Appl. Phys.

A39, 221-225 (1986)

Applied

Solids

Physics A Surfaces "'

9 Springer-Verlag1986

Exchange Interactions in
A. Isalgu6

BaFe12019

Departament de Fisica, E.T.S.A.B., Universitat Polit6cnica de Catalunya, Diagonal 649, E-08028 Barcelona, Spain A. Labarta, J. Tejada, and X. Obradors Facultat de Fisica, Universitat de Barcelona, Diagonal 645, E-08028 Barcelona, Spain Received 1 April 1985/Accepted12 July 1985

Abstract. In the scope of the mean field approximation the nine nearest neighbour exchange interactions existing among the ferric ions in BaFe~/O19 hexagonal ferrite have been determined from the experimental sublattice magnetizations. It is shown that these exchange interactions are well explained by means of the superexchange theory. It is also concluded that some direct exchange interaction does exist among the octahedral 4fw ions. The calculated magnetization, paramagnetic susceptibility, and Curie temperature are in good agreement with the corresponding experimental values. The stability of the collinear Gorter-type magnetic structure of BaFe120~9 is discussed as well. PACS: 75.30, 75.50, 76.80 M-type barium hexagonal ferrite (BaFe12019) has generated a large research effort in the past years because of its relevance in technologica! applications such as permanent magnets, microwave devices, and recording media [-1, 2]. The crystal structure of the M-type compounds consists in a close packed stacking of oxygen or bariumoxygen layers and it is usually described in terms of two structural blocks: R and S blocks, with composition (BaFe6011) 2- and (Fe608) 2 +, respectively [-3, 4]. The ferric ions in the BaFe12019 M-type structure are distributed on five different crystallographic sites and present a ferrimagnetic ordering below T~=723 K I5, 6]. In Table 1 we summarize the crystallographic and magnetic characteristics of all the magnetic sublattices, and in Fig. 1 the M-type crystal structure is represented. The collinear spin ordering reported in Table 1 was proposed for the first time by Gorter [5]. He did also some qualitative considerations on the strength of the different superexchange interactions existing among the ferric ions. Deeper insight into the magnetic interactions existing in BaFe12019 was gained from the study of the hyperfine interactions on ferric ions, as deduced from M6ssbauer and NMR measurements [6]. The linear decrease with temperature of the saturation magnetization was attributed to the unusual temperature dependence of the Fe(12k) sublattice magnetization. Indeed, this unusual behaviour of the Fe(12k) sublattice magnetization was interpreted as being due to the

9 _~ OO1 e.~:::::::~~ 9 O2 ~ @03 It OO5~045_ o F e 5 o ~

eFel 9Fe2 eFe3 |

Fig. 1. Crystallographicstructureand coordinationpolyhedraof the BaFelzO19 magnetoplumbitecompound

222
Table 1. Crystallographic and magnetic characteristics of the BaFelzO19 M-type

A. Isalgu~ et al.

hexagonal ferrite
Sublattice Coordination Block Number of ions per unit formula 1 1 2 2 6 Spin direction Up Up Down Down Up

1 (2a) 2 (4e) 3 (4fxv) 4 (4fw) 5 (12k)

Octahedral Pseudo-tetrahedral Tetrahedral Octahedral Octahedral

S R S R R-S

small exchange field acting on the Fe ions as a consequence of the strongly competing magnetic interactions existing in this sublattice [6, 7]. Similar arguments have been used to explain the magnetic data of A1 and Ga substituted hexagonal ferrites [7]. On the other hand, if isotropic exchange interactions existing within the R-block are reduced by a selective substitution of non-magnetic ions, new magnetic structures such as block-canted and block-helicoidal do appear [8-10]. The role of the antisymmetric DzialonsinskiiMoriya interaction in the stabilization of these noncollinear magnetic structures has been remarked [11, 12]. As a matter of fact, most studies on hexagonal ferrites refer to qualitative explanations of the magnetic interactions existing in these compounds. Few efforts have been concentrated on a quantitative determination of the magnetic interactions [13, 14], what would allow to put in a more firm basis a large spectrum of magnetic phenomena such as the stability of non-collinear magnetic structures and the single ion contribution to the magnetocrystalline anisotropy. With the aim to get a full determination of the magnetic interactions existing in BaFe12019, we have analized the hyperfine field measurements in the scope of the mean-field approximation taking into account all first nearest neighbours exchange interactions.

Mj stands for the j-sublattice magnetization, T is the temperature and 7ij are the mean-field coefficients which may be expressed as
7ij = -- (eijZzijJij)/(Njg2#2),

(2)

where z~j denote the number ofj-sublattice neighbours for an i-sublattice ion, Jij is the magnetic exchange integral among the i sublattice andj sublattice, g is the gyromagnetic factor, #B is the Bohr magneton, Nj is the number of ions at thej sublattice and eij= + 1 when the ith and jth sublattice magnetizations are parallel, and e~j-- - 1 when they are antiparallel. The sublattice magnetizations are calculated from

m, = Bs[g#BSHi/(KT)] ,

(3)

where mi(T) =M~(T)/Mi(O ) is the reduced sublattice magnetization and Bs is the Brillouin function for a spin S. The resultant magnetization of the collinear ferrimagnet may then immediately be expressed by M ( T ) = ~. a,M,(T)
i=1

(4)

Theoretical Model and Computational Details

First of all, let us present a brief outline of the theoretical basis of the mean-field theory, as applied to a multisublattice collinear ferrimagnet having the same magnetic ion in all the sublattices [15]. In a multisublattice ferrimagnet having a collinear magnetic structure, the total magnetic field acting on a magnetic ion located at the ith sublattice is written

for the cases when the i-sublattice magnetization is parallel, or antiparallel to the resultant magnetization ~ takes the values + 1 or - 1 , respectively. In the high-temperature low-field limit [g#BS 9Hi/(KT)~I ] the magnetization of each sublattice verifies the linear equation

Mi(r ) = C f l J T

(5)

with Ci=N,9Z#~S(S+ 1)/(3K) the Curie constant of the i sublattice. Taking (1) into account the set of n linear equations giving the different sublattice magnetizations can be written in matrix form

Hi(T)=Ho+Hex(T)=Ho+ ~ "hjMi(T),
j=l

(1)

(Ho) = (Ao) (Mi)

(6)

Ho and Hox being the external and exchange magnetic

fields, respectively, n is the total number of sublattices,

with the matrix elements A~i = T/C i - 7,j- In this way, in the paramagnetic phase we shall have det (A~j) different from 0, and the magnetic susceptibility Z may be easily

Exchange Interactions in BaFe12019 calculated as

223 Finally, we have calculated the Curie temperature T~ and the paramagnetic susceptibility z(T) by means of (7) using the exchange integrals deduced from the least squares fit. The relative accuracy of the Jij constants is of about 5%. Moreover, we have introduced in our fitting procedure a linear temperature dependence for the exchange integrals, Jij(T)=Jii(O) ( 1 - a T ) , as it has been observed by Aleonard [20] in ferrimagnetic iron garnets. The c~parameter was always much less than 10 -4 K - 1, affecting the J,j values by less than 5 %. Therefore, the temperature dependence of exchange interactions was overriden in our analysis.

(M3 = (A0
i=1

(Ho) ;

(7)

z(T)= ~ M~(T)/H o. Moreover, the Curie temperature T~is obtained as the highest root of the secular equation det(Aij ) = 0. Let us now to apply this general formalism to the case of the M-type BaFe12019 compound. In Table 2 we summarize the exchange interactions considered in our model and the number zij of nearest neighbours for each sublattice. With the only exception of the 4 f i v - 4 f l v interaction which is of the supersuperexchange type, all the other interactions act among nearest-neighbour ions. Furthermore, we assume that all the exchange interactions are antiferromagnetic, as it may be expected from the Goodenough-Kanamori rules [16, 17]. Finally, nine exchange integrals are included in our analysis. It is important to note the block nature of the magnetic interactions, which is made evident in Table 2. This arises from the structural R and S blocks composing the M structure. Hence, the 12k sublattice makes the link between both blocks. The calculation procedure used for us to get the nine different exchange interactions has been developed in a self-consistent way as follows: at each temperature, we have initially taken the experimental value for the m 5 sublattice magnetization, then, by using (3) the m2, m4 and ml, m 3 magnetization pairs have been independently calculated. With the calculated values of rn~ (i = 1.... ,4) the m 5 is calculated again and the process is repeated until the difference between two values of m~ consecutively calculated differ less than 10 -4. By a least squares minimization of the differences between the calculated and experimental m~(T) values, the values of the nine exchange integrals have been obtained. The experimental mi(T ) values have been taken from the hyperfine fields measured by M6ssbauer spectroscopy [6, 7] and N M R [18, 19], assuming proportionality between the sublattice magnetizations and the corresponding hyperfine fields.

Results and Discussion

In Table 3 are given the values of the nine exchange integrals obtained in the fit of the five magnetizations. In Fig. 2, the calculated and experimental m~(T) curves are compared. Furthermore, in Table 4 there are reported the exchange splittings at T = 0 K of the 6S ground state of the ferric ions located in the different sublattices. The small discrepancy observed in Fig. 2 between measured and calculated sublattice magnetization in the case of the 4f~v sublattice can be thought to be caused by our simplifying assumption of considering only the 4 f l v - 4 f v super-superexchange interaction, as competing with the dominant 4 f i v - 12k and 4 f i v - 2 a interactions. In order to get a better agreement between the calculated and experimental m3 sublattice magnetization, it would be necessary to include the 4 f ~ v - 4 f w super-superexchange interaction in our model. However, in this case the two-block character of the overall magnetic interactions would be destroyed, having as a consequence an enormous complication of the fitting procedure. Hence, we have not included the J34 exchange interaction in our model which, in any case, it is though to be small. With the exchange integrals deduced from our fit we have also calculated the resultant magnetization M(T) as a function of the temperature (Fig. 3), the paramagnetic susceptibility )~(T) (Fig. 4) and the Curie tempera-

Table2. Number of j-sublanice nearest-neighbours of an i-sublattice ion (zij) in BaFelzO19 M-type hexagonal ferrite / ~ 2 (40 4 (4fv0 5 (12k)
1 (2a)

Table 3. Values of the exchange integrals in degrees K obtained in the fit procedure described in the text. K stands for the Boltzmann constant J13/K - 22.(1.) Jz4/K - 22.(1.) J35/K -16.(1.) J4s/K -25.(1.) Jss/K -- 10.(1.) J44/K - 18.(1.) J33/K - 9.(1.) J15/K - 3.(1.) J25/K -3.(1.)

2 (4e) 0 3 1
0

4 (4fv~) 6 l 2
0

5 (12k) 6 6 4
6

1 (2a) 0 0 1
0

3 (4f~v) 0 0 3
6

3 (4fly)

224

A. Isalgu6 et al.

(c)

c5

0 ~-~.~

400

T(K)

800
o

0 ~

400

T(K) (d)

800

400

T(K)

800

(b)

400

T(K)

8oo

Fig. 2a-e. Comparison of the calculated and experimental, reduced sublattice magnetizations as a function of the temperature for the fivesublattices of the BaFe12019 M-type compound: (a) 1 (2a) sublattice; (b)2 (4e) sublattice; (c)3 (4flv) sublattice; (d) 4 (4fv0 sublattice; and (e)5 (12k) sublattice. Experimental values from [7, 18, 19]
800

400

T(K)

.$-

200

400

600 T(K

Fig. 3. Saturation magnetization of BaFe12019as a function of temperature: (O) experimental M measurements [21]; (A)calculated from the experimental hyperfine magnetic fields [7, 18, 19]; (-) calculated from the sublattice magnetizations deduced in the fit procedure 10-

~'6"
o 2~ a 9 Ae~

ID

700

1060

T(K)

1300

Fig. 4. Paramagnetic susceptibility of BaFet2019: (e) experimental values of Gorter [22] ; (A) our own measured values; ( - ) calculated values using the fitted exchange integrals

ture T~. The calculated value for T~ was TZh= K, 724 while the experimental value is T~eX=723 K [7, 21]. The main discrepancy between calculated and experimental magnitudes arises from the paramagnetic susceptibility z(T). It seems unlikely that this misfit has its origin in the unadapted nature of the mean field approximation which has its major failures near to the transition temperature. It is more likely that some accidental cancellation among the exchange integrals does occur in the calculation of m~(T)and T~. Hence, since the functional dependence of z(T) on the Ju

parameters is different, some discrepancies may appear. Let us finally to discuss on the relative strenght of the calculated exchange interactions on the basis of both the superexchange theory [16, 17] and crystallographic structure [3, 4]. Our calculations reproduce well the relative intensity of the four strongest exchange interactions (J13, J24, J35, and J45) in accordance with the F e - O - F e angles and their respective superexchange paths, which are of about 130 ~ thus being near to the value of 180 ~ corresponding to the strongest superexchange interaction among pairs of Fe 3+ ions. Moreover, the values of these exchange integrals are very similar to those found in ferrimagnetic spinels and garnets from studies based on the meanfield approximation [23-26]. The small calculated value of the J25 magnetic interaction agrees well with the unusually large F e - O distance existing in the pseudotetrahedral 4e polyhedron [4], causing a drastic reduction in the atomic orbitals overlap. As it could be expected, the exchange integrals arising from nearly 90 ~ superexchange paths (J15,J55) and super-superexchange interaction (J33) are much weaker than the dominant ones. The unexpected high value of the J44 magnetic exchange interaction can only be understood if we assume the existence of some direct exchange interaction between the Fe(4fvi) ions. In fact, these Fe ions are located in the octahedral sharing face, having in this way a small interatomic distance (d = 2.073 ). Therefore, a significant overlap between the cationic orbitals will exist, leading to an enhancement of the exchange interaction. The values of the Fe 3 ions exchange splittings reported in Table 4 indicate that the stability of the collinear Gorter-type magnetic structure of BaFe120 a9 is well stablished in all the sublattices of the M structure, except in the 12k octahedral, where a strong competition between both the spin down (4fw , 4fv 0 and spin up (2a, 4e, 12k) sublattices does

Exchange Interactions in BaFe12019

225 on the basis of the stabilization of new non-collinear magnetic structures observed in substituted M-type hexagonal ferrites. We conclude that the set of isotropic exchange interactions obtained in this work is an adequate tool for further theoretical investigations of the magnetic properties of M-type hexagonal ferrites.

Table 4. Exchange splitting at T = 0 K of the 6S electronic levels of the Fe a + ions in the five sublattices of BaFe120 19
Sublattice 1 (2a) 2 (4e) 3 (4f~v) 4 (4fw) 5 (12k)
g#B Hex/S [cm- 1]

336 330 528 566 144

References
exist. The 12k intrasublattice interaction is, in fact, the most effective in perturbing the Gorter ground state of BaFe120 19- This conclusion confirms previous suggestions of Albanese et al. [7]. As a matter of fact, the low stability of the spin arrangement in the 12k sublattice is determinant in the appearance of new non-collinear magnetic structures for the substituted M-type hexagonal ferrites [8-10, 27-29]. The stability of the new magnetic structures appearing in substituted M-type compounds is assured by second-order terms of the magnetic Hamiltonian, such as the DzyaloshinskyMoriya antisymmetric interaction, or by the isotropic exchange interactions themselves. Finally, let us emphasize the new possibilities opened by our work, in view of further studies on the single ion contribution to the magnetocrystalline anisotropy in BaFe12019. This is an important point in the comprehension of the fundamental magnetic properties of hexagonal ferrites which remains still controversial [30-32]. The knowledge of the exchange fields acting on the Fe 3+ ions will allow to undertake a proper evaluation of this term. 91. J. Smit, H.P.J. Wijn: Ferrites (Philips Technical Library, Eindhoven 1959) pp. 193-228 2. H. Kojima: In Ferromagnetic Materials, Vol. 3, ed. by E.P. Wohlfarth (North-Holland, Amsterdam 1983) pp. 305-390 3. W.D. Townes, J.H. Fang, A.S. Perrotta: Z. Krist. 125, 437 (1967) 4. X. Obradors, A. Collomb, M. Pernet, D. Samaras, J.C. Joubert: J. Solid State Chem. (in press) 5. E.W. Gorter: Proc. IEEE 104 B, 255 (1957) 6. G. Albanese: J. Physique 38, C1-85 (1977) 7. G. Albanese, M. Carbucicchio, A. Deriu: Phys. Stat. Sol. (a) 23, 351 (1974) 8. O.P. Aleshko-Ozhevskii, I.I. Yamzin: Soy. Phys.-JETP 29, 155 (1969) 9. M.I. Namtalishvili, O.P. Aleshko-Ozhevskii, I.I. Yamzin: Sov. Phys.-Solid State 13, 2137 (1972) 10. G. Albanese, A. Deriu, E. Lucchini, G. Slokar: Appl. Phys. A26, 45 (1981) 11. L.I. Koroleva, L.P. Mitina: Soy. Phys.-Solid State 13, 526 (1971) 12. L.I. Koroleva, L.P. Mitina: Phys. Stat. Sol. (a) 5, K55 (1971) 13. M.P. Petrov, A.V. Kunevich: Sov. Phys.-JETP 36, 1184 (1973) 14. A. Grill, F. Haberey: Appl. Phys. 3, 131 (1974) 15. J.S. Smart: Effective Field Theories of Magnetism (Saunders, Philadelphia 1966) pp. 58-68 16. P.W. Anderson: In Magnetism, Vol. 1, ed. by G.T. Rado, H. Shull (Academic, New York 1963) pp. 25-83 17. J.B. Goodenough: Magnetism and the Chemical Bond (Wiley, New York 1966) pp. 157-185 18. R.L. Streever: Phys. Rev. 186, 285 (1969) 19. K. Kareyama, K. Kohn, K. Uematsu: J. Phys. Soc. Jpn. 29, 791 (1970) 20. R. Aleonard: J. Phys. Chem. Solids 15, 167 (1960) 21. B.T. Shirk, W.R. Buessem: J. Appl. Phys. 40, 1294 (1969) 22. E.W. Gorter: Philips Res. Rep. 9, 295 (1954) 23. L. N6el: Ann. Phys. 3, 137 (1948) 24. R. Pauthenet: Ann. Phys. 3, 429 (1958) 25. G.T. Rado, V.J. Folen: J. Appl. Phys. 31, 62 (1960) 26. C.M. Srivastava, G. Srinivasan, N.G. Nanadikar: Phys. Rev. B 19, 499 (1979) 27. X. Obradors, A. Isalgu~, A. Collomb, M. Pernet, J. Rodriguez, J. Tejada, J.C. Joubert: IEEE Trans. MAG-20, 1636 (1984) 28. X. Obradors, A. Collomb, M. Pernet, J.C. Joubert, A. Isalgu6: J. Magn. Magn. Mater. 44, 118 (1984) 29. X. Obradors, A. Isalgu~, A. Collomb, M. Pernet, J. Tejada, J.C. Joubert: Adv. in Ceramics 15 (in press) 30. N. Fuchikami: J. Phys. Soc. Jpn. 20, 760 (1965) 31. G. Asti, S. Rinaldi: AIP Conf. Proc. 34, 214 (1976) 32. Y. Xu, G.L Yang, D.P. Chu, M.R. Zhai: J. Magn. Magn. Mater. 31-34, 815 (1983)

Summary and Conclusions

A mean-field analysis of the exchange interactions in BaFe12019 M-type ferrimagnetic hexagonal ferrite has been carried out. The experimental sublattice magnetizations of the five sublattices have been used for the evaluation of nine exchange interactions. The saturation magnetization, the paramagnetic susceptibility and the Curie temperature have been calculated using these exchange interactions. A good overall agreement among the calculated and experimental magnitudes is reached. It has been shown that the relative strenght of the exchange interactions is in accordance with the superexchange theory. For instance, we have concluded that, to some extent, a direct exchange interaction does exist among the Fe(4fvi) ions which have an anomalously short interatomic distance. We have found that the Fe(12k) sublattice, making the link among R and S structural blocks, is subjected to very strong competitive exchange interactions. This anomalous feature lies

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