Thin Solid Films 517 (2009) 4325–4328

Contents lists available at ScienceDirect

Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / t s f

Strain state of bismuth zinc niobate pyrochlore thin films

Juan C. Nino ⁎, Wei Qiu, Jacob L. Jones
Materials Science and Engineering Department, University of Florida, Gainesville, FL 32611, USA

a r t i c l e i n f o a b s t r a c t

Article history: The anisotropic strain of bismuth zinc niobate (BZN) cubic pyrochlore thin films deposited on Si, sapphire,
Received 3 April 2008 MgO, and Vycor glass substrates is characterized through four circle X-ray diffraction and Raman
Received in revised form 21 November 2008 spectroscopy. Based on the X-ray measurements, it is found that all the films exhibit a hydrostatic
Accepted 3 December 2008
compressive strain component with those on MgO substrate exhibiting the highest compressive strain
Available online 14 December 2008
component (0.4%). The effect of the compressive state on the local environment for the ions was investigated
through Raman spectroscopy. The observed shifts in the peak position for Raman-active modes are consistent
Keywords:
Bismuth with the measured strain states and correlate well with previously reported dielectric properties for BZN
Pyrochlore films on MgO, Si, and sapphire.
Relaxation © 2008 Elsevier B.V. All rights reserved.
Stress
X-ray diffraction
Raman spectroscopy

1. Introduction
Since the last quarter of the previous century bismuth-based
pyrochlores, (Bi,A)2(B1,B2)2O7 ± δ (where A, B1, B2 are cations, and
delta is between 0 and 1) have attracted the attention of scientists and
engineers due to their interesting dielectric properties and low firing
temperatures in the bulk that make them ideal for low temperature
cofired ceramic processing for capacitive applications [1–7]. The typical
dielectric response of bismuth pyrochlores exhibits a relatively high
dielectric constant (80 b K b200) and a temperature- and frequency-
dependent dielectric relaxation [3,6]. In an effort to understand the
origin of this peculiar behavior, most of the theoretical, experimental,
and computational work to date has concentrated on bismuth zinc
niobate compounds [8–16]. Inspired by the work in bulk materials,
McKinstry's group first synthesized BZN thin films, obtaining similar
dielectric properties as in bulk ceramics as well as observing a unique
dielectric tunability (i.e. variation of the relative permittivity as a
function of applied electric field). Dielectric tunability is very appealing
for devices such as phase shifters and tunable capacitors and microwave
filters [17]. This characteristic of the bismuth pyrochlore films (the fields
needed for the tunability are not realizable in bulk) further enhanced the
interest in these compounds with most of the recent work, including a
prototype device led by Stemmer's group and coworkers [18–23].
The work presented here focuses on the effect of strain on the
dielectric properties of BZN films. This topic has been addressed in the
past by Withers et al. [14] and it has been proposed that the short range
⁎ Corresponding author. 172 Rhines Hall, MSE Department 116400, University of
Florida, Gainesville, FL 32611, USA. Tel.: +1 352 846 3787; fax: +1 352 846 3355.
E-mail address: jnino@mse.ufl.edu (J.C. Nino).
ordering of metal ions and the associated strain are key factors
responsible for the structural and dielectric relaxation of BZN.
Furthermore, Lu et al. [20] have also proposed that the observed shift
of the dielectric relaxation to lower temperatures in BZN films is due to
the reduction in the activation energy for the relaxation processes due to
biaxial tensile strain.
Here we further characterize the strains in BZN films using X-ray
diffraction, investigate the variations in the lattice vibrations
(phonons) by Raman spectroscopy, and correlate these two with the
observed dielectric properties previously reported.
2. Experimental details
In this work, we have utilized BZN thin films with nominal
composition Bi1.5Zn1.0Nb1.5O7 and cubic pyrochlore structure that were
radio frequency sputtered by Prof. Susanne Stemmer's group at
University of California at Santa Barbara. The films were grown on
four different substrates (Vycor glass, (001) Si, (0001) sapphire, and
(001) MgO) by following the standard, substrate treatment, bottom
electroding, and deposition procedure previously reported by her group
[20]. It is important to note that the films here investigated had no top
electrode.
An X-Pert MRD system (Bruker AXS) was used to measure
anisotropic strain using a 4-circle goniometer and a Cu Kα tube source
(λ ≈ 1.54056 Å). The 2θ = 0° position was calibrated with the sample
removed using the direct beam. Each sample was positioned on the
sample stage such that it bisected the beam and the sample rotation
angle within the diffraction plane (ω) was centered using rocking scans
while measuring the direct beam. For all samples, diffraction patterns
were measured at various sample tilt angles (ψ) in increments of 10° up

0040-6090/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2008.12.010
4326 J.C. Nino et al. / Thin Solid Films 517 (2009) 4325–4328

Fig. 1. Portions of the diffraction patterns of the BZN film on the Vycor substrate at
Fig. 2. Change in interplanar spacing of the (222) reflection as a function of tilt angle (ψ)
various sample tilt angles (ψ). For this sample, the (222) reflection shifts to lower 2θ
and substrate. The linear fits correspond to Eq. (1). Although small and mostly hidden
with increasing ψ.
by the data points, vertical error bars are included.

to a maximum of ψ = 80° using a 2θ step size of 0.025° and containing The linear strain versus sin2ψ behavior for the films is presented in
the range 26.5° b2θ b32°. This range was sufficient to measure the (222) Fig. 2. From these data, standard X-ray stress formulations (e.g., see
reflection of the cubic pyrochlore structure. Repeatability of the Reference [24]) can be used to solve for the intrinsic strain tensor
measurements was ensured by removing one of the sample films coefficients. For the present thin film samples, the projected normal
(Vycor substrate) from the diffractometer, replacing it, and measuring strain as a function of sample orientation (sample tilt ψ and sample
the diffraction patterns a second time. spin φ) is given as
A dual confocal Raman-atomic force microscope (Alpha 300 R/A,
duψ − d0 n o 2
WITec GmbH, Ulm, Germany) was utilized to collect the Raman spectra ðeV33 Þuψ =
2 2
= e11 cos u + e12 sin 2u + e22 sin u − e33 sin ψ + e33
of the as-deposited films. A Nd:YAG laser with 532 nm wavelength and d0
a 100× air objective was utilized for excitation. Raman shift was ð1Þ
collected up to 3000 cm− 1 using an integration time of 5 s. Peak
analysis of the Raman spectra was performed using the commercially where ɛij is the strain tensor coefficient as a function of the diffraction
available software GRAMS (Thermo Fisher Scientific, Inc). geometry coordinate system (1 and 2 are in-plane perpendicular
directions and 3 is the out-of-plane direction). Assuming the samples
3. Results and discussion exhibit fiber symmetry (constant with respect to φ), it can be shown
that ɛ12 = 0 and ɛ11 = ɛ22. Simplifying Eq. (1) and fitting the equation
Examples of a portion of the diffraction patterns obtained for the to the experimental data in Fig. 2, strain coefficients ε11 (in the plane
sample on the Vycor substrate are shown in Fig. 1. Using the of the film) and ε33 (normal to the film) were extracted and are shown
commercial software package Origin (OriginLab Corporation, Pro Ver. in Table 2. The fits are shown in Fig. 2 as solid lines. With more positive
7.5), the (222) reflection was fit to a Gaussian peak shape function. in-plane strain, it can be seen that the out-of-plane strain decreases.
Based on the fitted peak center positions (2θ), the interplanar lattice These in-plane and out-of-plane strain measurements are directly
spacing was calculated using Bragg's law. This in turn was used to correlated. However, the differences are not perfectly compensating,
obtain a first approximation of the out-of-plane lattice parameter for as will be demonstrated through the calculation of the hydrostatic
each of the films. These results are presented in Table 1. strain component. Table 2 lists the hydrostatic strain component,
It can be seen that when compared with bulk BZN, the film on MgO determined using εhydrostatic = (ε11 + ε22 + ε33) / 3. Note that all films
substrate shows an expanded out-of-plane lattice parameter while the exhibit a compressive hydrostatic strain component. The fact that the
films on sapphire, Si and Vycor substrates present a contracted lattice hydrostatic strain component changes for each of the films on
parameter, with the film on the glass substrate showing the largest different substrates indicates that the change of in-plane and out-of-
contraction, 0.33%, twice as much as the one on the Si substrate. plane strains is not perfectly compensating and this results in a change
However, to correctly determine and differentiate the in-plane and in the sample volume for the different films.
out-of-plane strains (intrinsic strain tensor coefficients), lattice It is interesting to contrast these experimentally measured residual
spacings were also measured as a function of tilt angle and substrate. hydrostatic strain values with the estimated thermal strain analysis by
Lu and coworkers [20], indicating that the Vycor film should be under a
large biaxial tensile strain, whereas the film on MgO would be under
Table 1
Out-of-plane lattice parameters for BZN films on different substrates, calculated from
the (222) peak position. Table 2
In-plane strain (ε11) and the strain normal to the sample (ε33) as a function of substrate.
BZN substrate 2θ d-spacing a (A°) Strain (%)
Sapphire 29.276 3.048 10.559 − 0.027 Substrate ε33 ε11, ε22 εhydrostatic
MgO 29.236 3.052 10.573 0.106 Sapphire − 0.00029 ± 0.00002 − 0.00307 ± 0.00008 − 0.0021
Si 29.315 3.044 10.545 − 0.157 MgO 0.00115 ± 0.00008 − 0.00664 ± 0.00022 − 0.0040
Vycor 29.368 3.039 10.526 − 0.333 Si − 0.00172 ± 0.00004 − 0.00058 ± 0.00013 − 0.0010
Bulk (Levin et al.) 29.268 3.049 10.562 0.000 Vycor − 0.00330 ± 0.00003 0.00118 ± 0.00009 − 0.0003

For comparison, bulk data from Levin et al. [11] is presented and used to calculate the The hydrostatic strain component, εhydrostatic, is the average of the ε33, ε22 ε11 values.
relative strain. Errors are those from the linear fit in Fig. 2.
 J.C. Nino et al. / Thin Solid Films 517 (2009) 4325–4328 4327

compressive strain. First, it is clear that both the thermal strain estimates
and the present measurements show that the films on MgO substrate
exhibit a compressive in-plane hydrostatic stress component. Ranking
the films from more positive (tensile) to more negative (compressive)
stress (hydrostatic/thermal), the order is identical: the films on Vycor
exhibit the highest hydrostatic tensile strain component and thermal
strain, followed by those on Si, sapphire, and then those on MgO. Thus, a
direct correlation exists between the hydrostatic strain component
calculated in the present work and the thermal strain analysis by Lu and
coworkers [20]. This analysis is particularly important because of the
significant differences in the dielectric response that have been observed
in these films depending of substrate, with perhaps more importantly,
the fact that dielectric relaxation was not observed (or was heavily
suppressed) in the films on a Vycor substrate. Since the dielectric
relaxation involves high dielectric loss (tan δ), means of suppressing the
dielectric loss are extremely relevant for technical interest for device
applications. Furthermore, the possibility of stress-mediated dielectric
relaxation is of significant scientific interest.
To better understand the effects of the substrate (stresses or
otherwise) on BZN films, the Raman spectrum of the films was col-
lected as described above. A compilation of the spectra for all four
substrates is presented in Fig. 3 from 150 to 1100 cm− 1. Higher wave
numbers are not presented as the spectra were monotonically flat.
Lower wave numbers (frequency) spectral ranges are omitted due to
spectrometer signal to noise ratio limits.
From visual inspection of the spectra, several intensity peaks are
evident. It has been shown before, that factor group analysis of the
regular pyrochlore structure predicts an irreducible representation
with 6 Raman-active modes [25]. However, Nino and coworkers [10,12]
have shown that for the case of BZN, the dynamic displacements of the
ions from their regular pyrochlore atomic positions lead to the
possibility of up to 25 Raman-active modes. In earlier temperature-
dependent Raman studies of bulk BZN, however, only 10 Raman modes
have been experimentally observed [16]. More recent room tempera-
ture data, also on bulk, reported only 8 Raman modes observed [15].
Based on this preliminary work, the collected spectra were fitted to a
series of Gaussian peaks using GRAMS software. To aid the fit, peak
positions values for bulk BZN were utilized as initial guesses for the
peak positions of the BZN films. Fig. 4 shows the resulting fit for the
spectrum of the films deposited on the Si substrate as representative of
the goodness of the fit obtained for all the investigated films.
Table 3 shows a summary of the observed peak positions for the
films on the four different substrates compared with those observed in
bulk BZN. The previously determined mode assignments are also
included [15,26].
In general, the Raman peaks of the films have not shifted much
with respect to the bulk values (Table 3) and that 10 Raman-active
Fig. 4. Experimentally measured Raman spectrum of BZN films on Si substrate and
typical Gaussian peak fits.
modes reproduce well the observed spectra for thin films (Fig. 4).
Furthermore, a few trends can be observed: peaks for modes R1 and
R9 are almost identical across films and bulk. Compared to bulk values
peaks for modes R2 and R8 shift to higher frequencies. By contrast,
peak values for modes R3 through R6 and R10 have shifted to lower
frequencies. It is also clear that the films on the MgO substrate
consistently exhibit the highest mode frequencies, approaching bulk
values. For example, in the case of mode R7, film on Si, sapphire and
Vycor show an almost identical shift to lower frequency (~523 cm− 1)
with respect to bulk BZN (~ 547 cm− 1), while the film on MgO shows a
shift to higher frequency (~551 cm− 1).
Assuming identical composition and overall crystal structure for all
the films, shifts in the peak positions of the Raman spectra can be
interpreted as the result of changes in the local environment of the
vibrating ions. Specifically, they can point to stiffening of bonds
(shorter anion–cation bond distance) resulting in vibrations of higher
frequency, and vice versa (longer bonds, lower frequencies). There-
fore, the general shift towards higher frequencies of the modes for the
film on MgO substrate is consistent with the compression state of the
films calculated from the X-ray diffraction measurements and analysis
here presented.
As stated before, one of the interests in understanding the strain state
of BZN films is to explore the possibility of stress-mediated dielectric
response. If in fact this correlation between stress and dielectric
permittivity can be exploited, based on the strain states here reported,
one could expect the films on different substrates to exhibit a clearly
distinct dielectric behavior. In fact, based on reported dielectric data by
Stemmer's group [20], the films on MgO exhibit the lowest dielectric
permittivity (at a given frequency), with roughly 6% difference between
films on Si (K = 180) versus those on MgO (K = 170). This is certainly
consistent with the fact that films on MgO substrate exhibit a hydrostatic
compressive strain component, a stiffer, shorter bond is less polarizable

Table 3
Summary of Raman peaks and mode assignments.

Modes MgO Sapphire Glass Si Bulk Mode assignment

R1 199 194 194 194 194 F2g, A-O′15
R2 275 270 266 265 255 F2g, A-O15
R3 342 332 325 322 356 F2g, B-O26
R4 375 367 367 363 386 Eg, B-O15,26
R5 419 408 412 408 425 Eg, B-O
R6 469 457 462 457 487 A1g, B-O26
R7 551 523 525 520 547 F2g, BO6 breathing15,26
R8 706 623 625 622 602 F2g, B-O, O-B-O26
R9 769 763 766 761 768 Unassigned
R10 841 838 841 841 877 Unassigned
Fig. 3. Raman spectra for BZN films on different substrates.
4328 J.C. Nino et al. / Thin Solid Films 517 (2009) 4325–4328
and thus a reduction in the observed permittivity is expected. However,
the permittivity differences observed are perhaps too small to have
significant implications and application to general devices. Nonetheless,
the present work has identified a consistent strain state–phonon
(vibrational) correlation that can explain the reported dielectric
properties for the films on Si, sapphire and MgO substrates. The reasons
behind the lack of relaxation and the higher dielectric constant observed
in the films on Vycor substrates remain unexplained. It is clear however
that strain arguments by themselves cannot explain it, nor have any
unique features been observed in the Raman spectra of the BZN films on
Vycor. As it has been the case for bulk BZN [12], infrared spectroscopy
may help in better understanding the nature of the differing dielectric
behavior of the BZN films on dissimilar substrates.
4. Conclusion
The measurement of the anisotropic strain of bismuth zinc niobate
cubic pyrochlore thin films deposited on different substrates was
performed through detailed (four circle) X-ray collection and analysis.
Calculation of the hydrostatic strain component demonstrates that all
the films exhibit a compressive hydrostatic strain component with
those on MgO substrate exhibiting the highest compressive hydro-
static strain component (0.40%), followed by those on sapphire
(0.21%), Si (0.10%) and Vycor (0.03%). Analysis of the Raman spectra
collected has shown the effect of the compressive state on the local
environment for the ions through shifts in the peak position for
Raman-active modes that consistent with the measured strain states.
Further, in the case of BZN films on MgO, Si, and sapphire, these
measurements are consistent with the observed dielectric properties.
Acknowledgements
The authors are grateful to Prof. S. Stemmer at UCSB for supplying
the deposited thin films and want to thank WiTec for the AFM-Raman
measurements, and the Major Analytical Instrumentation Center in
the Department of Materials Science and Engineering at University of
Florida. J. Nino would like to acknowledge the financial support of the
U.S. National Science Foundation through the CAREER Award (DMR-
0449710).
References
[1] G.I. Golovshchikova, V.A. Isupov, A.G. Tutov, I.E. Myl'nikova, P.A. Nikitina, O.I.
Tulinova, Soviet Physics - Solid State 14 (1973) 2539.
[2] G. Jeanne, G. Desgardin, B. Raveau, Mater. Res. Bull. 9 (1974) 1321.
[3] D.P. Cann, C.A. Randall, T.R. Shrout, Solid State Commun. 100 (1996) 529.
[4] X. Wang, H. Wang, X. Yao, J. Am. Ceram. Soc. 80 (1997) 2745.
[5] J.C. Nino, M.T. Lanagan, C.A. Randall, J. Mater. Res. 16 (2001) 1460.
[6] J.C. Nino, M. Lanagan, C. Randall, J. Appl. Phys. 89 (2001) 4512.
[7] C.A. Randall, J.C. Nino, A. Baker, H.J. Youn, A. Hitomi, R. Thayer, L.F. Edge, T. Sogabe,
D. Anderson, T.R. Strout, S. Trolier-McKinstry, M.T. Lanagan, Am. Ceram. Soc. Bull.
82 (2003) 9101.
[8] M. Valant, P.K. Davies, J. Am. Ceram. Soc. 83 (2000) 147.
[9] H. Wang, X. Yao, J. Mater. Res. 16 (2001) 83.
[10] S. Kamba, V. Porokhonskyy, A. Pashkin, V. Bovtun, J. Petzelt, J.C. Nino, S. Trolier-
McKinstry, M.T. Lanagan, C.A. Randall, Phys. Rev. B 66 (2002) 054106.
[11] I. Levin, T.G. Amos, J.C. Nino, T.A. Vanderah, C.A. Randall, M.T. Lanagan, J. Solid State
Chem. 168 (2002) 69.
[12] J.C. Nino, M.T. Lanagan, C.A. Randall, S. Kamba, Appl. Phys. Lett. 81 (2002) 4404.
[13] J.C. Nino, I.M. Reaney, M.T. Lanagan, C.A. Randall, Mater. Lett. 57 (2002) 414.
[14] R.L. Withers, T.R. Welberry, A.K. Larsson, Y. Liu, L. Noren, H. Rundlof, F.J. Brink,
J. Solid State Chem. 177 (2004) 231.
[15] Q.A. Wang, H. Wang, X. Yao, J. Appl. Phys. 101 (2007) 104116.
[16] J.C. Nino, Ph.D. Thesis, The Pennsylvania State University, 2002.
[17] W. Ren, S. Trolier-McKinstry, C.A. Randall, T.R. Shrout, J. Appl. Phys. 89 (2001) 767.
[18] J.W. Lu, Z.Q. Chen, T.R. Taylor, S. Stemmer, J. Vac. Sci. Technol., A 21 (2003) 1745.
[19] J.W. Lu, S. Stemmer, Appl. Phys. Lett. 83 (2003) 2411.
[20] J.W. Lu, D.O. Klenov, S. Stemmer, Appl. Phys. Lett. 84 (2004) 957.
[21] J. Park, J.W. Lu, S. Stemmer, R.A. York, J. Appl. Phys. 97 (2005) 084110.
[22] A.K. Tagantsev, J.W. Lu, S. Stemmer, Appl. Phys. Lett. 86 (2005) 032901.
[23] J. Park, J.W.W. Lu, D.S. Boesch, S. Stemmer, R.A. York, IEEE Microw. Wirel. Compon.
Lett. 16 (2006) 264.
[24] I.C. Noyan, J.B. Cohen, Residual Stress: Measurement by Diffraction and Interpreta-
tion, Springer-Verlag, NY, 1987.
[25] B.E. Scheetz, W.B. White, J. Am. Ceram. Soc. 62 (1979) 468.
[26] N.T. Vandenborre, E. Husson, H. Brusset, Spectrochim. Acta 37A (1981) 113.