Thin Solid Films 515 (2006) 615 – 618

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AgTaO3 and AgNbO3 thin films by pulsed laser deposition

Jang-Yong Kim *, Alexander M. Grishin
Condensed Matter Physics, Royal Institute of Technology, Electrum 229, SE-164 40 Stockholm-Kista, Sweden
Available online 19 January 2006

Abstract

Silver tantalate AgTaO3 (ATO) and silver niobate AgNbO3 (ANO) films have been grown on to the LaAlO3 (001) and sapphire Al2O3 (0112, r-
cut) single crystals by pulsed laser deposition technique from stoichiometric ATO and ANO targets. X-ray diffraction study revealed epitaxial
quality of ATO and ANO films on the LaAlO3 (001) whereas on the sapphire r-cut substrate they are preferential (110) and (001) oriented. To
characterize microwave films properties in the range from 1 to 40 GHz, coplanar line interdigital capacitors were fabricated by photolithography
and lift-off technique. ANO film capacitors show superior properties: frequency dispersion was as low as 13%, voltage tunability (40 V, 200 kV/
cm) was about 4.6% at 20 GHz, loss tangent ¨0.106 at 20 GHz, K-factor = tunability / tand from 49% @ 10 GHz to 33% at 40 GHz.
D 2006 Elsevier B.V. All rights reserved.

PACS: 77.84.Dy
Keywords: Ferroelectric ceramics; Pulsed laser deposition; Epitaxial silver tantalate niobate films; Coplanar waveguides; Voltage tunable microwave devices;
Scattering parameters measurement

1. Introduction microwave properties of ATO and ANO thin films sintered by

pulsed laser deposition (PLD) technique. To our knowledge,
Ferroelectric materials of various compositions have been there were no reports so far on silver tantalate and silver
studied for many years for microwave applications: variable niobate films.
capacitors (varactors), filters, and phase shifters [1 –4]. On the
side of material properties, voltage tunable devices require high 2. Experimental
dielectric permittivity and low loss tangent. As a candidate for
new microwave ceramics, perovskite-type AgTax Nb1 x O3 AgTaO3 and AgNbO3 ceramic targets have been prepared
(ATN) solid solutions have been considered because of good by solid state reaction of basic oxides Ag2O, Ta2O5, and
dielectric properties in microwave and millimeter wave Nb2O5. Synthesis has been performed in three stages at
frequency ranges. Dielectric characteristics depend on Nb / Ta different temperatures shown in Table 1. In order to prevent
concentration ratio and they have been mainly verified for a reduction of Ag2O, the weighting and preparation of
AgNbO3 due to the presence of ferroelectricity in silver niobate chemicals have been carried out in a darkroom [7].
[5,6]. Bulk Ag(Ta,Nb)O3 ceramics showed weak dielectric After targets preparation, ATO and ANO films were grown
dispersion in a wide frequency range from 1 to 100 GHz and on LaAlO3 (001) and sapphire (Al2O3-0112, r-cut) single
negligible losses up to 30 GHz. Therefore, the characteristics of crystal substrates by pulsed laser deposition technique. A KrF
AgNbO3 (ANO) and AgTaO3 (ATO), as the ends of the
AgTa1 x Nbx O3 series of alloys, seem to be fundamentals to Table 1
understand and tailor the functional properties of the solid Sintering conditions of ceramic targets
solution ATN system. Parameters AgTaO3 AgNbO3
We report a fabrication of ATO and ANO bulk ceramics to
Density (g/cm3) 5.0 6.8
be used as targets for thin films processing, structural and Diameter (cm) 2.5 2.5
Thickness (cm) 0.5 0.5
1st sintering 900 -C/8 h 900 -C/4 h
* Corresponding author. Tel.: +46 8 790 4179; fax: +46 8 752 7850. 2nd sintering 1030 -C/3 h 1030 -C/3 h
3rd sintering 1100 -C/3 h 1060 -C/3 h
E-mail address: jang@imit.kth.se (J.-Y. Kim).

0040-6090/$ - see front matter D 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2005.12.213
616 J.-Y. Kim, A.M. Grishin / Thin Solid Films 515 (2006) 615 – 618

5
Table 2 10

Al2O3-0112

Al2O3-0224
Processing parameters of ATO and ANO films on LaAlO3 substrate 4
AgTaO3/Al2O3
10

001

002
Conditions

110

Al2O3-0336
220

330
004
3
Film/Substrate ATO/LaAlO3 ANO/LaAlO3 10
7 2
Vacuum (Torr) 5  10 10
Substrate temperature (-C) 650 550
1
Energy of laser (mJ/cm2) 400 10
Repetition rate (Hz) 15 0
Oxygen pressure (mTorr) 450 10
6
10
Distance between substrate and target (mm) 95
Deposition time (min) 20 10
5 AgTaO3/LaAlO3

Intensity(cps)

LaAlO3-001

002
001

LaAlO3-002

LaAlO3-003

LaAlO3-004
004
003
4
10
3
excimer laser (Lambda Physik-300) at a wavelength of 248 nm 10
was used to ablate rotating ceramic target at 400 mJ energy 10
2

fluence, 15 Hz repetition rate and 450 mTorr oxygen pressure. 10

1

Films growth parameters are presented in Table 2. They have 0

10
been optimized to achieve the highest degree of preferential
crystallites orientation (see the details below). Films deposition Ag2Ta4O11 AgTaO3 Ceramic Target
3
rate, about 20 nm/min, appeared to be strongly dependent on 10

002
120
001

111

121
110

220
221

004
222
103

213

330
laser pulse repetition rate and oxygen pressure.
2
Coplanar Waveguide Interdigital Capacitor (CPWIDC) 10
structures were fabricated on ANO and ATO films using

102
photolithography with Clariant AZ5214E photo resist for 10
1

image reversal process. Standard metal lift-off technique was

employed to make CPWIDC from evaporated Au(500 nm) film 10
0

with Cr (10 nm) adhesive layer. Each interdigital capacitor
contained 5 pairs of 12 Am long fingers with a fingers gap of 2
and 4 Am. The layout of the planar capacitor (CPWIDC)
structures is presented in Fig. 1.
3. Results
X-ray diffraction (XRD) patterns recorded with a powder
diffractometer (Siemens D5000) in CuK a radiation are
shown in Figs. 2 and 3. ATO and ANO films on sapphire
are single phase with a perovskite structure though a small
fraction of Ag2Ta4O11 phase was observed in ATO target in
the bottom panel of Fig. 2. In ANO/Al2O3 film, the
intensities of ANO (001) and (110) reflections are in the
ratio of I ANO(001) : I ANO(110) = 0.19, whereas it is only 0.015
for ANO ceramic target. In case of ATO/Al2O3 film, the
ratio of I ATO(001) : I ATO(110) was 0.07 compared to 0.23 in
ATO ceramic target. Therefore, we conclude ANO films
grow on r-cut sapphire preferentially (001) oriented whereas
20 30 40 50 60 70 80 90 100 110 120
2θ (deg)
Fig. 2. XRD h – 2h scans for AgTaO3 films and AgTaO3 ceramic target.
Asterisk * marks a small fraction of Ag2Ta4O11 phase in the target.
there is bigger fraction of (110) oriented crystallites in ATO
films compared to ATO ceramic target.
XRD scans in Figs. 2 –4 clearly show epitaxial quality of
ANO and ATO films on LaAlO3 (001) single crystal: they are
exclusively c(001)-axis oriented and have narrow rocking
curves with a full width at half maximum (FWHM) of 0.28-,
0.62- and 0.045- for ATO, ANO and LaAlO3 (002) Bragg
reflections, respectively. Also, the coincidence of the positions
of Bragg reflections from the oblique (103) planes from films
and substrate indicates strong in-plane films texture (Fig. 4).
Assuming tetragonal structure, the lattice parameters were
found to be a = b = 3.817 and c = 3.915 Å for ATO film and
a = b = 3.791 and c = 3.947 Å for ANO film.

Fig. 1. The layout of the coplanar waveguide interdigital capacitors: device under test—DUT – left panel, Open – middle panel, and Through – right panel test
structures.
 J.-Y. Kim, A.M. Grishin / Thin Solid Films 515 (2006) 615 – 618 617

On-wafer microwave measurements were carried out using 4 LaAlO3 002

network analyzer (Agilent Technologies E8361A), LRM 15

Intensity (10 cps)

3

LaAlO3-103
ATO-103x5
(Line-Reflection-Thru) calibration technique and 150 Am

4
2
pitch signal– ground – signal microwave probe (GGB Indus-
1
tries). Scattering parameter measurements were performed in 10
0.045˚
a wide frequency range from 45 MHz to 40 GHz to 0

determine device capacitance and loss tangent. DC bias 0 50 100 150 200 250 300 350 ATO 002
was applied to the interdigital capacitor through the internal ϕ (deg)

Intensity (10 cps)

5
0.28˚
bias tees of the network analyzer. Modified de-embedding

4
method [8] has been applied to extract true capacitance and AgTaO3 /LaAlO3
loss tand of device under test from the measured scattering 0
parameters S. The de-embedding procedure consists of S- LaAlO3 002
parameters measurements for three CPWIDCs: device under 15 6

Intensity (10 cps)

ANO-103x10

LaAlO3-103
test (DUT) and two test structures Open and Through (Fig.

4
4
1). Then, the rf-properties of the DUT capacitance C, tand as
well as parasitic admittances between signal and ground lines 10
2

and parasitic serial impedances from the metal interconnects 0

between the port 1 and 2 are calculated [8]. Results are 0 50 100 150 200 250 300 350
presented in Fig. 5. 0.045˚
ϕ (deg)
5 ANO 002
As we expected from the properties of bulk ANO ceramics
[5,6], ANO films (left and central panels in Fig. 5) in 1 to AgNbO3 /LaAlO3
0.62˚
40 GHz microwave range show 13% dispersion of the dielectric
permittivity ( and slight increase of tunability at higher 0
20.0 20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0
frequencies. Voltage tunability = 1 C(40 V) / C(0) (40 V,
200 kV/cm) was about 4.6% at 20 GHz, loss tangent ¨0.106 θ (deg)
at 20 GHz, and K-factor = tunability / tand ¨45% at 20 GHz. Fig. 4. XRD rocking curves (x-scans) of (002) Bragg reflections for AgTaO3/
LaAlO3 and AgNbO3/LaAlO3 film structures. The insets show u-scans of
(103) oblique planes recorded at h sam = 57.12-, 2h det = 77.17- for ATO(103),
h sam = 56.83-, 2h det = 76.59- for ANO(103), and h sam = 58.51-, 2h det = 79.94-
5 for LaAlO3(103).
10
AgNbO3/Al2O3
Al2O3-0112

Al2O3-0224

4
10
Right panel in Fig. 5 also shows that non-ferroelectric ATO
002
001

330
110

Al2O3-0336

004
220

10
3
film does not demonstrate frequency dispersion of ( as well as
2 no voltage tunability was observed in microwave range. Loss
10
tangent ¨0.010 at 20 GHz was 10 times lower than that for
1
10 ANO. It is clear that the main contribution to the electric
10
0 polarizability of niobate –tantalate ceramics comes from the
6
fast dynamics of Nb ions. Controlling Nb / Ta concentration
10 AgNbO3/LaAlO3 ratio, microwave properties of ATN system can be tailored
Intensity(cps)

5
10
LaAlO3-002
LaAlO3-001

towards low loss, high tunability and low frequency dispersion

003
LaAlO3-003

LaAlO3-004
004
001

002

4
10 [8].
3
10
2
10 4. Summary
1
10
0
103 Pulsed laser deposited silver niobium oxide AgNbO3 and
10
silver tantalum oxide AgTaO3 thin film coplanar waveguide
AgNbO3 Ceramic Target
tunable capacitors have been fabricated on to the LaAlO3 (001)
2
and sapphire (Al2O3-0112, r-cut) single crystals. X-ray
111
002
001
110

220
121
120

222
103

10
213

330
004

diffraction revealed epitaxial quality of ANO and ATO films

1
on LaAlO3(001) whereas strong (001) preferential and slight
10
(110) orientation of ANO and ATO films, respectively, on r-cut
sapphire. Microwave on-wafer test revealed superiority of
10
0 ANO films on sapphire in the whole frequency range from
20 30 40 50 60 70 80 90 100 110 120 45 MHz to 40 GHz. De-embedding analysis of the scattering
parameters enables a trustworthy determination of the ferro-
2θ (deg)
electric properties without being affected by parasitic imped-
Fig. 3. XRD h – 2h scans for AgNbO3 films and AgNbO3 ceramic target. ance and admittance of coplanar transmission line. ANO/Al2O3
618 J.-Y. Kim, A.M. Grishin / Thin Solid Films 515 (2006) 615 – 618

0 10 20 30 40 0 10 20 30 40 10 20 30 40
0.145 0.039
9

Tunability ΔC/C @ 40V (%)

Tunability ΔC/C @ 40V (%)

Tunability ΔC/C @ 40V (%)
0.054 7.5
8
AgNbO3/Al2O3 AgNbO3/LaAlO3 0.6
AgTaO3/Al2O3
0.140
7 7.0
0.052 0.4
6
0.135
5 6.5
0.038
0.2
0.050 4
Capacitance C (pF)

0.130
6.0
3
0.0
0.125 0 10 20 30 40 0 10 20 30 40
0.048 2 Frequency f (GHz)
0 10 20 30 40 Frequency f (GHz)
Frequency f (GHz)
0.120 0.037
0.046

0.115

0.044

0.110
0.036
0.042
0.105
0V
10V 0.26
Tunability / tan δ @ 40 V (%)

Tunability / tan δ @ 40 V (%)

0.15 20V 400
30V 0.24 AgNbO3/LaAlO3 0.05 400
AgTaO3/Al2O3
40V 300
0.22

200 200
0.20
0.04

0.18 100
0.10 0
0.16 0
0 10 20 30 40 0.03
Loss tan δ

10 20 30 40
Frequency f (GHz) Frequency f (GHz)
Frequency f (GHz) 0.14
0 10 20 30 40
Tunability / tan δ @ 40 V (%)

0.12
0.02
300
AgNbO3/Al2O3 0.10
0.05
0.08
200 0V 0V
0.01
0.06
10V 10V
20V 20V
100
0.04 30V 30V
40V 0.00
40V
0.02
0
0.00
0 10 20 30 40 0 10 20 30 40 10 20 30 40

Frequency f (GHz) Frequency f (GHz) Frequency f (GHz)

Fig. 5. Frequency dependence of the capacitance, loss tand, tunability, K-factor = tunability / tand for ANO/Al2O3, ANO/LaAlO3, and ATO/Al2O3 2 Am gap
CPWIDC structure at various dc bias voltages.

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