NL2668

Ferromagnetism and Ferroelectricity

NL2668

Ferromagnetism and Ferroelectricity

Iron, nickel, cobalt and some rare earths (e.g. gadolinium) are characterized by long-range ferromagnetic order. This originates at the atomic level and causes the unpaired electron spins to line up parallel to each other within a region of space called a magnetic domain. Domains range from 0.1 mm to a few mm in size. Within each domain, the net magnetization is large and homogenous, but over the entire sample it averages out to zero due to their random orientations. An externally applied magnetic field can cause the material to become macroscopically magnetized as the magnetic domains already aligned in the direction of this field grow at the expense of their neighbors and those neighbors reorient their magnetizations towards the field direction. Ferromagnets have very high magnetic susceptibilities, , ranging from 1000 up to 100,000. They tend to stay magnetized following the application of an external magnetic field. This tendency to "remember their magnetic history" is called hysteresis. All ferromagnets have a maximum temperature, called the Curie temperature (for iron it is about 1043 K), above which the ferromagnetic phase is transformed into a paramagnetic one as a result of thermal agitation. Ferromagnets respond mechanically to an applied magnetic field, changing length slightly in the direction of the applied field. This property is called magnetostriction. In addition to ferromagnets, there exist other magnetically ordered compounds with parallel oriented sublattices. The simplest such example is antiferromagnetism with two antiparallel sublattice magnetizations. To measure the degree of order in a complex magnetic phase, as many order-parameter components as there are distinct sublattices, may have to be used. For ferromagnets the order parameter is the net magnetization. In r r r r antiferromagnets the order parameter is the staggered magnetization: M 1 M 2 , where M 1 and M 2 are the magnetization vectors for the two sublattices. In 1907 Pierre Weiss proposed a phenomenological theory of ferromagnetism building on the model of H 1 (where x = ) paramagnetism of Langevin introduced in 1905. The Langevin function : L = coth x x kT describes the paramagnetic susceptibility of N non-interacting classical spins in a magnetic field H. Weiss assumed that spins interact with each other through a molecular field proportional to the average magnetization in the sample. So that

H eff = H + M .

(1)

Therefore, by replacing spin-spin interactions with the interaction of a single spin and all its neighbors taken as an average field, the non-linear problem was approximately solved giving rise to ferromagntism for T below Tc= C where
C= N S ( S + 1) 3k

(2)

As a consequence, the Langevin expression for susceptibility in paramagnetism

=
becomes the Curie-Weiss relation below Tc

M C = H T

(3)

C (T Tc )

(4)

for ferromagnets. This is characteristic of a second order phase transition. Spin alignment stems from the exchange interactions between spins whose energy can be expressed via the Ising Hamiltonian H in the case of strong uniaxial anisotropy favoring alignment parallel or antiparallel to the z-axis of quantization depending on the sign of the exchange constant J:

NL2668

Ferromagnetism and Ferroelectricity

H =

JS S
i i, j

(5)

In the absence of anisotropy one uses the Heisenberg Hamiltonian that couples the spin vectors in a scalar product. Free energy expansion of the Landau type can be obtained within the Curie-Weiss approximation for a Hamiltonian that includes the Zeeman interaction with an external magnetic field and an Ising-type spin-spin interaction. Ferroelectricity was discovered in the beginning of 20th century as a property of ionic, covalent, molecular crystals and even polymers that possess electrical polarization either spontaneously (e.g. the Rochelle salt) or under mechanical stress (piezoelectricity) or temperature changes (pyroelectricty). The net polarization of a ferroelectric crystal can be reoriented applying an electric field. In ferroelectric phase transitions a change in the crystal structure is accompanied by the appearance of spontaneous polarization. Ferroelectric phase transitions can either be displacive or order-disorder type. In displacive transitions (e.g. BaTiO3), atoms or molecules exhibit small, compared to the unit cell, positional shifts with long-range correlations. These transitions are caused by phonons and the order parameter is the amplitude of the related lattice distortion giving rise to a change of the lattice structure. Displacive transitions are described using a continuous Landau-Ginzburg model with ensuing solitary waves. In order-disorder transitions (e.g. NaNO2), atoms or molecules order themselves on distances comparable to the unit cell. A transformation between randomly distributed atomic positions of in their local double-well potential bottoms (T > Tc) and an ordered arrangement (T < Tc) takes place. Models of order-disorder transitions use the Ising Hamiltonian with an effective (not real) spin variable Ferroelectric phases transitions involve symmetry changes in the crystal structure which are manifested by r the emergence of an order parameter: spontaneous polarization vector P . For second order transitions, the symmetry group of the ferroelectric phase is a subroup of that in the paraelectric phase. In some cases, such as the onset of ferroelectricity with a transverse optical branch, a so-called soft mode is responsible for the transition. The softmode's frequency k for the wave vector k tends to 0 as T Tc. A special type of ferroelectric phase transition involves incommensurate phases where spontaneous polarization develops a spatial modulation with a wavelength that is incommensurate with lattice periodicity. The occurrence of incommensurate phases is usually explained by competition between long- and short-range forces, e.g. in the Frenkel-Kontorova model. As in ferromagnets, ferroelectrics develop domains in which a particular orientation of polarization is selected. These domains can range in sizes from submicroscopic to macroscopic depending on the conditions used. The region between two neighboring domains is called a domain wall. JACK A. TUSZYNSKI See also critical phenomena, order parameters, domain walls, hysteresis Further reading Bruce, A.D. and Cowley, R.A. 1981. Structural Phase Transitions. London: Taylor and Francis Kittel, C. 1956. Introduction to Solid State Physics. New York: Wiley Landau, L.D. and Lifshitz, E.M. 1959. Statistical Physics. London: Pergamon Lines, M.E. and Glass, A.M. 1977. Principles and Applications of Ferroelectric and Related Materials. Oxford: Clarendon Press Stanley, H.E. 1971. Introduction to Phase Transitions and Critical Phenomena. Oxford: Oxford University Press White, R.H. and Geballe, T. 1979. Long Range Order in Solids. New York: Academic Press