Synthesis and Characterization of Ba0.5Sr0.

5TiO3 Oxide Thin Film deposited on Silicon

(100) Substrate using Pulsed Laser Deposition Technique

Indah Darapuspa1,a, Mardiyanto2, Abu Khalid Rivai2, Salim Mustofa2, Bambang Sugeng2,
Deswita2, A. Agung Nugroho1
1
Institut Teknologi Bandung, Jl.Ganesha No. 10, Bandung 40132, Indonesia
2
Badan Tenaga Nuklir Nasional (BATAN), Puspiptek, Tangerang Selatan 15314, Indonesia
a
email : darapuspa.indah@gmail.com

ABSTRACT

Barium Strontium Titanate Oxide (BSTO) thin film has been deposited on Silicon (100)
substrate using Pulsed Laser Deposition (PLD) technique. Considerable amount of research has
recently focused on the growth of ferroelectric thin films. The ferroelectric BaTiO3 thin film is
very attractive for a large field of application. BSTO thin film is used in electronic and electro-
optic devices due to its high permittivity phenomena, associated with the basic ferroelectric
behaviour. For these applications it is important to have high-quality epitaxial thin films with
smooth surfaces. Actual efforts are being concentrated on reducing the size of electronic devices.
A related challenge is that of finding new materials or improving the dielectric properties of
existing materials used in the fabrication of ceramic capacitors and dynamic random access
memories (DRAMs) which require a high dielectric constant in the case of small dimensions. In
the high frequency range, it has high application potential. BSTO films have recently received
much attention for its high electric field tuneability and low dielectric loss. It can be used as
phase shifters, delay lines, tunable filters, steerable antennas. BSTO system must processes the
following characteristics: high dielectric constant, high tuneability, low dissipation factor amd
low temperature dependence when it will be applied in these devices. In this research, BSTO
bulk ceramic was used as the target for thin film deposition using Pulsed Laser Deposition
(PLD). Thin films of stoichiometric BSTO was deposited on Si (100) substrate. Film deposition
was carried out at 750°C by maintained the pressure at 190 mTorr. Nanometer-thick
BaSrTiO3 film on Si substrate was characterized using XRD and AFM. AFM images show that
BaSrTiO3 film has growth on Si substrate uniformly. XRD also support the growth of single
phase BaSrTiO3 film on Si substrate.

Keywords : thin film, barium strontium titanat oxide, pulsed laser deposition, XRD, AFM

Background of Research
The ferroelectric BaTiO3 thin film is very attractive for a large field of application, such
as memory cells, IR detectors, and electro-optic elements. BSTO thin film is used in electronic
and electro-optic devices due to its high permittivity phenomena, associated with the basic
ferroelectric behaviour. For these applications it is important to have high-quality epitaxial thin
films with smooth surfaces. Actual efforts are being concentrated on reducing the size of
electronic devices. A related challenge is that of finding new materials or improving the
dielectric properties of existing materials used in the fabrication of ceramic capacitors and
dynamic random access memories (DRAMs) which require a high dielectric constant in the case
of small dimensions. In the high frequency range, it has high application potential. Due to the
non linear variation of the permittivity with the applied electric field. This property offer the
opportunity to realize the electrically controlled of microwave devices. For this type of
applications, ferroelectric materials are made in the paraelectric phase in order to avoid high loss
in microwave domain and thermal hysteresis. The dielectric loss in ferroelectrics is not as small
as that of common dielectric materials and the loss tangent (tan d) is an important characteristic
of the material, which should be taken into account in the device design. The temperature
dependence of the dielectric permittivity over the operating temperature interval is another
important issue. This is of particular concern in the vicinity of the ferroelectric transition
temperature, where the material exhibits a strong tuneability, which depends strongly on the
temperature.
BSTO films have recently received much attention for its high electric field tuneability
and low dielectric loss These materials are very promising for practical applications such as
phase shifters, delay lines, tunable filters, steerable antennas. To be used in these devices, a
BSTO system must processes the following characteristics: high dielectric constant, high
tuneability, low dissipation factor amd low temperature dependence when it will be applied in
these devices.
In most cases, SrTiO3 (STO) single crystals are used as the substrate as it also has a
perovskite structure and its lattice parameters are close to those of BSTO. It is easy to obtain
epitaxial growth of BSTO films on STO crystals. However, new and promising applications have
created a demand to deposit BSTO films on different types of substrate, semiconducting Silicon.
Presently, silicon wafers are extremely utilized substrate to build electronic devices, such as
complementary metaloxidesemiconductor (CMOS) chips. If one could deposit BSTO thin films
on the Si substrates, it would pave the way to integrate BSTO into microelectronic devices.
BSTO is an important perovskite ferroelectric oxide due to its high-dielectric constant and large
piezoelectric coefficient. BTO thin films have been studied for many applications such as
piezoelectric detectors, thin film capacitors, and magnetoelectric (ME) devices.

So, in this research, I synthesized Barium Strontium Titanate Oxide (BSTO) thin film,
deposited on Silicon (100) substrate using Pulsed Laser Deposition (PLD) technique in order to
get the good ferroelectric thin film that further can be used in electronic application.
Method
Pulsed Laser Deposition
The pulsed laser deposition (PLD) named also, pulsed laser ablation (PLA) technique
offers many advantages for film growth, including epitactic or crystalline growth at low substrate
temperatures, congruent deposition of materials with complex stoichiometries, facile deposition
of materials with high melting points and ability to form metastable microstructures [19].
Conceptually and experimentally, PLD is extremely simple, probably the simplest among all thin
film growth techniques. It consists of a target holder and a substrate holder housed in a vacuum
chamber. A high-power laser is used to vaporize materials and to deposit thin films. Norton et al.
[19,21,22] demonstrated that epitactic BaTiO3 thin films could be grown on (001)-oriented
single-crystal MgO by pulsed laser ablation. The films produced were oriented with their c-axis
perpendicular to the film-substrate interface plane (c-axis oriented). It has been shown that the
microstructure of the films can be varied by changes in the deposition parameters.
Optimizing these variations permits the formation of thin films with controlled microstructures
and properties [23]. They obtained thin films of BaTiO3 with a Curie temperature of 110 °C by
PLD at 670 °C temperature of the substrate and 53 Pa ambient oxygen pressure.
Nakata et al. [24-27] make interesting studies onto the plume dynamics and the relationship
between the deposition conditions and film characteristics. They obtained BaTiO3 thin films on
MgO substrate by PLD at an oxygen pressure of 0-500 mTorr and at a heater temperatures of
800 and 850 °C. The lattice parameter of the film BaTiO3 was decreased as the oxygen pressure
was increased. The similar behavior has been reported by T. -F. Tseng et al. [28] for (1-
x)SrTiO3- xBaTiO3 films deposited on Si by PLD. The oxygen pressure also greatly influences
the surface morphology of these films. The size of the grain observed on the film surface is
larger as the pressure increase. At 10 mTorr, BaTiO3 thin film with smooth surface could be
obtained. Fig. 4 shows an AFM image of Ce-doped BaTiO3 surface film with a mean surface
roughness of 48 nm deposited by PLD in a small ambient oxygen pressure (30 Pa) [29].
Pulsed laser deposition or PLD is a reliable method to fabricate oxide thin films [1, 2].
Deposition parameters play an important role in achieving good-quality thin films. Key PLD
deposition parameters include deposition temperature, laser pulse repetition rate, laser energy,
and ambient gas pressure. Further, all of these conditions depend on the lattice parameters and
atomic coordinations of the substrate and thin film material. Previous experiments have shown
that the substrate can be adjusted to change the qualityand nanostructure of the films to satisfy
different needs [3]. For example, single-crystal substrates with different lattice parameters can be
used to tune the lattice mismatch of a film [4]: a suitable epitaxial strain can then enhance the
ferroelectric properties [4]. Clearly, understanding the behavior of oxide films on various
substrates is a meaningful approach to control the film quality and performance. Barium titanate
(BTO) is an important perovskite ferroelectric oxide due to its high-dielectric constant and large
piezoelectric coefficient. BTO thin films have been studied for many applications such as
piezoelectric detectors, thin film capacitors, and magnetoelectric (ME) devices [3]. In most
cases, SrTiO3 (STO) single-crystals are used as the substrate as it also has a perovskite structure
and its lattice parameters are close to those of BTO [5]. It is easy to obtain epitaxial growth of
BTO films on STO crystals.However, new and promising applications have created a demand to
deposit BTO films on different types of substrates: these include semiconducting Si and
magnetic/magnetostrictive Ni.
Presently, silicon wafers are extremely utilized substrate to build electronic devices, such as
complementary metaloxide- semiconductor (CMOS) chips. If one could deposit BTO thin films
on the Si substrates, it would pave the way to integrate BTO into microelectronic devices [6].
Epitaxial BiFeO3 films have previously been deposited on SrRuO3-(or SRO-) buffered Si by
PLD [7]. Epitaxial BTO thin layer with a TiN bottom layer has also been deposited on Si by RF
sputtering technique [8]. These prior successes inspire us to find a method to grow BTO on Si by
PLD technique. In addition to deposition, Si and metallic substrates offer other unique
opportunities for deposition of BTO layers. In particular,growth of BTO on
magnetic/magnetostrictive metals offers opportunity for multifunctionality [9]. Deposition of
BTO films on metallic substrates and the study of the functional properties of each layer could be
useful in the design of novel heterostructures, offering opportunities for BTO thin films in new
applications such as magnetoelectricity or magnetocapacitance. For example, the
magnetostriction of Ni is ∼34 ppm at room temperature. If we could grow a BTO film on Ni, one
could then develop heterolayered magnetoelectric (ME) laminates: where open application of an
external magnetic field would induce elastic shapes in the Ni foil, which would then be
transferred to the BTO layer generating a voltage. Such heterostructured ME laminate
Metglas/PZT-fiber composites show giant ME voltages [10, 11]. Deposition of BTO on Ni
would offer a means to fabricate miniaturized engineered ME structures that does not require any
epoxy bonding presently needed for the laminated composites. Here, after discussing BTO film
deposition on (111) STO substrates, we will demonstrate successful growth of BTO films on (i)
Pt-buffered Si and (ii) directly on magnetostrictive Ni foil. We believe that our findings will help
in the understanding of the role of various substrates on BTO films: ranging from insulating
oxide to semiconducting Si and to magnetostrictive metals.

Figure 1. a) BSBM – PSTBM (BATAN) PLD System, b) Vacuum chamber

Figure 2. Laser Deposition Process

Table 1. Parameter of the Deposition Process

Parameter Experimental Condition

Target Ba0.5Sr0.5TiO3
Substrate Silicon (100)
Laser Energy 23.5 j/cm2
Laser Pulse Number 72000
Laser Frequency 220 Hz
Substrate Temperature 750°C
MFC 37sccm
Gas Pressure (O2) / P shots 189 -190 mTorr
P Base 10-5 torr
Deposition Time 2 hours
Coding Rate ±1 hours (10°C/min)

the relationship between the deposition conditions and film characteristics. They obtained
BaTiO3 thin films on MgO substrate by PLD at an oxygen pressure of 0-500 mTorr and at a
heater temperatures of 800
as the oxygen pressure was increased. The similar behavior has been reported by T. -F. Tseng et
al. [28] for (1-x)SrTiO3- xBaTiO3 films deposited on Si by PLD. The oxygen pressure also
greatly influences the surface morphology of these films. The size of the grain observed on the
film surface is larger as the pressure increase. At 10 mTorr, BaTiO3 thin film with smooth
surface could be obtained. Fig. 4 shows an AFM image of Ce-doped BaTiO3 surface film with a
mean surface roughness of 48 nm deposited by PLD in a small ambient oxygen pressure (30 Pa)

Hasil dan pembahasan (image)

Atomic Forced Microscopy (AFM)

BST Target Preparation and Characterization
Ba1¡xSrxTiO3 ceramic compounds with the molar formula Ba0:5Sr0:5TiO3 (BST)
were prepared by standard solid-state reaction. SrCO3, BaCO3, and TiO2 oxide
powders of higher purity than 99.9% were used as starting materials. The BST
samples were doped with 1.0 mol. % MgO and 0,5 mol. % MnO2 in order to improve
the granular growth and to control the porous structure [10]. Mixing was carried out
for 2 hours in an agate bottle containing agate balls. The mixing-milling media were
distilled water. The mixtures were calcinated at T = 1 100±C for 2 hours, crushed,
mixed with polyvinyl alcohol (PVA) and then pressed in a cylindrical mold to yield
cylindrical pellets. The samples BST were sintered for 2 hours in air at temperatures
between 1 220 ¥ 1 320±C.
Structural and morphological analysis was performed on BST samples by using
X-ray di®raction (XRD) and Scanning Electron Microscopy (SEM). The values of the
dielectric constant "r and of losses at microwave frequencies were measured by using
the Hakki-Coleman dielectric resonator method [11].
The doped BST ceramic sintered at 1 285±C with good quality from the point
of view of morphology, structure and dielectric properties ("r » 1 100 and tan ± » 2 £ 10¡3) [12]
were selected as target for ¯lm deposition.

Film Deposition
Thin ¯lms of BST on platinum coated alumina and sapphire were performed by
pulsed laser deposition-PLD and radiofrequency assisted pulsed laser deposition, RF-
PLD. The RF-PLD system consists in a clasical PLD system added with a radiofre-
quency plasma beam source, which is made up by a double-chamber discharge system
supplied by a CESAR 1310 RF power generator of 13.56 MHz, and 1 kW maximum
power. The discharge is generated in the active chamber in °owing oxygen between
two parallel electrodes: it expands into the ablation chamber due to the pressure
Dielectric Properties of (Ba,Sr)TiO3 Thin Films 349
gradient as a plasma beam through an aperture performed in the bottom electrode,
which acts as a nozzle. This type of system was needed in order to improve the surface
roughness and to avoid oxygen vacancies inside the ¯lm.
First, with the help of RF-PLD system, a platinum bottom electrode was de-
posited on sapphire and alumina substrates in radiofrequency argon plasma discharge
at 100 W. Next step was to deposit BST on platinum coated sapphire and alumina in
radiofrequency oxygen plasma discharge at 100 W. The beam of a Nd:YAG solid-state
laser with wavelength 265 nm, pulse length 5 ns and the repetition rate 10 Hz, was
focused through a spherical lens on BST ceramic target at 45± incidence. In order to
achieve a uniform ablation, the target was simultaneously rotated and translated.
The substrates were heated to the deposition temperature with a ramp of 20±C/min
and then after deposition, cooled with 10±C/min, at 150±C for Pt/sapphire thin ¯lms
and 650±{720±C for BST/Pt/sapphire thin ¯lms. The substrates used were placed at
a distance of 4{5 cm from the target. The vacuum system allows obtaining a base
pressure of about 10¡6{10¡5 mbar before deposition.
The deposited ZST ¯lms were annealed ex situ for 2 h in a conventional thermal
oven, at the 800±C for 6 hours, for crystallization of the deposited layer.

Film characterization
The characterization of BST thin ¯lms was carried out by X-ray di®raction, Scan-
ning Electron Microscopy (SEM) and dielectric measurements.
The structure of BST thin ¯lms was investigated by X-ray di®raction (XRD) us-
ing a TUR-M62 di®ractometer (Cu Ka = 0.1541 nm). The layers morphology was
analyzed via Scanning Electron Microscopy (SEM), with a Hitachi S2600 N micro-
scope. The electrical measurements were performed using an Agilent LCR meter. The
capacitance-voltage (C-V) characteristics of BST ¯lms were recorded using a computer
controlled Keithley multimeter at 100 kHz in the temperature range {237 ¥ +27±C.
The temperature control was made by using a Cryostat Janis CCS - 400EB.

Results
The X-ray di®raction patterns of the BST thin ¯lms, deposited on sapphire
(BST 1) and alumina (BST 2) substrates, are shown in Fig. 1. The temperature
substrate was of 650±C for both BST 1 and BST 2 samples. In addition, the BST 1
sample was post-annealed at 800±C for 6 hours.
The X-ray di®raction patterns of the BST thin ¯lms show narrow peaks, proving a
good crystallization of the ¯lms. After the thermal treatment, a better crystallization
degree and a decrease of the amorphous component contribution were obtained. Some
peaks, related to the alumina substrate and Pt, are visible on the X-ray diagrams.
The crystallite mean dimension (D) was calculated from the formula:
D (nm) = k¸(nm)=¯ cos µ; (1)
where ¯ is half of the linewidth (rads), µ is the Bragg angle and k a constant depending
350 A. Ioachim et al.
on the crystallites shape. In a spherical coordinate system, k = 1.0747 for crystalline
plans with Miller indices (hkl) greater than (110). For BST 1 and BST 2 the crystallite
mean dimension are given in Table 1.
The lattice constants of thin ¯lm samples were determined and compared with
the values of the BST target. They correspond fairly very well to the values of
Ba0:5Sr0:5TiO3 [10] and are also presented in Table 1.

The SEM analysis revealed BST ¯lms with rough surface due to the randomly
oriented grain morphology as resulting from Fig. 2. The SEM image is for the BST
¯lm surface annealed at 800±C at 6 hours. It can be seen submicronic grains, randomly
oriented due to the ¯lm deposition on the alumina polycrystalline substrate. The
majority of grains exhibit spherical shape with sizes in the range of 0.1 ¥ 0.2 ¹m.
Few larger cubic well faceted grains with dimension 0.3 ¥ 0.5 ¹m are also present.
Next, copper was evaporated on BST thin ¯lm PLD deposited on alumina and
a metallic interdigital structure was realized by photolithography. At room temper-
ature, the measured capacitance for this BST interdigital structure was 45.7 pF. In
order to focus on the BST e®ects, the measured values will be normalized in the
Dielectric Properties of (Ba,Sr)TiO3 Thin Films 351
following to 30.2 pF, which is the capacitance of the same interdigital structure on
alumina, in the absence of BST.

Conclusion
Ferroelectric BST thin films was successfully deposited on Silicon (100) substrate using PLD. A
BSTO bulk ceramic with 1 inch in diameter was used as a target for PLD the thin film
deposition. Film deposition was carried out at 750°C by maintained the pressure at 190 mTorr.
The laser frequency pulse at 220Hz was apllied during the deposition process. The
BaSrTiO3 thin film on Si substrate was analyzed using XRD and its pattern show the films are
single crystal with the same plane direction. XRD also support the growth of single phase
BaSrTiO3 film on Si substrate. AFM images indicate that BaSrTiO 3 film has growth on Si
substrate uniformly, well crystallized and crack free. However, it is not very smooth and pinhole
free. The thickness of the BSTO thin film are about 1 nm to 20 nm in an area of 1 µm x 1 µm, 1
nm to 25 nm in an area of 3 µm x 3 µm and 1 nm to 20 nm in an area of 10 µm x 10 µm,
respectively.

Thanks to Mr. A. Agung Nugroho as my supervisor in doing my undergraduate research project,

Mr. Mardiyanto as my research project supervisor at BATAN, Mr. Abu Khalid Rivai as my
supervisor in PLD technique at BATAN, Mr. Salim Mustofa as an expert in PLD and Mr.
Bambang Sugeng as an expert in XRD Characterization.

References
[1] A. Ioachim, M. I Toacsan, L. Nedelcu, et al., “Dielectric Properties of (Ba,Sr)TiO3 Thin
Films for Applications in Electronics,” Romanian Journal of Information Science and
Technology, vol. 10, number 4, pp. 347-354, 2007.
[2] M. P. Warusawithana, C. Cen, C. R. Sleasman, et al., “A Ferroelectric Oxide made directly
on Silicon,” Science, vol. 324, number 5925, pp. 367–370, 2009.
[3] R. Eason., “Pulsed Laser Deposition of Thin Films,” 2007.