Optical Materials 30 (2007) 101–105

www.elsevier.com/locate/optmat

Pyroelectric properties of high-resistivity rubidium titanyl

phosphate crystals in the 4.2–300 K temperature range
Yu.V. Shaldin a, S. Matyjasik b, M. Tseitlin c, M. Roth d,*

a
Institute of Crystallography, Russian Academy of Sciences, 119333 Moscow, Russian Federation
b
International Laboratory of High Magnetic Fields and Low Temperatures, 53-421 Wroclaw, Poland
c
The Research Institute, College of Judea and Samaria, Ariel 44837, Israel
d
Faculty of Science, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

Available online 12 December 2006

Abstract

Pyroelectric properties of high resistivity RbTiOPO4 single crystals cut from different growth sectors ({1 0 0}, {1 1 0} and {2 0 1}) have
been studied using the modified static method in a broad temperature interval, from 4.2 to 300 K. A substantial scatter of the room tem-
perature pyroelectric coefficient values has been observed, ranging from 1.3 to 4.6 105 C/m2 K, for samples of distinct stoichiometry.
Different types of low-temperature anomalies in the pyroelectric coefficient behavior have been revealed in samples related to the various
growth sectors. Crystals cut from the {1 1 0} sector exhibit particularly interesting anomalies at 90 and 250 K which are attributed to
oxygen deficient PO4(1) and PO4(2) coordinational tetrahedral and their relaxor contribution. This and other anomalies are discussed
in terms of the growth related variation of the RTP crystals’ nonstoichiometry and point defect structure.
 2006 Elsevier B.V. All rights reserved.

1. Introduction cause a substantial decrease in specific resistivity along

The wide family of isomorphic MTiOXO4 compounds,
where M = {K, Rb, Tl} and X = {P, As} is an important
class of crystals for application in laser systems utilizing
frequency conversion and electro-optic modulation [1,2].
These crystals exhibit large optical nonlinearities and elec-
tro-optic coefficients, high laser damage threshold and
excellent thermal stability. However, the properties of these
crystals may alter due to the variation of their chemical
composition and defect distribution during growth from
self-fluxes [2–4]. In particular, generation of color centers
under green light illumination (gray tracking) with a grad-
ual degradation of optical transparency takes place [5],
while the oxygen nonstoichiometry has been claimed to
*
Corresponding author. Tel.: +972 2 566 3878; fax: +972 2 658 6364.
E-mail address: mroth@vms.huji.ac.il (M. Roth).
the z-axis, which has been interpreted also in terms of an
increase of the alkali metal superionic conductivity [1].
In similarity with its potassium isomorph, the RbTiO-
PO4 (RTP) structure is described as a three-dimensional
framework comprising PO4 tetrahedra and TiO6 octahedra
[6]. The unit cell of the low-temperature ferroelectric RTP
phase contains eight formula units, and it is described as
belonging to the noncentrosymmetric mm2 point group
(Pna21 space group) symmetry. The rubidium ions are
localized in the main framework cavities, strictly around
the polar axis direction. Helical structural channels have
been identified in this direction [7] which, at certain temper-
atures, facilitate the drift of rubidium ions, or the ionic
conductivity, and an abrupt resistivity decrease along the
z-axis.
Recently [8], we have suggested an alternative view on
the structure of KTP-type crystals as composed of meso-
tetrahedra (Fig. 1). The A and B mesotetrahedra form
two oppositely polarized sublattices with respective P(A)
and –P(B) spontaneous polarizations. They form infinite

0925-3467/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.optmat.2006.11.005
102 Yu.V. Shaldin et al. / Optical Materials 30 (2007) 101–105
Fig. 1. Structural fragment of the RTP single crystal viewed as an infinite
sequence of A and B mesotetrahedra along the polar (z) axis. Mesotetra-
hedra are formed by Ti(1) and two types of tetrahedral, PO4(1) and
PO4(2), connected by Ti(2) ions.
chains along the polar axis direction, which determines the
packing order. The mesotetrahedra are linked by Ti(2) ions
thus stabilizing the chains. With such representation of the
RTP structure, the role of rubidium ions localized around
the 21 screw axis in forming the crystal’s spontaneous
polarization is secondary.
As-grown RTP crystals obviously contain point defects
typical for oxide crystals. Inherently present oxygen vacan-
cies induce the formation of compensating vacancies in the
alkali metal sublattice, and alkali ions are partially moved
into interstitial positions. This process can be substantially
depressed by evening out the oxygen/alkali ion vacancies
concentrations which, in turn, is expected to reduce the
ionic conductivity. Thus induced donor–acceptor pairs, at
certain concentrations, may create a defect subsystem
exhibiting its own dipole moment and influencing signifi-
cantly the behavior of the overall pyroelectric coefficient
cS [9–14]. The latter is defined from
DP S ¼ cS  DT ;
where DPS is the change in spontaneous polarization under
a small temperature change DT. According to an empirical
rule [15], P 2S  T c , where Tc is the ferroelectric transition
(Curie) temperature depending on the composition and de-
fect structure of KTP-family crystals [2,5].
In the present work, an investigation of the pyroelectric
properties of RTP crystals in the 4.2–300 K temperature
range is carried out, and it is primarlily aimed at revealing
the influence of the melt composition and crystal nonstoi-
chiometry on the temperature dependence of the pyroelec-
tric coefficient.
2. Experimental
RTP crystals were grown by the top-seeded solution
growth (TSSG) method with pulling on X- or Z-oriented
seeds from self-fluxes containing initial Rb to P atomic
ratios from 1.5 to 2. Solutions of RTP in self-fluxes were
prepared by reacting the Aldrich 3N purity TiO2, Rb2CO3
and Merck (Suprapur) NH4H2PO4 and (NH4)2HPO4 in
appropriate proportions. The charges were loaded into
200–1000 ml Pt crucibles and subjected to 24 h soaking
through homogenization aided by a Pt stirrer. Crystal
growth proceeded in a custom resistance furnace with a
long hot zone allowing to obtain a uniform temperature
distribution with a gradient 62 C in the solution. The seed
rotation and pulling rates varied from 70 rpm to 20 rpm
and from 0.02 to 1 mm/day respectively. The general tem-
perature range for growth of RTP crystals was 980–880 C,
while the temperature lowering rates changed from 0.5 to
3 C/day. As a result, RTP crystals of up to 50 · 60 ·
50 mm3 dimensions along the X, Y and Z axis could be
grown.
Z-cut plane parallel crystal samples with thicknesses
varying from 0.5 to 1.5 mm were used for determination
of the Curie temperatures and pyroelectric measurements.
They were cut from different growth sectors (volumes ter-
minated by specific facets) shown schematically in Fig. 2.
The Tc was measured using a standard dielectric technique
(with an accuracy of ±0.5 K) by thermal ramping and
recording the capacitance anomaly at the ferroelectric tran-
sition temperature. The samples coated with Pt electrodes
on both sides were linked into an ac impedance bridge cir-
cuit based on a Hewlett-Packard model 4276A LCZ meter
operating at a 20 kHz frequency. The substantial difference
in Tc values of samples cut from the top and bottom of the
{1 0 0} growth sector (Fig. 3) manifest the apparent varia-
tion of the RTP crystal stoichiometry in course of the
growth process. This implies that the gradual variation of
the defect structure, practically not studied in RTP [1],
must be reflected in the corresponding pyroelectric effect
measurements.
Samples for pyroelectric measurements were prepared
from three growth sectors: {2 0 1}, {1 0 0} and {1 1 0}. The
respective Tc and electrical resistivities values and the
ð1Þ
Fig. 2. Schematic vertical cut of RTP crystal grown on X- and Z-oriented
seeds showing the various growth sectors.
 Yu.V. Shaldin et al. / Optical Materials 30 (2007) 101–105
6
Capacitance, nF
0
1020 1040 1060 1080
Temperature, K
Fig. 3. Curie temperatures (measured by capacitance method) of two RTP
samples cut from the top (circles) and bottom (squares) of the {1 0 0}
growth sector.
sample areas were: 1049.6, 1066.6 and 1058.0 K; 2 · 1012,
1011 and 1011 X cm; 34.0, 47.0 and 30.0 mm2. One {2 0 1}
sample of a 24.7 mm2 area was annealed at T = 800 K in
vacuum for 7 h. Silver paste was used as an electrode and
current guiding material in pyroelectric measurements.
Investigation of the pyroelectric properties of RTP crys-
tals cut from the various growth sectors has been carried
out using the modified static method. A helium open-flow
cryostat was used, and the samples were mounted on a cold
finger equipped with a Cemox-1050CD thermocouple.
Temperature control at a level of better than ±0.001 K
was performed using a resistive coil connected to a stabi-
lized power supply. The electric charge generated by the
samples in course of temperature change was measured
by a Keithly-17F universal digital electrometer.
Each sample was shortened at the start of the experi-
ment and then immersed into liquid helium. When the
4.2 K temperature was reached, the sample was connected
to the electrometer in order to check for the zero drift of
the entire measurement circuit. The exposure time at liquid
helium temperature was defined by the possibility of linear
approximation of the zero drift as a function of time. The
typical proportionality coefficient in our experiments was
1014 C/s. The sample extraction from the liquid helium
was a delicate procedure which could be accompanied by
generation of extra charge due to temperature gradients.
This, in turn, could cause a systematic error effecting pri-
marily the initial set of measurements.
3. Results and discussion
All measurements of the electrical charge variation as a
function of temperature were carried out on temperature
increase. The experimental data were used to calculate
the temperature dependencies of the polarization change,
DPS, as shown in Fig. 4 for all four types of samples.
The results obtained for the two {2 0 1}-sector samples,
curves (a) and (b), are identical within the experimental
error, and at T = 300 K the polarization change reaches a
value of 102 C/m2, which is comparable with the typical
data for lithium niobate. The {1 0 0}-sector sample, curve
103
1100
Fig. 4. Temperature dependences of spontaneous polarization change
for z-plates cut from the {2 0 1} sector (a), {2 0 1} sector after annealing at
T = 800 K in vacuum (b), {1 0 0} sector (c) and {1 1 0} sector (d); d+ and
d curves taken after electric field (±103 V/cm) removal at 4.2 K.
(c), exhibits some anomalies at 90 and 230 K, while the
room temperature DPS is half the value of curve (a).
In the case of the {1 1 0} sample, control measurements
of the DPS dependence under conditions of a fixed surface
charge (that may stem from a possible drift of Rb-ions in
the ±103 V/cm field) show that the main difference between
the curves is at temperatures above 280 K. The apparent
scatter of the DPS values and the existence of anomalies
points at the variable stoichiometry of the different
samples.
The DPS(T) dependencies described above have been
used to calculate the unclamped pyroelectric coefficients,
from Eq. (1), for all RTP samples cut from different crystal
growth sectors, and the results are presented in Figs. 5–7.
Apparently, cS exhibits no anomalies in the lower temper-
ature range as compared to low-resistivity KTP crystals
[9–11]. Moreover, the cS/T2 versus temperature dependen-
cies, shown for the {2 0 1}- and {1 0 0}-sector samples in
Fig. 8, are linear at least in the 4.2–30 K range. The latter
result is suffiucient to confirm the universal c  T3 depen-
dence characteristic for all pyroelectrics [16].
At higher temperatures, certain kinds of anomalies
emerge, like shown for the {1 1 0}-sector crystal in Fig. 5,
which are presumably associated with the oxygen sublattice
Fig. 5. Temperature dependence of the unclamped pyroelectric coefficient
of RTP crystal cut from the {1 1 0} growth sector.
104 Yu.V. Shaldin et al. / Optical Materials 30 (2007) 101–105
Fig. 6. Temperature dependences of the unclamped pyroelectric coeffi-
cients of RTP crystals cut from the {2 0 1} growth sector; a – as-grown
crystal, b – after vacuum annealing at T = 800 K.
Fig. 7. Temperature dependence of the unclamped pyroelectric coefficient
of RTP crystal cut from the {1 0 0} growth sector.
Fig. 8. 4–30 K segments of temperature dependences of unclamped
pyroelectric coefficients (cS) of RTP crystals cut from (a) {2 0 1} and (b)
{1 0 0} growth sectors and their representation in terms of cS/T2
temperature dependences.
nonstoichiometry. The dipole moments of the coordina-
tional PO4(1) and PO4(2) tetrahedra change on loss of oxy-
gen, and the latter may be assumed as relaxors [17,18]
which are altering the pyroelectric coefficient temperature
dependence significantly around 90 and 250 K. Similar,
but weaker, anomalies are observed also in as-grown
{2 0 1}-sector crystals (Fig. 6, curve (a)). Annealing in vac-
uum at T = 800 K results in a tangible transformation of
the anomaly (Fig. 6, curve (b)) providing an evidence for
the important role of color centers in formation of the crys-
tal’s pyroelectric properties. A detailed analysis of cS(T)
anomalies above 280 K, such as shown for the {1 0 0}-sec-
tor crystal in Fig. 7, is difficult due to the onset rubidium
ions’ drift along the helical channels (Fig. 1) within the
RTP crystal lattice. It is noteworthy that high resistiv-
ity KTP crystals exhibit a similar behavior to the {1 0 0}-
sector RTP sample, namely showing no anomalies at low
temperature but rather above 250 K [8]. The cation drift
in both KTP and RTP is presumed to be assisted by the
oxygen vacancies present, and an indepth study of this pro-
cess is currently underway.
Since no direct experimental data on the RTP spontane-
ous polarization are yet available, it can be evaluated based
on the optical and pyroelectric measurements according to
the methodology suggested earlier [19]. With the existing
approximate data on the RTP birefringence and its temper-
ature derivative [1], one can only roughly estimate the value
of spontaneous polarization to be as large as P  0.5 C/m2.
This does not contradict the empirical rule suggested by
Abrahams et al. [15], namely the higher is the ferroelectric
phase transition temperature the larger is the spontaneous
polarization of ferroelectrics containing oxygen octahe-
drals, according to: T c  P 2S . In view of the large magnitude
of spontaneous polarization in high resistivity RTP crys-
tals, even the observed significant scatter of the room tem-
perature values of pyroelectric coefficients (between 1.3 and
4.6 · 105 C/m2 K for samples cut from different growth
sectors) is not apt to affect the nonlinear optical susceptibil-
ity. However, the issues of optical uniformity and stability
do relate to the variable stoichiometry in the various
growth sectors.
4. Conclusions
Since the choice flux composition and pulling direction
determine the crystal morphology and composition, our
present results show that growth conditions of RTP crys-
tals have a tangible impact on their pyroelectric properties.
Samples cut from different growth sectors, such as {1 0 0},
{1 1 0} and {2 0 1}, known to be of different stoichiometry,
also exhibit essentially distinct low-temperature anomalies
in the pyroelectric coefficient behavior. A substantial scat-
ter in the room temperature values of the pyroelectric coef-
ficients related to samples of different stoichiometry is
observed, from 1.3 to 4.6 · 105 C/m2 K, indicating that
a problem of optical uniformity and stability exists, and
it should be taken into account in manufacturing of RTP
nonlinear and linear optical elements.
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