Microscopic theory of the electrocaloric effect in the paraelectric phase of potassium dihydrogen phosphate

Lawrence J. Dunne, Matjaz Valant, George Manos, Anna-Karin Axelsson, and Neil Alford Citation: Appl. Phys. Lett. 93, 122906 (2008); doi: 10.1063/1.2991443 View online: http://dx.doi.org/10.1063/1.2991443 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v93/i12 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 93, 122906 2008

Microscopic theory of the electrocaloric effect in the paraelectric phase of potassium dihydrogen phosphate
Lawrence J. Dunne,1 Matjaz Valant,2,3,a George Manos,4 Anna-Karin Axelsson,2 and Neil Alford2
1 2

Department of Engineering Systems, London South Bank University, London SE1 0AA, United Kingdom Department of Materials, Imperial College, Exhibition Road, London SW7 2AZ, United Kingdom 3 Laboratory for Electronic and Environmental Materials, University of Nova Gorica, Vipavska 13, 5000 Nova Gorica, Slovenia 4 Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, United Kingdom

Received 18 August 2008; accepted 8 September 2008; published online 26 September 2008 Here we present a microscopic theory of the electrocaloric effect in potassium dihydrogen phosphate, KH2PO4, based on Slaters lattice model. The model reproduces the essential features of the experimentally observed behavior and also gives a remarkably accurate description of the electric eld dependence of the electrocaloric effect. The basic principle of the theory also gives guidelines for a theoretical analysis of other dielectrics and for the further development of materials with an enhanced electrocaloric effect. 2008 American Institute of Physics. DOI: 10.1063/1.2991443 The electrocaloric EC effect occurs when an electric eld applied under reversible and adiabatic conditions changes the temperature of a polarizable material.1,2 Because of the detrimental impact of conventional vapor compression refrigeration system on the environment, effective EC materials are a possible alternative for the development of environmentally friendly, solid-state refrigeration technology. Considerable effort has been devoted to the discovery of materials displaying a large EC effect;3 however, the theory of this phenomenon is not well understood. Application of an electric eld to an electrically polarizable material under reversible and adiabatic conditions causes partial alignment of electric dipoles. In turn, to keep the total entropy constant, an increase in temperature of the material occurs. A general theory of the EC effect has not yet been developed and a phenomenological approach is sometimes used to describe the relationship between the polarization P, strength of external electric eld E, and temperature change T. Such an approximate relationship for the reversible and adiabatic EC effect can be written as T/ES = T/CE P/TE , 1 greater compared with the effect far away from TC. For example, an EC effect of 2.3 K was obtained for modied PbSc1/2Ta1/2O3 in a temperature range of TC 5 K.7 Mischenko et al.8 reported a giant EC effect in a PbZr0.95Ti0.05O3 thin lm. The results were obtained through an indirect method by measuring the temperature dependence of the polarization. The authors inferred an EC effect of 0.48 K / V in a 350 nm lm 12 K at 480 kV / cm. Other authors1,911 have other experimental results, which cannot be explained within an existing theoretical framework. For example, Wiseman1 reported the simultaneous measurement of the polarization and the EC effect in potassium dihydrogen phosphate KDP both above and below TC as a function of an external eld. The effect is strongest near ferroelectric phase transitions as shown in Fig. 1 taken from the work of Wiseman. He was able to t the experimental data for the paraelectric state with Eq. 1 and the CurieWeiss law. However, the ts for the ferroelectric state were not good even when he applied a high-order Gibbs equation of state. The basic principle of the reversible and adiabatic EC effect is that the tendency of the electric eld E to reduce the entropy SE , T by alignment of electric dipoles has to be compensated by a rise in temperature of the sample thereby keeping the total entropy constant. Hence, SE1 , T1 = SE2 , T2 where the 1,2 subscripts refer to initial and nal states. To calculate an EC effect under reversible and adiabatic conditions as a function of electric eld strength, the expression for a eld dependent entropy and lattice specic heat of the particular system should be known. From these two expressions the temperature rise due to the entropy transfer from polar to acoustic modes can be calculated. Slater12 introduced a lattice model of hydrogen bonded KDP treating the model by mean eld theory. The model has since been widely discussed1315 and the two-dimensional variant of the model has been solved exactly by Lieb.16 A fragment of the crystal structure of KDP is shown in Fig. 2. Each phosphorous atom is tetrahedrally coordinated by four
2008 American Institute of Physics

where and CE are material density and heat capacity at constant electric eld, respectively.4 The earliest experimental measurement of the EC effect was performed on Rochelle salt and reported in 1930.5 Because the temperature change was small 1 K, it was only later in 1956 that the EC effect became more widely discussed.6 The investigation of suitable EC materials intensied after 1960 when a signicant number of dielectrics were studied. The EC-induced temperature change by an external eld of 25 kV cm1 was generally lower than 1 K. This has been the main reason that the EC effect has not been considered as a candidate for solid-state cooling. Recent work has focused on ferroelectrics and it is often found that around Curie point TC the EC effect can be signicantly
a

Electronic mail: matjaz.valant@p-ng.si.

0003-6951/2008/9312/122906/3/$23.00

93, 122906-1

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122906-2

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Appl. Phys. Lett. 93, 122906 2008

FIG. 2. A fragment of the crystal structure of KH2PO4 showing phosphate tetrahedra linked by the hydrogen ions. The OHO groups are polar with mainly covalent bond on one oxygen and hydrogen bond on another. The two adjacent blue spheres in the structure represent the two possible positions of the hydrogen atom in the double well potential as shown in the lower gure. The polarity distribution of the OHO groups over the crystal corresponds to Slaters model.

m =

Np , N

p =

Np , N

o =

No . N

These represent the fraction of dipoles in the m and p congurations and the fraction of nonpolar o congurations. Slater then dened the polarization parameter x by x = p m ,
FIG. 1. Color online Experimental measurements of polarization and EC effect of KDP as a function of electric eld strength for a the system above TC and b below TC as reported by Wiseman Ref. 1. TC of KDP is 122.68 K. The shaded area shows the eld strength range, in which the ferroelectric domain growth represents the major contribution to polarization. No signicant EC effect was measured in this range.

which is a measure of the net dipole moment of the crystal and ranges from 1 to +1. Above the Curie point, Slater derived an approximation for the electric eld dependence of x given by x=

oxygen atoms with a hydrogen atom joining each tetrahedron with its neighbors. The Slater12 and Lieb16 models have been widely discussed as classes of so-called ice models where ice rules apply to the conguration of hydrogen bonds around each phosphate group. Following Slater we suppose that there are N phosphate groups in the crystal and N hydrogen atoms. Of the six arrangements of the hydrogen atoms about a phosphate group, two of these m and p have a dipole with energy E of 4.3 1030 C m calculated from the density and saturation polarization, which points in the c direction, while the other four nonpolar arrangements o lie at right angles to these polar congurations. is the dipole moment and E is the electric eld. The transition temperature TC in the model is TC = . k ln2 2

E , 2kT exp kT kT

2 kT

and the following relations describing the temperature dependencies of the polar and nonpolar fractions given by

o =

4 exp

x2 4 exp 2 kT + exp 4 exp

2 kT

2 kT

1/2

Experimentally, TC for KDP is 122.68 K. In a somewhat different notation from Slater, we dene the variables

p =

1 o + x , 2

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122906-3

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Appl. Phys. Lett. 93, 122906 2008

FIG. 3. Calculated a decrease in entropy of KH2PO4 crystal structure per phosphate group caused by dipole alignment at a xed temperature. To compensate for this, the crystal temperature must rise to keep the total entropy constant, under adiabatic conditions. b Crystal temperature increase due to the EC effect as a function of the electric eld strength. The circles in the plot represent the experimental data obtained by Wiseman Ref. 1.

m =

1 o x . 2

The electric eld dependent contribution to the entropy from the hydrogen bonded system is given by

S = p ln

1 p + o 2 p

1 + o ln 4 p + o 2

+ m ln

1 m + o 2 m

1 m + o 2 o

In addition to the entropy due to the hydrogen bonded system, the acoustic phonons in the lattice have also an entropy contribution, which can be derived from the lattice specic heat. The lattice specic heat CG for KDP has been estimated by calorimetric measurements above TC to be14 CG = 21.43 + 0.3466T J mol1 K1 . 10 Integration of CG / T produces an entropy change per phosphate group in units of k due to population of the acoustic phonon modes given by Slattice =

21.43 R

T T + 0.3466 . T R

11

elds. However, some observations seem pertinent. It is remarkable that within the domain growth regime only a small EC effect can be measured as shown in Fig. 1b,1 and only when saturation polarization is reached does the EC effect start to appear. For an estimation of the EC effect from measured polarization values, one should be aware of different contributions as there are two types of polarization mechanisms occuring: domain growth and dipole alignment. Equation 1 may give a reliable result only when the polarization change occurs within a linear regime. In summary, in this paper we have presented a microscopic theory of the EC effect in the paraelectric phase of KDP based on Slaters lattice model. The model reproduces the essential features of the behavior observed experimentally by Wiseman and also provides a satisfactory account of the electric eld dependence of the EC effect. The underlying principle of the phenomenon above TC is the propensity of the electric eld to reduce the entropy by aligning the electric dipoles, and this is compensated by a rise in temperature of the sample thereby keeping the total entropy constant under adiabatic conditions. Our model also suggests further approaches for a theoretical analysis of the EC effect in other dielectrics and for the development of materials with an enhanced EC effect.
G. G. Wiseman, IEEE Trans. Electron Devices ED-16, 588 1969. J. F. Nye, Physical Properties of Crystals Oxford University Press, London, 1957. 3 G. Akcay, S. P. Alpay, J. V. Mantese, and G. A. Rosetti, Jr., Appl. Phys. Lett. 90, 25909 2007. 4 B. A. Tuttle, Ph.D. thesis, University of Illinois at Urbana-Champaign, Urbana, Illinois, 1981. 5 P. Kobeco and Y. Kurtshatov, Z. Phys. 66, 192 1930. 6 H. Granicher, Helv. Phys. Acta 29, 210 1956. 7 L. Shebanovs, K. Borman, W. N. Lawless, and A. Kalvane, Ferroelectrics 273, 2515 2002. 8 S. Mischenko, Q. Zhang, J. F. Scott, R. W. Whatmore, and N. D. Mathur, Science 311, 1270 2006. 9 G. G. Wiseman and J. K. Kuebler, Phys. Rev. 131, 2023 1963. 10 G. Akcay, S. P. Alpay, J. V. Mantese, and G. A. Rosetti, Jr., Appl. Phys. Lett. 90, 252909 2007. 11 J. H. Qiu and Q. Jiang, J. Appl. Phys., 103, 84105 2008. 12 J. C. Slater, J. Chem. Phys. 9, 16 1941. 13 H. B. Silsbee and E. A. Uehling, Phys. Rev. 133, A165 1964. 14 W. Reese and L. F. May, Phys. Rev. 162, 510 1967. 15 F. Y. Wu and Z. R. Yang, J. Phys. C 16, L125 1983. 16 E. H. Lieb, Phys. Rev. Lett. 19, 108 1967.
1 2

T is the temperature rise assumed small from an initial temperature T. The two entropy contributions given in Eqs. 9 and 11 enable a temperature rise with electric eld to be calculated using a numerical search procedure. In Fig. 3a we show a decrease in entropy due to a partial alignment of dipoles under an inuence of an external electric eld. Under reversible and adiabatic conditions this decrease must be compensated by an increase in temperature to keep the total entorpy constant. The temperature rises are shown in Fig. 3b, which may be compared to the experimental results of Wiseman,1 as shown in Fig. 1. Considering the limitations of the model the agreement is very satisfactory. Below TC, the external electric eld causes ferroelectric domain growth and the theory presented above does not seem to be applicable A theory of the EC effect in this regime has a number of challenges and will need to consider the coupling between the elastic and electric and polarization

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