Magnetic Polarons, Charge Ordering and Stripes

24.10.2002

Magnetic Polarons, Charge Ordering and Stripes

There is intensive research going on worldwide in order to unravel the mechanisms responsible for the remarkable properties of a whole family of complex materials. In these materials, competing interactions lead to the spontaneous formation of nano-sized regions of a different phase. In the case of magnetoresistive manganites, these might be metallic or polaronic in nature, their size may depend sensitively on temperature and magnetic field. High-Tc superconductors may present charge-ordered stripes that are superconducting, separated by antiferromagnetic regions which act as Josephson junctions by a proximity effect. In relaxor ferroelectric also, there are nano-sized polar domains. The issues confronted by current researchers working with strongly correlated systems are enormous, intricate and complex. The challenge both to experimental and theoretical physics stems from the fact that the relevant physical mechanisms and the material science aspects cover a very wide range of properties, such as the interplay of charge, spin, orbital degrees of freedom. The purpose of this chapter is to bring out some interesting phenomena that one might expect to observe in magnetic semiconductors and transition metal oxides. The descriptions are meant to develop in the reader an intuitive idea of what might be happening in the prototypical systems considered in these notes. Hopefully, these simple heuristic arguments may help give a sense that some heterogeneity can be expected, which is intrinsic to the physics that drives their properties. I am not considering here any kind of heterogeneity due to crystalline imperfections.

Magnetic Polarons
Consider an antiferromagnetic semiconductor, doped with electron donors. Assume further that the extra electrons are confronted to a large on-site exchange repulsion. Because of it, you could assume the simplistic senario below left (shown for one electron).

However, this constitutes a severe confinement of this electron. The kinetic energy of an electron tends to increase with confinement. We expect a kinetic energy of the form h2k 2 E= 2m

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with some quantization rule for k. If the electron is confined to a sphere of radius R, then k will be of the order of 2 R This entity is referred to as a magnetic polaron. Lets call J the exchange coupling of an s electron on the ion with the core electron, typically an f electron, of the same ion. A typical value for J is a tenth of an eV. Now, when the electron is spread (figure above, right), the exchange is reduced. Call Jeff the exchange 2 energy. Since the exchange integral contains an integrand of the order of s , the effective coupling is scaled by the ratio : 4 3 R J 3 that is : J eff = = 4 3 a 3 in which R is the radius of the presumed polaron and a is the radius of the ion carrying the magnetic moment. At each site, the exchange interaction is of the order of r r J eff S s

The electron so partially localized interacts with a number of sites (carrying a magnetic moment) equal to . Hence the magnetic energy due to the coupling of the partially delocalized spin is : Emag J eff S z 3 = JS z where Sz is meant to be the average spin of the magnetic moment at one site. Now we just need to work out what Sz might be under these circumstances. We follow the usual mean field treatment, stating that the spin Sz is the Curie susceptibility times the magnetic field composed of the field due to the exchange coupling to the electron (strength Jz) and the coupling among the local moments (strength J ferro ). Generally, if an interaction has the form : rr H int = JSs r r we can think of it as the spin S coupled to the field Js / g B . So we have : J S z = Curie eff + 6 J ferro S z 2 From this, we deduce a Curie-Weiss susceptibility , that is the susceptibility of the ferromagnet, and J J S z = eff = 3 2 2 With this result the magnetic coupling amounts to J2 E 3

Recall that the J here is describes the s-f coupling and the susceptibility has the form :

=
The total energy has the form :

T Tc

Magnetic Polarons, Charge Ordering and Stripes Etot = A B

24.10.2002

r We cannot assume freely that 0 in the above, because this would make S diverge,

which contradicts the fact that S is limited to a finite value (e.g. 7/2 for Eu in EuO), and contradicts also our assumption of linear response. We can consider that solution may arise if the general form of the dependence of Etot leaves a region of negative values inside the region where Sz is reasonable.

Sz < S
0 1

We see from these considerations however that it may be possible to have a gain in energy in such a process. The gain is more likely when the susceptibility is large, hence near Tc. As the J J radius is to be taken rather small, our expression S z = eff = 3 implies that Sz is 2 2 saturated to its maximum value S. This is a characteristic feature used e.g. in an NMR study as evidence for magnetic polaron formation : while the magnetization decreases with temperature, the NMR frequency, that is, the hyperfine field, remains unchanged! 1

We have not considered above the possibility that the electron is bound near a donor by electrostatic interactions. This is the case for example when EuO is doped with Gd. Eu is divalent, Gd is trivalent, hence gives out an extra electron. It is known that Gd substitutes for Eu in EuO. It was found that this doping increases Tc enormously. This can be taken as an indication of enhance ferromagnetic coupling in the doped system compared to the stoichiometric one.

Coey, Viret et al, J. Physics C : Cond. Mat.

Magnetic Polarons, Charge Ordering and Stripes

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Figure 4.120 of Electronic conduction in oxides, Springer Solid State Physics Series, vol. 94. Temperature dependence of the magnetitzation of EuO, substituted by 2% Gd(+++) and a thin film with excess Eu(). The electrical resistivity of the latter specimen is about 5x10-3 Ohm.m The solid curve in the figure is the thermomagnetic curve of stoichiometric EuO.

One dimensional model for polarons and introduction to double exchange

From S. Pathak and S. Satpathy, Columbia, Missouri, PRB 63, 214413 (2001) We consider the fate of a conduction electron in an antiferromagnetic one-dimensional chain of localized moments. This electron experiences an exchange coupling with the local moments. The author refers to the paper of Anderson and Hasegawa on double exchange to state that the kinetic energy of the electron comprises a term of the form : t cos ( / 2 ) where t is the transfer integral. See my notes on exchange where this exchange intergral appears. is the angle between the local moments on the two adjacent sites for which the transfer integral is calculated. This term can be thought of as follows. It is known in quantum chemistry (see e.g. Coulsons Valence) that the estimate of the energy of the ground state of a diatomic hydrogen molecule is enhanced if one includes the possibility for both electrons to be on the same atom. This leads to the transfer integral term t in the energy. Now, Anderson and Hasegawa consider a diatomic molecule that carry each a core electron magnetic moment.

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They assume a very strong exchange coupling of the valence electrons with these core moments. Therefore, the eigenstates of the atoms have the spin of the valence electron parallel to the core moment. Now the transfer integral, which in essence describes the probability of an electron hopping from one atom to the other, will include a spin term. The hopping probability of going to atom 1 to atom 2 now includes the probability for the spin of the r r electron at site 1 in the direction of S1 to be at site 2 along S2 . Elementary quantum mechanics of spin particles dictates that this probability is cos ( / 2 ) . Then the authors write the electron wave functions in terms of creation operators at site n where the local moment is in the plane normal to the chain, at an oritentation given by the angle n :
* = cn an 0
n

In view of the general result about the lowering of energy by hopping, we get the energy :

J describes the exchange coupling among the localized moment. Note that in this model, this coupling is external to the existence of this electron that is put in the system. Mauger et al. (PRL 53, 1594 (1984), PRB31 8024 (1985) ) takes a radically different approach in which the conduction electrons are responsible of this coupling (J). Now, we need to set the zero of energy somewhere. We want to compare the energy of the polaron to the energy of conduction electron, that is, a fully delocalized electron in an antiferromagnetic lattice. This is a Kronin-Penning type of problem, or a one-dimensional tight-binding problem, where the periodic potential is the exchange interaction with the local antiferromagnetic moments. The energy band would be :
Ekr = J H S 2 + 4t 2 cos2 ( ka )
2

where a is the lattice constant, J H the exchange constant for the electron and the localized moment. In the limit of very large exchange coupling compared to t, then this energy is about J H S in the ground state. The authors wish to take out of the energy expression the energy of the antiferromagnetic lattice. Taking this term out, and the energy of the electron in a conduction band state, they get : m * E = t cn cn cos( n ) + cc + JS 2 ( cos( n m ) + 1) 2 n.n. n.n. In order to apply a simple variational method, they turn this expression into a continuum limit. This would be valid if the polaron size was much larger than the lattice constant. It turns out not be really like that, but this approach is sufficient to get a feel for what might happen. Hence they make the remplacement : cn a ( x ) where x is measured in units of a, the lattice constant. n +1 n ( x )

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The work out the passage from discrete terms to continuous terms by a Taylor development of . The schematics below shows that the first order terms cancel out in the summation.

( x) a

d dx

( x)

( x) + a

d dx

The c.c term doubles the contribution, so the energy in the continuous limit is given by :

The authors find the minimum either by an exact method, or using a function of their choice, which they justify in their text. Their calculation demonstrates that for any value of the transfer integral, the formation of polarons is favored. That is, the electron is trapped somewhere in space and the antiferromagnetic lattice at this point is transformed into a ferromagnetic region (see schematics).

Magnetic Polarons, Charge Ordering and Stripes

24.10.2002

This calculation yields a size of the polaron of the order of a few lattice constants. The angle between adjacent local moments jumps from parallel to antiparallel in about one lattice spacing. The paper refers to the model of Mott (Metal-Insulator Tranistions, N. Mott, Taylor & Francis, 1990) who assumed a jump from ferro to antiferromagnetism at one lattice spacing. Overall, the proposed calculation does not improve much over the Mott model. One usuful outcome of this paper is that ,based on a simple idea, it shows how carrier delocalization can lead to ferromagnetism. The authors calculated the size of the magnetic polaron as a function of the parameter = t 2 , the ratio of the transfer integral and the JS antiferromagnetic coupling of the localized moments.

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Type II polarons are saturated (region with = 0 ) whereas so-called type I have the moment fully saturated. Hence, this model finds that when the carriers are delocalized, the magnetic moments align. This notion was first introduced by Zener (Phys. Rev 82, 403 (1951) as the double exchange mechanism. It is supposed to be one of the leading mechanism of the ferromagnetism in manganites, the materials that exhibit colossal magnetoresistance. We can well imagine at this point that one of the questions that one might want to address is the following. What happens as the electron doping is increased and one gets to have a dense system of self-trapped magnetic polarons. This question was addressed recently in the literature. (M. Umehara, PRB 63, 134405 (2001) )

Bound magnetic polarons

The magnetic transition metal oxides, in particular the manganites, and related systems such as EuO, EuTe, EuS, are prone to defects, excess metal ions, oxygen vacancies etc Hence, the polaron might form around such a defect and the electrostatic interaction might be the one responsible for the trapping of the polaron. Furthermore, polarons in dilute magnetic

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semiconductors, like Mn doped CdTe have clearly charged defects at the Mn site. The literature on bound magnetic polarons is abundant. If the polaron is not bound, then it contributes to the conductivity of the material. Hence the question of the trapping of magnetic polaron is relevant to the modeling of the colossal magnetoresistance of materials such as EuO. Here we consider a theoretical description made in terms of the linear response of an electron gas coupled by exchange to an array of localized magnetic moments. This is the work of P. Leroux-Hugnon (PRL 29(14), 939 (1972), who was then at CNRS Meudon, and is now at Paris VII. (His recent work might be of interest : PRB65, 125210 (2002) Application of a self-consistent LSDA-CPA method to the MottAnderson transition in doped semiconductors, see also PRB 28(7), 3929 (983)Functionalintegral approach to the linear responses of the Hubbard model : role of exchange-field fluctuations, for functional integral, see Philippe Martin, PPUR, EPFL, Initiation lintgrale fonctionnelle)

Charge Ordering
I continue the exploration of reasons why intrinsic heterogeneities can be present in transition metal oxides with an argument put forth as early as 1955. Koehler and Wollan of Oak Ridge National Laboratory used neutron scattering and demonstrated the coexistence of antiferromagnetic and ferromagnetic regions in La1-x Ca x MnO3 . (Phys. Rev. 100(2), 545 (1955) ). LaMnO3 has Mn in a Mn 3+ state. Oxygen is 2, La is La 3+, so Mn has to be Mn 3+ . Now Ca is divalent, so the addition of Ca constitutes a hole doping. As a consequence, the system presents a mixed valence of Mn 4+ and Mn 3+ . The exchange coupling is known to be : strongly ferromagnetic between Mn 4+ and Mn 3+ , antiferromagnetic between Mn 4+ ions, either ferro- or antiferromagnetic between Mn 3+ ions, depending on their separation.

Consider now a doping at 25% Mn 4+ . Then you can imagine a charge ordering of the crystal which favours the ferromagnetic interactions between Mn 4+ and Mn 3+ . Indeed, a unit cell can be as shown below. +3 +4

+3 +3

+3 +3

+4

+3

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In this unit cell, every Mn 4+ is surrounded by Mn 3+ ions. Hence we perceive the possibility for ferromagnetism with this charge ordering. Indeed, the onset of ferromagnetism and metallic behaviour is at 25%, as shown on the phase diagram below.

Jaime and Salamon, Cond-Mat/9902284 (1999)

If the doping goes to 50%, then we might have the following charge-ordered unit cell : +4 +3 +3 +4 +4 +3

+4

+3

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Again, this structure favors ferromagnetism. At intermediate doping, one could expect an ordered array of alternating structures. Such a structure would have produced superlattice lines in the neutron diffraction pattern. They were not observed by Koehler and Wollan. But wait a few decades an read below about stripes !

Now, what can happen if the doping is below 25% ? It can happen (as Kohler and Wollan showed in 1955) that the Mn 4+ cluster in regions where this ratio of 2 Mn 4+ for 6 Mn 3+ is satisfied so as to take advantage of the strong Mn 3+ - Mn 4+ interaction.

Stripes
The idea about stripes started, as far as I can tell, from a theoretical paper by Haanen and Gunnarsson of the Max Plank Institut, Stuttgart (Phys. Rev. B40(10) 7391 (1989) ) These authors considered the antiferromagnetism of high-Tc oxide superconductors. They considered a strong on-site Coulomb repulsion of d electrons, U. They considered a hybridisation of p and d orbitals assumed to require an energy V small compared to U. Finally they considered charge hopping in which a d9 atom becomes a d10 atom, leaving a p hole. This process is assumed to require an energy D, also somewhat small compared to U. The main result of the numerical calculation based on a two-band Hamiltonian is shown in the figure below.

This is supposed to represent a copper - oxygen plane in perovskites. The density of excess holes on the oxygen ions is proportional to the radius of the circles and the spins on the Cu

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lattice are represented by the arrows. Case a) is a 9x10 array, case b a 10x10 array. Periodic boundary conditions force the formation of a loop in case b). A so-called Nel line forms. The periodicity of spins has a discontinuity on the line with spin zero on the line : up down up down zero up down up down up

as opposed to the regular up down up down zero down up down up down

It turns out that the stripes that form in doped antiferromagnets can be either insulating or conducting. Current theoretical research points to the possibility that stripes could form some sort of electronic quantum liquid crystal which would constitute a new state of matter. (Nature, S.A. Kivelson, E. Fradkin, V.J. Emery, Electronic liquid-crystal phases of a doped Mott insulator, vol. 393 1998, p. 550) Clear evidence for stripes was reported in manganites thin films. (Nature, S. Mori, C.H. Chen, S.W. Cheong, vol. 392, 473(1998) and Physics Today June 1998 page 19). High resolution electron microscopy carried out on manganite thin films showed that stripes form stable pairs which repeat periodically. Because these pervoskites are three-dimensional, the stripes here are actually planes. The sharing of electrons between Mn3+ and oxygen causes a distortion of lattice which produced the contrast in the image. The regions around Mn 4+ were less distorted and yielded less contrast. Increasing the doping level simply separated the pairs from one another.