 deposition,

the native oxide (GeOx) layer was removed by annealing
at 420 C for 20 min under an ultrahigh-vacuum condition
(<7 106 Pa).18,19) The laser ablated a sintered TiO2
ceramic target under an O2 partial pressure of 1.3 103
Pa. The substrate temperature (Tsub) was 390, 420, or 450 C.
Note that the temperature of 420 C is the threshold
temperature for the decomposition and desorption of GeOx.20)
The laser energy density (Ld ) was 0.7, 0.35, or 0.17 J=cm2,
for which the deposition rates were 1.40, 0.80, and 0.37
nm=min, respectively. Table I shows the combinations of
Tsub and Ld for all samples and their labels, which were
denoted as Ld-Tsub-TiO2. When the one condition was
changed, the labels indicate the changed condition such as
Ld-TiO2 and Tsub-TiO2. For example, Ld0.17-TiO2 means that
the samples were deposited at Ld = 0.17. After deposition,
some of the samples were annealed in oxygen at 400 C for
30 min. A 150-nm-thick Ru top electrode with a diameter of
100 m was deposited by DC sputtering using a shadow
mask. The crystal structure and crystallinity were analyzed by
two-dimensional X-ray diraction (2D-XRD) with a 5 kW
rotating anode Cu target and a high-resolution 2D detector
(Bruker AXS D8 Discover Super Speed with GADDS). A
section of the DebyeScherrer ring was studied using a 2DXRD image. In this approach, a 2 mapping around the
(110) peak of rutile TiO2 is acquired simultaneously. The
dispersion in the crystallographic alignment can be estimated from the full width at half maximum (FWHM) of
angle . The surface morphology was observed by atomic
force microscopy (AFM; Hitachi-High-Tech AFM5000 and
AFM5300E). The chemical bonding states were analyzed by
X-ray photoelectron spectroscopy (XPS) using a monochromated Al K X-ray source (h = 1486.6 eV, Thermo Scientic Theta Probe). The total energy resolution in XPS was set
to 700 meV. The XPS data were calibrated against the
Au 4f7=2 peak (84.0 eV) and the Fermi level of Au set at the
same ground level as the sample. To analyze the XPS results,
core-level spectra were tted using the Voigt function after
the background had been removed by employing the Shirley
function.21) Electrical properties were evaluated by current
voltage (IV) and capacitancevoltage (CV) measurements

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Jpn. J. Appl. Phys. 55, 06GG06 (2016)

Y. Suzuki et al.

Table I. Substrate temperature and laser energy density matrix of fabricated samples.
Laser energy density
(J=cm2)

Substrate temperature (C)

Deposition rate
(nm=min)

390

420

450

1.4

Ld0.70-Tsub390-TiO2

Ld0.70-Tsub420-TiO2

Ld0.70-Tsub450-TiO2

0.8

Ld0.35-Tsub390-TiO2

Ld0.35-Tsub420-TiO2

Ld0.35-Tsub450-TiO2

0.17

0.37

Ld0.17-Tsub390-TiO2

Ld0.17-Tsub420-TiO2

Ld0.17-Tsub450-TiO2

FWHM [deg]

0.70
0.35

8.0
@ 30 nm

7.0

0.70 J/cm

0.35 J/cm

6.0

0.17 J/cm

390
(a)

(b)

400 410 420 430 440

o
Substrate temperature [ C]

450

Fig. 2. (Color online) Substrate temperature and laser density

dependences of -FWHM for TiO2(110) reection.

(c)
Fig. 1. (Color online) (a) 2D-XRD pattern and (b) pole gure image of
30-nm-thick TiO2=Ge stack structure deposited at Tsub = 420 C and
Ld = 0.35 J=cm2. (c) Calculated pole gure image of the {101} plane for
rutile TiO2.

using a semiconductor parameter analyzer (Keysight Technologies B1500A).

3.

Results and discussion

Figure 1(a) shows the 2D-XRD pattern of Ld0.70-Tsub420TiO2 as an example. All the samples except for Ld0.17Tsub450-TiO2 exhibited spots corresponding to the 110
reection from the rutile structure at 2 = 27.3. X-ray pole
gure measurements revealed that the crystallographic
relationships of TiO2 with Ge were (110) TiO2 (001) Ge
and [100] TiO2 [100] Ge with a 90 rotated domain as
shown in Figs. 1(b) and 1(c), which was consistent with
our previous reports.17) In contrast, the crystal structure of
Ld0.17-Tsub450-TiO2 was conrmed to be amorphous.
Figure 2 shows the substrate temperature and laser density
dependences of the FWHM of angle . Up to the substrate
temperature of 420 C, the FWHM decreased with increasing
laser density. In contrast, at 450 C, this tendency disappeared. Ld0.35-Tsub450-TiO2 showed higher crystallinity than
Ld0.70-Tsub450-TiO2.
Figures 3(a)3(c) show AFM images of Ld0.70-Tsub450-,
Ld0.70-Tsub420-, and Ld0.70-Tsub390-TiO2, respectively.
With decreasing substrate temperature, the root-mean-square

(RMS) roughness of the AFM images decreased as shown in

Fig. 3(d). At the substrate temperature of 450 C, the grain
growth was markedly enhanced. The dependence of the laser
density also showed a similar tendency up to the substrate
temperature of 420 C. With increasing laser density, the
RMS roughness increased.
According to our previous results, at the substrate
temperature of 450 C, Ge diuses into the TiO2 layer.17)
To investigate the Ge diusion, the chemical bonding states
were investigated by XPS as shown in Fig. 4. Figures 4(a)
4(c) show core-level spectra of Ti 2p, Ge 2p3=2, and O 1s for
the 30-nm-thick Ld0.35-Tsub450-TiO2, respectively. Ge 2p3=2
spectra corresponding to the GeO2 bonding state at 1220.5
eV2224) were observed. The inelastic mean free path (IMFP)
of a photoelectron from the Ge 2p3=2 core level in XPS
calculated using the TanumaPowellPenn (TPP-2M) equation is 0.9 nm, meaning that the detection depth of Ge 2p is
about 2.7 nm (3 IMFP).25,26) Therefore, in Fig. 4(b), the
GeO2 bonding state originated from the Ge atoms diusing
into the TiO2 lm, which nearly reached the surface. Thus,
from the O 1s spectra, TiO2 and GeO2 bonding states were
conrmed.27) The intensity ratio of Ge 2p3=2 to Ti 2p3=2
was plotted as functions of the substrate temperature and
laser density as shown in Fig. 4(d). With increasing substrate temperature, the ratio increased, meaning that the Ge
diusion was enhanced by the high substrate temperature.
Furthermore, the Ld0.35-TiO2 samples showed a higher
amount of Ge diusion into the TiO2 lm than other samples.
This phenomenon can be explained by the correlation
between the growth rate and the ability of Ge diusion. In
the case of a crystalline structure, the grain boundaries induce
metal diusion.28,29) In contrast, an amorphous structure and
a dense (small grain) structure prevent metal diusion.
Furthermore, from the viewpoint of the thermal diusion of
the metal, under the vacuum condition, Ge can easily diuse
into Ti.30,31) The thermal diusion equation includes the
temperature and time, meaning that a long growth time (low

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Jpn. J. Appl. Phys. 55, 06GG06 (2016)

Y. Suzuki et al.

(a)

(b)

(c)

RMS [nm]

16
12
2

0.70 J/cm

0.35 J/cm

0.17 J/cm

4
390

400 410 420 430 440

o
Substrate temperature [ C]

450

(d)

Ti2p

3000
2000
1000

Ti2p5/2

Experiment
Sum
Background
Ti5/2
Ti3/2

Ti2p3/2

0
470

465

460

455

2400

Ge2p

Experiment
Sum
Background
Ge

2000
1800
1600

Binding energy [eV]

1224

1220

1216

Binding energy [eV]

TiO2

Experiment
Sum
Background
TiO2
GeO2

3000
2000

GeO2

1000
536

1212

534

532

530

Binding energy [eV]

528

(c)
2

Annealed 0.70 J/cm

Annealed 0.35 J/cm

Annealed 0.17 J/cm

As-depo. 0.70 J/cm

1.9

As-depo. 0.35 J/cm

As-depo. 0.17 J/cm

As-depo. 0.70 J/cm

2
2
2

As-depo. 0.35 J/cm

O1s/Ti2p

Ge2p/Ti2p

O1s

4000

(b)

@30 nm

0.6

5000

1400

(a)
0.8

Ge2p3/2

2200

Intensity (arb unit)

4000

Intensity (arb unit)

Intensity (arb unit)

Fig. 3. (Color online) AFM images of TiO2 lms deposited under the conditions of (a) Tsub = 450 C and Ld = 0.70 J=cm2, (b) Tsub = 420 C and
Ld = 0.70 J=cm2, and (c) Tsub = 390 C and Ld = 0.70 J=cm2. (d) Substrate temperature and laser density dependences of RMS roughness.

As-depo. 0.17 J/cm

0.4
0.2

1.8
1.7
1.6

0.0
390

400
410
420
430
440
o
Substrate temperature [ C]

450

1.5
390

(d)

400

410

420

430

440

Substrate temperature [ C]

450

(e)

Fig. 4. (Color online) Core-level spectra of (a) Ti 2p, (b) Ge 2p3=2, and (c) O 1s. Intensity ratios of (d) Ge 2p3=2 to Ti 2p3=2 and (e) O 1s to Ti 2p3=2 as
functions of substrate temperature and laser density.

deposition rate) and a high growth temperature should

enhance the Ge diusion. Ld0.35-TiO2, which had a slower
deposition rate and a higher crystallinity than Ld0.17-TiO2
(Fig. 2), showed the highest Ge incorporation in the TiO2
layer, as shown in Fig. 4(d). Furthermore, at a substrate
temperature of 450 C, the GeOx decomposition and adsorption were enhanced,20) which should aect the growth of
TiO2. The Ge incorporation aected the crystallinity of TiO2

at the temperature of 450 C. The laser energy dependences

of the crystallinity and surface roughness of Tsub450-TiO2
were consistent with the laser energy dependence of the Ge
concentration.
Figure 5(a) shows the IV characteristics of Ld0.70Tsub420-TiO2 before and after the postgrowth annealing as
an example. Figure 5(b) shows the current density at a bias
voltage of 0.5 V plotted against the substrate temperature

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Y. Suzuki et al.

(a)
(b)

(c)

(d)

Fig. 5. (Color online) (a) IV characteristics of Ld0.70-Tsub420-TiO2 before and after postgrowth annealing. (b) Current density at a bias voltage of 0.5 V
as functions of the laser density and the substrate temperature of the Ru=TiO2=Ge=Ru structure. (c) CV characteristics of Ld0.70-Tsub420-TiO2. (d) Band
alignment of TiO2 and Ge.17)

and laser density. All as-deposited samples showed high

leakage currents regardless of the lm growth conditions.
According to our previous report, an oxygen partial pressure
of 1.3 103 Pa is required to form oxide vacancies.17)
Below and above the oxygen partial pressure of 1.3
103 Pa, the formation of oxygen vacancies and the formation
of GeOx at the Ge surface were enhanced, respectively. Thus,
the oxygen partial pressure was xed as 1.3 103 Pa in this
work. To reduce the number of oxygen vacancies, postgrowth annealing was performed. After annealing, some
samples showed an improved leakage current as shown in
Figs. 5(a) and 5(b). By considering the intensity ratio of
the O 1s to Ti 2p3=2 (O 1s=Ti 2p3=2) core-level spectra, the
oxygen vacancies were also investigated as shown in
Fig. 4(e). As a reference, a rutile TiO2(110) substrate
(Shinkosha) was also investigated. The O 1s=Ti 2p3=2 ratio
of the substrate was 2.0. All the as-deposited samples showed
a ratio of around 1.6 regardless of the substrate temperature
and laser density. These results suggest that the as-grown
TiO2 lms had more oxygen vacancies than the TiO2
substrate. After annealing, the TiO2 lms grown at 450 C
showed an increase in the O 1s=Ti 2p3=2 ratio regardless of
the laser density, as shown in Fig. 4(e). The O 1s=Ti 2p3=2
ratio of the annealed Ld0.70-Tsub450-TiO2 was almost the
same as that of the substrate. Tsub450-TiO2 has fewer oxygen
vacancies after the postannealing than the other samples
grown at 390 and 420 C, and showed an improvement in
the leakage current of approximately 3 orders of magnitude
[Fig. 5(b)]. However, from the viewpoint of MOS application, the Ge incorporation reduced the dielectric constant, and

the rough surface is also not suitable. Under the various

conditions, Ld0.70-Tsub420-TiO2 showed lower dielectric loss
than Tsub450-TiO2.
Figure 5(c) shows the CV characteristics of Ld0.70Tsub420-TiO2. At a negative bias, the capacitance increased
linearly with increasing bias voltage. At a voltage from 0.1 to
0.2 V, the capacitance abruptly decreased with dispersion of
the dielectric loss. This CV behavior can be explained by the
valence band oset between Ge and rutile TiO2. Our previous
report revealed that the valence band oset between Ge and
rutile TiO2 is 2.5 0.1 eV with a type II band alignment
and a pn junction structure as shown in Fig. 5(d).17) This
band alignment is consistent with the CV characteristics of
Ld0.70-Tsub420-TiO2. These results suggest that the intrinsic
TiO2 properties are unsuitable for a Ge-based MOS structure.
However, it is still possible to improve these properties
by acceptor doping to TiO2. Additionally, according to a
previous report, some TiO2 acceptors such as Mg and Mn
promote the crystallization of the rutile phase.32)
4.

Conclusions

The growth conditions of rutile (110) TiO2 on a p-type (100)

Ge substrate were optimized by varying the laser energy
density (growth rate) and the substrate temperature in the
PLD process. The Ge diusion strongly aected the growth
of TiO2. Ld of 0.35 J=cm2 (0.37 nm=min) enhanced the Ge
diusion and improved the crystallinity and surface roughness at a temperature of 450 C. However, the Ge diusion
into TiO2 degraded the electrical properties. Ld = 0.7 J=cm2
and Tsub = 420 C with postgrowth annealing, resulted in the

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Y. Suzuki et al.

formation of a TiO2=Ge structure with pn-junction-type

capacitancevoltage characteristics.
Acknowledgements

We are grateful to Ms. A. Ogawa for technical support with

the PLD deposition. WPI-MANA was established by the
World Premier International Research Center Initiative
(WPI), the Ministry of Education, Culture, Sports, Science
and Technology, Japan (MEXT). This work was partly
supported by Precursory Research for Embryonic Science
and Technology (PRESTO), Japan Science and Technology
Agency (JST).

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