APPLIED PHYSICS LEITERS VOLUME 73, NUMBER 16 19 OCTOBER 1998

Dielectric properties of epitaxial BaTi0 3 thin films

B. H. Hoerman, G. M. Ford, L. D. Kaufmann,a) and B. W. Wessels b)
Department ofMaterials Science and Engineering and Materials Research Center, Northwestern University,

Evanston, Illinois 60208

(Received 23 April 1998; accepted for publication 18 AUgUst 1998)

The dielectric response of epitaxial BaTi03 thin films deposited on MgO was measured through

surface electrodes as a function of applied bias, frequency, and temperature. The room temperature

value of the dielectric constant was -500 with a dissipation factor, tan(8), of 0.05 at 100 kHz.

Measurements varying the bias field showed hysteresis of the dielectric response and a tunability of

30% for a maximum applied field of -7 MV/m. The frequency response of the dielectric constant

is well described by a Curie- von Schweidler power law with an exponent -0.04 in the range 1

kHz-13 MHz. The films undergo a diffuse phase transition at temperatures higher than the bulk

Curie temperature. The behavior of the dielectric response is attributed to the presence of residual

strain in the epitaxial thin films. © 1998 American Institute ofPhysics. [S0003-6951(98)00642-1]

Ferroelectric thin film materials such as BaTi03 and rine present in the film from the fluorinated barium precur­
BaxSr(l _x)Ti03 (BST) promise to bring about a new genera­ sor.
tion of high-frequency devices such as tunable capacitors, 1 X-ray diffraction indicated that the films were phase
microwave phase shifters,2 and electro-optic modulators. 3 pure BaTi03 • Diffractometer measurements revealed broad,
Thin film ferroelectric devices offer several advantages over tetragonally split (h 00) peaks with a full width half maxi­
their bulk counterparts, such as lower driving voltages, mum (FWHM) (200) of 0.51°. The measured out-of-plane
higher speeds, and the potential for monolithic integration lattice parameters of3.995 and 4.015 A were between a- and
with Si. 1 A major barrier, however, to their widespread use c-axis lattice spacings for bulk BaTi03• Alignment of the
in a number of high-frequency applications is their high di­ film to the substrate was confirmed with x-ray diffractometer
electric loss.4 phi scans of the off-axis (220) planes in the BaTi03 crystal
While bulk BaTi03 and other ferroelectric crystals dis­ lattice. The requisite fourfold symmetry was observed, in­
play very pure Debye resonances,5,6 the frequency response dicative of epitaxy. Atomic force microscopy was used to
in thin films shows a power law dependence with concurrent analyze the surface morphology of the films . A columnar
high dielectric Iosses.1,4 This type of power law has been subgrain structure was noted. The mean size of the subgrains
observed in a wide range of structurally disordered dielec­ was 200 nm and the rms surface roughness was in the 5-10
trics. In polycrystalline thin films, this behavior has been nm range. Film thickness was measured using a Metricon
attributed to inhomogeneities reSUlting from either the pres­ 2010 prism coupler. Films of 120 and 320 nm thickness were
ence of grain boundaries7 or point defects 8 which modify the used for this study, and no differences in their structural or
local charge density. electrical characteristics were observed.
For dielectric constant measurements, interdigital elec­
To understand, and eventually minimize, the factors
trodes (IDEs) were deposited on the film surfaces by stan­
leading to these losses, we have investigated epitaxial films
dard lift-off techniques. The structure is shown in Fig. 1.
of BaTi03 grown directly on MgO. For epitaxial films, losses
Bilayer electrodes of total length 0.20 m and thickness of
resulting from the presence of high angle grain boundaries
300 nm were deposited by electron-beam evaporation and
are eliminated. In this letter, we report our investigations on
consisted of a 150 nm Cr adhesion layer covered by 150 nm
the frequency, bias, and temperature response of the in-plane
of Au. The use of Cr-Au facilitated fine-line lithography.
dielectric constant of epitaxial BaTi03 thin films. Dielectric Electrical connection to a Hewlett Packard HP16047C test
response measurements indicate a power law frequency de­
pendence of the dielectric constant, significant bias response,
and the presence of a diffuse phase transition at elevated
temperatures.
Films were grown on MgO (100) substrates by low­
pressure metalorganic chemical vapor deposition (MOCVD)
at 725 °C. 9 Titanium tetraisopropoxide and barium hexafluo­
roacetylacetonate (tetraglyme) were utilized as metal organic
precursors, and Ar was used as the carrier gas. The oxidant
was oxygen saturated with water in order to remove the fluo­

a)Present address: Department of Chemistry, Greenville College, Greenville,

IL 62246.
b)Electronic mail: [email protected] FIG. 1. Schematic representation of the interdigital electrode structure.

0003-6951/98173(16)/2248/3/$15.00 2248 © 1998 American Institute of Physics

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Appl. Phys. Lett., Vol. 73, No. 16, 19 October 1998 Hoerman et a/. 2249

1000

- ...c
-•
$
c
.:! 500
c
...as
•c
0
o (,)
=
(,)
()
o E'(fI» = E'(o) - A' m 0.0314
() i:
A" = 15.2
:s
()
450 0
.!!

100
A' = 319
.!! .!!
e '(0) = 951
.!! Q
c G)
G) >
;:
~ 400
:; .!
G) ~tmml!iQoo<D=t!t. tiiitJIi2~
G)
a:
a:
350~"~U.~u. . .~. .~u.~~. .~. .~
-40 -30 -20 -10 0 10 20 30 40
Applied Bias (V) Frequency (Hz)
FIG. 2. Bias field response of the dielectric constant at room temperature
and 100 kHz. Data were taken after an initial ramp to +35 V. FIG. 3. Frequency spectrum of the dielectric constant at room temperature.
Data follow a Curie-von Schweidler power law.

fixture was made with short (10 cm) copper leads.

The impedance of the structures was obtained with a tunability of 25% for fields of 5-10 MV1m, and 55% for
HP4192A impedance analyzer over the frequency range 1 fields of 20- 80 MV/m. 1,15 Impedance-bias measurements
kHz-13 MHz. After nulling out the parasitic impedance of also show hysteresis, indicating the films are ferroelectric.
the test apparatus at the frequency of interest, the electrode­ The frequency response of the dielectric constant was
film structure was modeled as a parallel resistor and capaci­ studied from I kHz to 13 MHz at a bias level of 1.1 VRMS'
tor to obtain the capacitance and dissipation factor (tan 8). The behavior of the real (E') and imaginary (I' = E' tan 8)
The dielectric constant of the film was then calculated from portions of the dielectric spectrum are shown in Fig. 3. A
the capacitance, electrode geometry, film thickness, and di­ power law dispersion of E' and E" is noted. The behavior is
electric constant of the MgO substrate. 10 The dielectric con­ given by the Curie- von Schweidler relationship:s
stant and dissipation factor of the MgO substrate were ob­ , , A' w,
m
E(w)=e(O)-
tained through the above method. The calculated value of 9.9
was in good agreement with the accepted value ll of 9.65 for 6:" m
"" ( w) =A"w •
the dielectric constant, and showed negligible dependence on
frequency or applied bias. In these expressions, w and E(O) are the angular frequency
Temperature dependence of the dielectric constant was and the static dielectric constant, respectively, and A I, A", m
measured by placing samples in a small tube furnace and are constants. The curves in Fig. 3 are obtained by first fitting
heating them in air. Impedance measurements were taken at the imaginary portion of the spectrum to obtain m, which is,
100 kHz and 1.1 VRMS as the sample cooled from a tempera­ in turn, used to fit the real portion. Values for the exponent m
ture slightly above 200°C to ambient. The maximum rate of were in the range 0.03-0.05. An m value of zero would
cooling for the sample was less than 2 °C/min. indicate the frequency independent behavior expected of a
For the BaTi03 films, measured capacitances of the pure Debye system above, or below, the resonant frequency.
IDEs were· -60 pF with dissipation factors of -0.05 at 100 The weak dependence of E', and consequently I', on fre­
kHz. A dielectric constant of -500 was calculated for the quency is consistent with observations in thin film polycrys­
BaTi03 films, which is between the a- and c-axis values for talline BST and BaTi03,I,4 and has been reported to persist
bulk crystals (2200 and 56, respectively).6 A value of 500 is up to the GHz range. 16
half that reported for the highest dielectric constant BaTi03 Although the Curie-von Schweidler relation is empiri­
thin films, and measured dissipation factors are similar. 12- 14 cal, there are many models which link it to physical proper­
Reports on BST thin films reveal comparable dielectric con­ ties. The majority of these models are based on the presence
stants with losses of -0.005. 1,2 Losses are typically lower in of compositional or structural inhomogeneities and/or many­
BST since it is in the lower-loss paraelectric state. 2 bodyeffects. 4,5,13
The bias dependence of the dielectric constant was in­ To detennine the frequency response of the thin films in
vestigated to determine the ferroelectric state of the films. A the paraelectric state, measurements were performed up to
0.3 VRMS signal was used to measure the small signal capaci­ temperatures of 210°C. Data taken for one sample are
tance at 100 kHz as the bias voltage was ramped between shown in Fig. 4. A broad transition peak in both E' and I' is
-35 and +35 V. The bias dependence shown in Fig. 2 is observed. The maximum, where the value is frequency de­
typical of the films. A decrease in the dielectric constant with pendent, occurs at temperatures higher than the Curie tem­
increasing bias from -500 to -350 was observed. Thus an perature of 120°C for bulk BaTi03. 17 Maxima of the E'
applied field of -7 MV/m results in a tunability of 30%. For peaks occur from 145- 170 °C, and maxima in If at slightly
comparison, polycrystaline BST thin films have reported a lower temperatures.
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2250 Appl. Phys. Lett., Vol. 73, No. 16, 19 October 1998 Hoerman et al.

surface electrodes indicate a dielectric constant - 500 with a

.<0>
dissipation factor -0.05 at 100 kHz. The frequency depen­
dence obeys a Curie-von Schweidler power law with an
-
-<0>

C
650 40
C
.
! exponent of -0.04 over the range 1 kHz-I3 MHz, similar to
that observed in polycrystalline films. An electric field of-7
..
.! 600
c
o
35 g
Co) MV1m resulted in a 30% modulation of the dielectric con­
~ stant. Temperature dependent measurements indicate a dif­
o 550
Co) 30 ..
o fuse phase transition slightly above that of the bulk.
:so :!•
.! 500 25 Q The authors are grateful to A. DiVenere and D. M. Gill
.!
Q
.
~ for their assistance with electrode fabrication, and to T. J.
Marks and J. Belot for supplying the Ba metal organic pre­
G
o 450
II:
20 =
..
Q
cursor. This work was supported under AFOSRlARPA
.Ii award No. F49620-96-I-0262 and NSFIMRSEC award No.
DMR-9632472.
10 50 90 130 170 210

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