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OPEN Photoelectrocaloric effect

in ferroelectric oxide
Subhajit Pal, Manu Mohan, K. Shanmuga Priya & P. Murugavel*

The enhanced electrocaloric (EC) effect in solid-state-based lead-free ferroelectric

­Ba0.875(Bi0.5Li0.5)0.125TiO3 system is investigated under light as an external stimulus. The sample
exhibits an analogous value of maximum change in entropy at Curie temperature, extracted from
the two different measurements process. Notably, the sample depicts maximum value of adiabatic
change in temperature (ΔT) as 1.27 K and isothermal entropy change (ΔS) as 2.05 J/K kg along
with the EC coefficient value of 0.426 K mm/kV, under dark conditions. In addition, the sample
exhibits > 0.5 K adiabatic temperature change over a broad temperature range (~ 35 K). Remarkably,
the EC parameters display ~ 27% enhancement upon 405 nm light illumination. The demonstrated
photoelectrocaloric effect is found to be in accordance with theoretical formalism. The present work
elucidates the light as an additional degree of freedom to widen the potential of solid-state-based
technologies for advanced environment-friendly cooling devices.

Search for materials having potential usage in the forefront of alternative energy and related applications are vital
for future technology. The cooling devices, which consume a giant part of global energy, are currently based on
inefficient and non-eco-friendly vapor compression ­technology1,2. Efforts are made to develop environment-
friendly solid-state cooling technologies as an alternative to the existing ­refrigerant3–5. In this context, pyro-
electric materials are getting attention due to their large electrocaloric (EC) e­ ffect6,7. In particular, ferroelectric
compounds showing a large pyroelectric response near phase-transition temperature (TC) could be envisaged
as a potential candidate for modern EC ­devices3–8. There are proposals reported in the literature to improve the
EC response in ferroelectrics by geometrical ­optimization9, modifying the energy landscape among the coexist-
ing ­phases10, integrating the positive and negative caloric ­responses11, and incorporating additional degrees of
­freedom12,13.
In addition, applying external degrees of freedom such as electric field, mechanical stress, strain gradient, and
pressure reveal significant enhancement in the EC effect of ferroelectric ­systems12–17. For example, the electric
field-induced enhanced EC effect with tunable characteristics is reported in ­PbMg1/3Nb2/3O3–PbTiO3 near room
­temperature16. Additionally, the phenomenological model suggests the possibility of tuning the TC at which the
EC effect is maximum under hydrostatic p ­ ressure12. In fact, this idea has been experimentally verified on metal-
free ferroelectric [MDABCO](NH4)I3 sample, where the maximum observed EC response is reported to shift
from 450 to 293 K ­ 17. Also, lattice strain-induced EC enhancement is theoretically predicted on S­ rRuO3/BaTiO3/
SrRuO3 thin fi ­ lm14. Recently, there are reports to couple the EC effect with flexoelectric efffect originated from
the strain-gradient engineered in thin film s­ amples18. Note that the extent of enhancement and tunable charac-
teristics of the EC effect can vary with types of external stimuli.
In this context, the reported light-induced phenomena on the ferroelectric systems such as photovoltaic
effect, photostriction, and photoferroelectric effect highlight the strong correlation between the polarization
dynamics with l­ight19–22. In particular, photoferroelectric effect is attributed to the photo-induced changes in
polarization dynamics caused by altering the surface screening e­ ffect21,22. Since the EC response also depends on
the polarization dynamics of the material, it is envisaged to enhance its performance characteristics using light as
an external stimuli. To explore such light-induced EC response, lead-free ferroelectric B ­ a0.875(Bi0.5Li0.5)0.125TiO3
(BBLT) compound exhibiting a giant photovoltaic response is considered as a model ­system23. The studies carried
out under dark and light conditions revealed a remarkable ~ 27% enhancement in the EC effect. The photoelec-
trocaloric effect presented in this work demonstrates the application of light as an additional degree of freedom
to tune the EC response suitable for advanced solid-state cooling devices.

Functional Oxides Research Group (FORG), Department of Physics, Indian Institute of Technology Madras,
Chennai 600036, India. *email: [email protected]

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Figure 1.  Stutural, dielectric and optical properties of BBLT. (a) Reitveld refined XRD pattern recorded at
300 K and (b) temperature-dependent ε′ plotted at different frequencies for the BBLT sample. The inset shows
the dielectric loss factor at 10 kHz. (c) The reflectance spectrum of the BBLT sample. The inset shows the
corresponding Kubelka–Munk plot.

Materials and experimental techniques

The BBLT compound is synthesized by a conventional solid-state reaction method using stoichiometric mixtures
of analytical reagent-grade B
­ aCO3 (99.9%), B ­ i2O3 (99.9%), L
­ i2CO3 (99.9%) and T­ iO2 (99.9%) powders by follow-
ing the synthesis conditions reported e­ arlier23. The pellet made from the calcined powder is sintered at 1000 °C
for 2 h and the density of the pellet is found to be 96% of the theoretical value.
The X-ray diffraction (XRD) experiment is carried out by the Rigaku X-ray diffractometer for the structural
information. The temperature-dependent dielectric measurements at various frequencies from 100 Hz to 1 MHz
are obtained using Nova Control (Alpha-A) high-performance frequency analyzer. For optical bandgap, a dif-
fused reflectance spectroscopy experiment is performed using Ultraviolet–Visible-Near Infrared (Jasco V-650)
spectro-photometer. The pyroelectric measurements are performed on 8 mm diameter and 300 μm thick pellet in
a closed-cycle cryostat (Advance Research System) using Keithley electrometer (6517B) as a current measuring
unit. The polarization versus electric field measurement is carried out using Radiant Technology loop tracer at
300 K. The polarization measurement under illumination is performed on 12 mm diameter and 0.2 mm thick
sintered pellet. The heat capacity is carried out by a Quantum Design (DynaCool-D212) physical properties
measurement system. Light-induced pyroelectric measurements are carried out by employing a 405 nm diode
laser (MDL-III-405) as a light source having 1.5 mm beam diameter. For light-induced measurements, 1.0 mm
diameter Ag dots are used as top electrodes with Ag coating as a bottom electrode. The power density of the
incident light is measured using a Coherent PM-10 power meter. To verify the change in temperature upon light
illumination, the IR images are taken at room temperature under dark and light conditions using MIKRON
(HT7600M) camera having 0.1 °C minimum sensing capacity in auto focusing mode. The images clarify that
the temperature of the sample remains unaffected by the light within the measurement limit.

Results and discussions

The XRD pattern shown in Fig. 1a indicates the formation of the BBLT compound, which is free from impurity
phases. The obtained pattern is subjected to Rietveld refinement. The obtained goodness of fit (χ2 = 2.07), and
the weighted profile factor (Rwp% = 8.13) suggest the satisfactory fitting. The refinement shows the coexistence
of tetragonal (P4mm) and orthorhombic (Amm2) phases with 84.79% and 15.21% phase fractions, respectively.
The temperature-dependent real part of permittivity (ε′) measured at 1 kHz to 1 MHz frequency range is plot-
ted in Fig. 1b. The plot unveils the ferroelectric to paraelectric transition (TC) at 351 K, and it is further verified
from the temperature-dependent tangent loss (tanδ) measured at 10 kHz, shown as an inset in Fig. 1b. The value
of tanδ over the temperature range indicates that leakage contribution is insignificant in the sample. A notice-
able smeared nature of ε′ near TC indicates that the transition could be associated to diffuse phase t­ ransition24.
However, frequency-independent TC seen in Fig. 1b shows a non-relaxor characteristic of the BBLT sample. To
obtain the optical bandgap, the diffused reflectance spectrum recorded on the sample is2 shown in Fig. 1c. The
corresponding [F(R)hν]2 versus hν plot is shown as an inset in Fig. 1c, where F(R) = (1−R) 2R is the Kubelka–Munk
function, R is the reflectance, h is the Planck’s constant, and ν is the ­frequency25. The bandgap of the sample
extracted from the plot is 3.2 eV.
To investigate the EC response in the BBLT sample, the indirect method is adopted. To obtain the EC param-
eters, the temperature-dependent polarization data are extracted from two different approaches; Method (I):
polarization (P) versus electric field (E) and Method II: pyroelectric current m ­ easurements4,7,10,26,27. For this
purpose, temperature-dependent P–E measurement from 300 to 380 K recorded on the sample at 4 Hz is shown
in Fig. 2a. The P–E hysteresis at 300 K reveals the typical hysteresis loop depicting the switchable polarization
characteristics of the ferroelectric system. Temperature-dependent pyroelectric current measurement is per-
formed to extract the corresponding P values. Prior to the pyroelectric current measurements, the sample is

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Figure 2.  Temperature-dependent P and ΔS measurements of BBLT sample. (a) P–E hysteresis loop at
different temperature. (b) Temperature-dependent P extracted from the pyroelectric measurements at positive
and negative poled states. The inset shows the respective pyroelectric current response. (c) ΔS extracted from
pyroelectric and polarization methods.

heated up to 390 K without any field and then cooled down to 300 K at 5 K/min under 30 kV/cm positive poling
field. Then the pyroelectric current is measured during the heating cycle by maintaining the heating rate at 5 K/
min in the absence of poling field. The experiment is repeated but this time under the negative poling field of same
magnitude. The polarization values are extracted from the observed pyroelectric current using P = Aβ 1
idT ,
where A, i, β, and dT are the surface area, pyroelectric current, heating rate, and change in temperature of the
sample, ­respectively28. The temperature-dependent P values extracted under positive and negative poled states
are plotted in Fig. 2b. The respective pyroelectric currents are shown in the inset of Fig. 2b. The symmetric nature
of the P curves under positive and negative poled states indicates the ferroelectric characteristics of the sample.
The P value of the samples extracted from the pyroelectric measurement is ~ 7.5 µC/cm2 at 300 K, which is nearly
matching with the value (8.3 µC/cm2) obtained from the P-E hysteresis loop. The P shows a decreasing trend with
temperature followed by a drop in value near the vicinity of TC. Also, the P response shows nearly saturating fea-
tures over a narrow range of temperatures. These observed features could be attributed to the diffuse-phase tran-
sition characteristics and structural inhomogeneity in the sample, reported in several ferroelectric ­systems29–31.
To extract the EC characteristic parameter, the isothermal entropy change (ΔS) and adiabatic tem-
perature change (ΔT), the respective thermodynamic Maxwell’s equations (∂P/∂T)E = (∂S/∂E)T ,
and (∂T/∂E)T = − CTP ρ (∂P/∂T)E are ­u sed 4. The EC characteristic parameters can be expressed as
�S = − Aβρ 1
i(T)�E , and �T = − AβC T
Pρ
i(T)�E26,27. Here, i(T) = A ∂P
∂t = A ∂T ∂t = Aγβ, where dT = γ is a
∂P ∂T dP

pyroelectric coefficient, ρ and CP are mass density and heat capacity, r­ espectively . The E = E1 − E2 is the
26,27

difference in initial (E1) and final (E2) poling fields. For comparison, the pyroelectric coefficient γ is calculated
from both temperature-dependent P–E hysteresis (Method-I) and pyroelectric current (Method-II) measure-
ments. The corresponding ΔS is extracted from the Maxwell’s equation by considering the poling fields lower
limit E1 = 0. The obtained ΔS from Method-I and Method-II as a function of temperature are plotted in Fig. 2c.
The ΔS obtained from both the methods shows an increasing trend with temperature below TC, and displays
maxima at TC. The calculated ΔS at TC (351 K) by the Method-I and Method-II are 1.99 and 2.05 J/K g at 30 kV/
cm, respectively.
Looking at the perspective of the reported light-induced effect on ferroelectric characteristics of the non-
centrosymmetric system, it would be interesting to study the EC phenomenon in the BBLT sample under the
influence of l­ight21,22,32–36. To investigate it, pyroelectric measurement is repeated under the illumination of
405 nm with 11.9 mW/mm2 intensity of light at 30 kV/cm poling field. The corresponding temperature-depend-
ent polarization graphs under dark and light illumination conditions are plotted in the inset of Fig. 3a. As the
ΔS obtained from the two methods is comparable in value, Method-II is chosen owing to its ease in performing
the experiment under light. The graphs exhibit enhanced polarization characteristics of the sample upon light
illumination. This is in accordance with the variation shown by the P-E hysteresis loops measured under dark
and light illumination conditions displayed in Fig. S1a (Supplementary information). The obtained Pr value
plotted as a function of light intensity in Fig. S1b (Supplementary information) depicts the linear variation of
Pr with light intensity. The unsaturated feature in polarization response derived from the pyroelectric current
measurement below transition temperature could be due to the leakage current contribution upon light illumi-
nation. However, the intrinsic origin of the phenomenon can be elucidated from the light-enhanced dielectric
characteristics with negligible tanδ variations observed on BBLT ­sample22. In fact, a theoretical model is also
proposed by V. M. Fridkin on the origin of photoferroelectrics, where the effect is correlated to the change in
surface screening conditions associated to the trapped and surface ­charges21. Few mechanisms are also proposed
to explain the photoferroelectric effect in the material. For instance, the increase in Pr in ­(K0.49Na0.49Ba0.02)
(Nb0.99Ni0.01)O2.995 sample is observed by Bai et al. which is claimed to be originated from the ferroelectric
domains ­contribution34. Importantly, the contributions of ferroelectric domain and lattice deformation on the

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Figure 3.  Photoelectrocaloric effect. Temperature-dependent (a) ΔS and (b) ΔT of BBLT sample measured
under dark and light illumination conditions at + 30 kV/cm field. The insets show the respective P versus T
curve, an enlarged version of ΔT versus T plot near TC, and temperature-dependent heat capacity of the sample.

Systems TC (K) Emax (kV/cm) ΔT (K) ΔT/ΔE (K mm/kV) T span (K) Pr (μC/cm2)
BaTiO337 403 55 0.78 0.142 40 (ΔT ≈ 0.6 K) ~ 12
0.98BaTiO3-0.02(BiMg1/2Ti1/2)O337 416 55 1.21 0.220 50 (ΔT ≈ 0.9 K) ~9
Ba0.85Ca0.15Ti0.90Hf0.10O338 396 35 0.74 0.211 75 (ΔT ≈ 0.6 K) ~7
Ba0.94Sm0.04TiO339 347 30 0.92 0.306 7 (ΔT ≈ 0.8 K) ~9
BaTi0.885Sn0.105O340 303 20 0.61 0.305 27 (ΔT ≈ 0.5 K) ~7
(Ba0.835Ca0.165)(Zr0.09Ti0.91)O341 404 12 0.46 0.38 15 (ΔT ≈ 0.4 K) ~ 11
BaTi0.89Hf0.11O342 343 10 0.35 0.35 31 (ΔT ≈ 0.2 K) ~6
0.9Ba(Ti0.89Sn0.11)O3-0.1(Ba0.7Ca0.3)TiO310 323 40 0.91 0.35 30 (ΔT ≈ 0.6 K) ~8
(Ba0.85Sr0.15)(Sn0.05Ti0.95)O343 309 20 1.44 0.52 NA* ~4
Ba(Ti0.8Zr0.2)O3–(Ba0.7Ca0.3)TiO344 363 30 1.32 0.43 50 (ΔT ≈ 0.6 K) ~9
0.98BaTiO3-0.02NaNbO345 350 200 3.6 0.18 35 (ΔT ≈ 3.2 K) ~4
BBLT Present work (Dark) 351 30 1.27 0.426 13 (ΔT ≈ 0.5 K) ~ 15.8
BBLT Present work (Light) 349 30 1.61 0.536 35 (ΔT ≈ 0.5 K) ~ 8.3

Table 1.  The comparison of EC characteristics of ­BaTiO3-based ferroelectric systems obtained from the
indirect measurements. Here mentioned Pr values are measured at room temperature. *NA not available.

photoferroelectrics properties are also demonstrated by Pal et al. in the BBLT ­system22. Consequently, enhanced
dielectric and ferroelectric characteristics are reported on several ferroelectric systems under light illumination,
including BBLT, (­ K0.49Na0.49Ba0.02)(Nb0.99Ni0.01)O2.995,and Pb[(Mg1/3Nb2/3)0.68Ti0.32]O3 ­systems21,22,34–36.
To investigate the photoelectrocaloric response, ΔS and ΔT derived using Maxwell’s equations under dark
and illumination conditions are displayed in Fig. 3a,b. Prior to that the specific heat CP is measured, and the
temperature variation of CP is displayed in the inset of Fig. 3b. Interestingly, the EC response plotted in Fig. 3
illustrates significant changes in both ΔS and ΔT values throughout the temperature of measurements upon light
illumination conditions. The maximum changes are seen near TC, where the ΔS and ΔT are enhanced from 2.24 to
2.87 J/K kg and 1.27 to 1.61 K, respectively. It is noteworthy to mention that the sample exhibits ~ 27% enhance-
ment in EC response under light illumination condition. In addition, the TC of the BBLT sample is decreased to
349 K under light illumination. This could be correlated to the photo-generated non-equilibrium carriers, which
facilitate the transition to happen at a lower ­temperature21,22. Importantly, the observed ΔT is maintained above
0.5 K over a broad range of temperature (~ 35 K) under light illumination. This could be attributed to the diffused
phase transition characteristic associated with the ferroelectric to paraelectric transition in BBLT sample. It is
noteworthy to mention that the observed EC effect in the sample is superior compared to the reported results
on other ­BaTiO3-based ferroelectric systems measured by indirect method, as evidenced from the comparison
table given in Table 1. Table 1 also emphasizes the increase in EC coefficient (ΔT/ΔE) 0.42–0.54 K mm/kV at
30 kV/cm under dark and light illumination conditions. The detailed comparison of the EC effect observed in
several ferroelectric systems is tabulated in Table 1.
To rule out the optical heating effect, if any, IR images recorded on the sample surface before and after 20 min
of light illumination are provided in Fig. S2 (Supplementary information). Figure S2 depicts that the sample did
not show any appreciable change in temperature before and after light illumination. This eliminates the possibility
of optical heating effect on the EC response of the BBLT sample. To ascertain it further, the photographic images
of the temperature controller (having sensitivity of 0.001 K) displaying the temperature of the sample under
dark and light illumination conditions at different timing are shown in Fig. S3 (Supplementary Information).

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In this case, the thermocouple is connected to the bottom of the sample and the light is shined from the top the
samples. Top and bottom sample surfaces are linked via thermally conductive silver paint. Note that 30 min of
light illumination caused only 0.092 K change in temperature on the surface, validating the negligible optical
heating effect. In addition, if it is believed that the variation in ΔT under light illumination condition is caused
by the optical heating effect, then the variation in ΔT is expected to be noticeable even above TC. But, negligi-
ble variations in ΔT observed above TC under light illumination conditions rule out the heating effect on the EC
response throughout the measured temperature range, as displayed in Fig. 3b. Hence, the photoelectrocaloric
effect observed on the BBLT sample is indeed an intrinsic property of the ferroelectric system.
The correlation between ΔS and P under the influence of light can be understood from the free energy
­perspective21,22. After solving the free energy
 equation, the spontaneous polarization of a ferroelectric system
under light can be expressed as, P0N 2 = P 2 1 + bN − cN where P , b, and c are constants representing ferroelectric
0 β γ 0
polarization, fourth, and sixth-order partial derivative of total energy near TC, ­respectively21. N is the energy
level, β, and γ are coefficients in the free energy e­ xpression21. In the first-order phase transition, the ΔS can be
expressed as, �S = 1/2αP02, here α is a phenomenological c­ oefficient46. However, under light illumination, the
ΔS is expected to show the enhancement upon replacing P0 by P0N . These indeed validate the observed photo-
electrocaloric effect in the BBLT sample. Similarly, the light-induced change in Curie temperature TC is
expressed as �TC = TCN − TC = − 2π C
aN , where C is the Curie–Weiss constant, a is constant representing
second order partial derivative of total energy with respect to polarization near the phase transition temperature,
and TCN is the Curie points under the l­ight21. The minimum free energy condition gives a > 0, and hence the
light-induced charge carriers are expected to lower the TC.

Conclusion and outlook

In summary, the dielectric and pyroelectric measurements on lead-free BBLT sample revealed diffused phase
transition near TC and switchable polarization characteristics, respectively. The EC studies on the BBLT sample
carried out at different poling fields displayed the maximum of ΔS = 2.05 J/K kg and ΔT = 1.27 K at 30 kV/cm
field. The sample revealed remarkable ~ 27% enhancement in EC response under 405 nm light illumination with
ΔS = 2.87 J/K kg and ΔT = 1.61 K at 30 kV/cm. Though the EC response is observed throughout the measurement
temperature range, it is noteworthy to mention that the ΔT > 0.5 K is perceived over 35 K temperature range
under light illumination condition. Furthermore, the observed photoelectrocaloric response is in correlation
with the reported theoretical model. Although there are differences in quantifying the EC response obtained
from the direct and indirect measurements reported in the literature, the observed light-enhanced EC effect in
the BBLT system obtained from the indirect measurement establishes the light as an external stimulus to tune
the EC characteristics in the ferroelectric system. In conclusion, the demonstrated photoelectrocaloric effect can
be extended to other systems to exhibit needed EC responses suitable for solid-state cooling device applications.

Data availability
All data generated or analyzed during this study are included in this published article [and its supplementary
information files].

Received: 14 February 2022; Accepted: 4 April 2022

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Acknowledgements
The authors acknowledge the DST-FIST funding (Project No. SR/FST/PSII-038/2016) for the PPMS facility
in the Department of Physics, IIT Madras, India. The authors acknowledge the Centre of Excellence program
through Institute of Eminence (IoE) initiative scheme by the IIT Madras for the financial and logistical supports.

Author contributions
S.P. and P.M. designed the experiments and supervised the obtained results. S.P. synthesized the materials and
carried out the XRD, dielectric, ferroelectric, and optical measurements. K.S.P. measured ferroelectric hysteresis
loop under light illumination condition. S.P., M.M., and K.S.P. performed the pyroelectric and electrocaloric
measurements. P.M. co-wrote the paper with input from all the contributing authors.

Competing interests
The authors declare no competing interests.

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