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M ATERIALS 286G

Materials 286G: Review of polar materials.

cation T TC

anion T TC

applied eld T TC

pyroelectric

ferroelectric

antipolar

antiferroelectric

Piezoelectric materials: There is coupling between electrical and mechanical energies. For example, an applied stress results in the generation of polarization. Pyroelectric materials: A material with a temperature dependent polarization. This requires a unique polar axis. Ferroelectrics: A subgroup of pyroelectric materials in which the spontaneous polarization can be reoriented between equilibrium states by applying an electric eld. All ferroelectrics are both pyroelectric and piezoelectric. The possibility of inorganic crystals being polar (pyroelectric or piezoelectric) is strictly a function of their point group symmetry:
32 crystallographic point groups

11 centrosymmetric

21 non-centrosymmetric

20 piezoelectric

1 non-piezoelectric

(432)

10 pyroelectric

10 non-pyroelectric

The ferroelectric phase transition (for example, in PbTiO3 ) is characterized by the development of a spontaneous (zero eld) polarization, changes in the dielectric constant, and crystal structural changes.:

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P (C/m2)

T (K) r

T (K) cell parameters

T (K)
At the origins of such a phase transition are developments of a dipole within the unit cell, due to the centers of positive and negative charges not coinciding:

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PbTiO3 Pm3m

PbTiO3 P4mm

In the particular case of PbTiO3 , the phase transition from the cubic, paraelectric phase to the tetragonal ferroelectric phase (a displacive phase transition) is associated with the freezing of a phonon mode that is referred to as the soft mode. Phonon modes are specic vibrational modes of the crystal lattice. In the case of PbTiO3 , this phonon mode is associated with the Ti atom in the center of the octahedron:
h (meV) frozen Ti

vibrating Ti

T K

The frequency (energy) of the soft mode goes to zero as the phase transition is approached. Ferroelectric materials are also characterized by hysteresis of the polarization below the ferroelectric TC , just as are ferromagnets are characterized by a hysteresis of the magnetization:

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As is true for ferromagnets, the hysteretic behavior is a consequence of the presence of domains in the material. Some materials undergo an order-disorder phase transition from the paraelectric phase to the ferroelectric phase. An example is NaNO2 (sodium nitrite):

O N

      

Na

Room temperature ferroelectric structure of NaNO2 projected on (001). The rigid NO2 groups + have been shown as little chevrons, and the Na ions as circles. Hatching indicates that the atoms are at a height of -1/2.

Above the phase transition at 438 K, the structure is non-polar and has the Immm space group. Below this temperature, the material is ferroelectric and has the space group Im2m; the ferroelectric structure is displayed. The dipole moment is lost in the high temperature structure because of disorder. Half the chevrons point to the left and half to the right, and correspondingly, the Na ions also occupy two different sites at random. Antiferroelectrics: These are usually characterized by antiparallel dipole moments in the unit cell. The formation of antiparallel moments (as in antiferromagnetic systems) results in the formation of larger unit cells. 4

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cation anion a parameter paraelectric

a parameter ferroelectric

a parameter antiferroelectric

An example of an antiferroelectric is PbZrO3 , which is cubic ( Pm3m), paraelectric above 503 K. Below this temperature, a combination of two effects, the tendency of the ZrO6 octahedra to tilt as a consequence of the tolerance factor being less than 1, and the tendency of the Pb2+ ions to go off-center, result in the antiferroelectric, orthorhombic crystal structure.

In this depiction of the crystal structure of PbZrO3 , the lone pairs on the Pb atoms are visualized using DFT calculations of the electronic structure. Note that the lone pairs creates a structural distortion that cancels itself. What are lone pairs ? The three ions Tl+ , Pb2+ and Bi3+ have the electronic conguration [Xe]4 f 14 5d10 6s2 . The pair of s electrons in the valence shell (the lone pair) should have spherical symmetry if they retain pure s character. However, they like to mix with anion (oxygen) p orbitals, and this mixing results in their going off center. Such off-centering is a good recipe for obtaining polar behavior. 5

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Sketch displaying the tendency of a lone pair ion (blue) such as Pb2+ to go off-center in its coordination polyhedron, leaving in the center of the polyhedron, the s2 lone pair. Such a sketch is quite accurate for describing the crystal structure of PbO in the litharge modication. Antiferroelectrics do not display hysteresis, except at high elds, where they develop separate loops at positive and negative elds. A similar dependence of magnetization on the magnetic elds is seen in metamagnets.
P

Ordered double perovskites (elpasolites) and relaxor ferroelectrics: Ordered double perovskites have the general formula A2 BB O6 . One kind of octahedra in the structure is BO6 and the other is B O6 . For the octahedra to be distinct, meaning that there is no mixing of B and B in the lattice sites of the structure, there must usually be a large difference in size and charge between B and B . For example, in the ordered double perovskite Ba2 MgWO6 , there is no mixing of Mg2+ and W6+ on a single lattice site. Instead of the Pm3m space group of simple ideal perovskites (which have cell parameters of the order ideal double perovskites crystallize in the Fm3m space group with a cell parameter around 8 A. of 4 A), Indeed, the two kinds of octahedra in the elpasolite structure are arranged as in the rock salt structure:

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BO6

B O6

The yellow squares indicate the unit cell. Many elpasolite-like compositions with Pb in the A-site display disorder of some sort, because the ordering between the B and B sites is not complete. Many of these disordered materials display relaxor behavior. For example, Pb2 Mg2/3 Nb4/3 O6 (PMN), Pb2 ScNbO6 (PSN) etc. In PMN and PSN, there are two different kinds of octahedra in the structure; one that is Nb-rich and the other that is Nb-poor. Such disorder seems to be important for observing relaxor behavior, which is characterized by: Broad phase transitions Dispersion characteristics of the dielectric constant: The T behavior is frequency dependent.
r 100 Hz 10 kHz 1 MHz

T (K)

Relaxors are useful since they have a high dielectric constance even at radio frequencies and they saturate at low voltages. Because of the broad phase transition, the T dependence of r does not create problems in devices. In addition, the hysteresis is small, the energy densities are high and the materials are eldtunable.