Ferroelectrics

The term ferroelectrics arose by analogy with ferromagnetics, mainly because they have similar characteristics: under electric elds for ferroelectric phenomena and under magnetic elds for ferromagnetic phenomena. The prex ferro- derived from ferum, which means iron in Latin. The term is perfect for ferromagnetics, since all ferromagnetic phenomena are associated with the special type of spin arrangement of the iron atoms. But in ferroelectrics there are no iron atoms, so the prex does not mean iron. Rather, it implies the similarity in characteristics to ferromagnetics. Like ferromagnetics, ferroelectrics exhibit a spontaneous electric polarization below the Curie temperature, a hysteresis loop, and an associated mechanical strain. However, ferroelectrics differ from ferromagnetics in their fundamental mechanisms and also in some of their applications

The prex piezo- in the word piezoelectrics is derived from a Greek word, piezein, meaning pressure. Piezoelectrics are materials in which electricity can be generated by an applied mechanical stress or a mechanical stress can be produced by an applied electric field. The piezoelectric phenomena occurs in both the ferroelectric and the nonferroelectric states. In general, all materials undergo a small change in dimension when subjected to an external force, such as an applied electric field, a mechanical stress, or a change in temperature. (heat). Depending on the material structure, such a small change in dimension may result in a change in electric polarization and hence give rise to the occurrence of the ferroelectric, piezoelectric, or pyroelectric effects. It can be imagined that materials exhibiting these effects must be polar and have an electrical order implying that they must be crystals or polycrystalline materials composed of crystallites. A crystal or a crystallite must have a definite chemical composition, with the molecules made up of positive ions (atoms sharing part of their valence electrons with others) and negative ions (atoms receiving part of electrons from others) occupying lattice sites to constitute a crystal structure lattice. The smallest repeating unit of the lattice is called the unit cell, and the specic symmetry of the unit cell determines whether the crystal exhibits ferroelectric, piezoelectric, pyroelectric, or electro-optic effects.

On the basis of the symmetry elements of translational position and orientation, there are 230 space groups. Ignoring translational repetition, these 230 groups break down into 32 classes, known as the 32 point groups. Point groups are based on orientation only. Of the 32 classes (or point groups), 11 classes are centrosymmetric and 21 classes are noncentrosymmetric, possessing no center of symmetry. The latter is the necessary requirement for the occurrence of piezoelectricity. However, one of the 21 classes, though classified as the noncentrosymmetric class, possesses other combined symmetry elements, thus rendering no piezoelectricity. So, only 20 classes of noncentrosymmetric crystals would exhibit piezoelectric effects. In 10 of these 20 classes, polarization can be induced by a mechanical stress, while the other 10 classes possess spontaneous polarization, so they are permanently polar and thus can have piezoelectric as well as pyroelectric effects. There is a subgroup within these 10 classes that possesses spontaneous polarization and reversible polarization; this subgroup can exhibit all three effects ferroelectric,

piezoelectric, and pyroelectric. In fact, the ferroelectric effect is an empirical phenomenon distinct from piezoelectric and pyroelectric effects in that it exists with a reversible polarization. The relationship between polarization behavior and crystal structure is shown in Figure

Six typical ferroelectric materials are Barium titanate (BaTiO3)type ferroelectrics Potassium dihydrogen phosphate (abbrevi- ated KDP, KH2PO4)type ferroelectrics Potassium-sodium tartrate tetrahydrate (Rochellesalt, KNaC4H4O64H2O) type ferroelectrics Triglycine sulphate (abbreviatedTGS, (NH2CH2COOH)3H2SO4)type ferroelectrics Alloys of lead, zirconium, and titanium oxide (abbreviated PZT, alloys of PbO, ZrO2, and TiO2)type ferroelectrics Polyvinylidene fluoride (abbreviated PVDF, (CH2-CF2)ntype ferroelectrics.

BaTiO3-Type Ferroelectrics BaTiO3 belongs to the family of ABO3 Perov- skite mineral (CaTiO3) structures, in which A and B are metals. The total charge of the A and B positive ions must be +6, and A and B must be of quite different sizes; the smaller ion, with a larger charge, must be a transition metal. For BaTiO3, Ti is a 3d transition element and has the d orbital for electrons to form covalent bonds with its neighbors. The radius of Ti4+ ion is about 0.68 , and that of Ba2+ is about 1.35 . These ions form nice octahedral cages, with the O2- ions held apart. At temperatures higher than the Curie temperature (>120C), Ti4+ stays in the cage, rattling around it to make the unit cell maintain a symmetrical cubic structure, as shown in Figure 4-10(a). However, the structure of the unit cell is tem- perature dependent. At a certain transition temperature, the particular structure of the unit cell becomes unstable and must transform to a more stable one. So, at the Curie temperature Tc, the octahedral cages distort and the positive ions move to off-center positions. The crystal takes a tetragonal form, resulting from the stretching of the cubic unit cells along one edge, as shown in Figure 4-10(b). In fact, the Ba2+ ions shift 0.05 upward from their original position in the cubic structure; Ti ions shift upward by 0.1 , and the O 2- ions downward by 0.04 to form the tetragonal structure. As a result of the ion shifts, the centroid of the positive charges no longer coincides with the centroid of the negative charges; therefore, the unit cells become permanently polarized and behave as permanent dipoles, leading to spontaneous polarization. The direction of the displacement can be reversed by a sufficiently high electric field of opposite polarity. This possibility of dipole reversal distinguishes ferroelectric materials from nonferroelectric ones. At temperatures below Tc and between 120C and 5C, the structure is tetragonal and the polar axis (i.e., the direction of the spontaneous polarization) is along the c-axis of the unit cells, in which c > a. At about 5C, the tetragonal unit cells undergo a transition for a higher stability to the orthorhombic structure, which is formed by stretching the cell along the face-diagonal direction with the polar axis also along the same direction. This structure will remain stable for temperatures between 5C and -90C. Similarly, at around -90C, a rhombo- hedral structure, formed by stretching the unit cell along the body-diagonal direction, becomes preferred, as shown in Figure 4-10(c). The direction of spontaneous polarization is

always along the direction of the unit cells elongation, that is, the stretching direction. This is also referred to as the ferroelectric polar axis. BaTiO3-type ferroelectrics are nonpiezoelec- tric in the unpolarized state. The cubic symmetry implies that, depending on the temperature, spontaneous polarization may occur along several axes. For example, there is a set of three (100) axes, a set of six (110) axes, and a set of four (111) axes. The three sets are non- equivalent.

Figure 4-10 Schematic diagrams showing (a) the unit cell of BaTiO3, (b) the ion displacement due to the cubic- tetragonal distortion in BaTiO3, and (c) the temperature dependence of the structure of the unit cell.