PARAMAGNETIC RESONANCE AND STATIC SUSCEPTIBILITY MEASUREMENTS IN GdZn2

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PARAMAGNETIC RESONANCE AND STATIC SUSCEPTIBILITY MEASUREMENTS IN GdZn2

D. Debray, E. Ryba

To cite this version:

D. Debray, E. Ryba. PARAMAGNETIC RESONANCE AND STATIC SUSCEPTIBILITY MEA- SUREMENTS IN GdZn2. Journal de Physique Colloques, 1971, 32 (C1), pp.C1-1130-C1-1132.

�10.1051/jphyscol:19711404�. �jpa-00214445�

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JOURNAL DE PHYSIQUE Colloque C 1, supplkment au no 2-3, Tome 32, Fe'orier-Mars 1971, page C 1 - 1 130

PARAMAGNETIC RESONANCE

AND STATIC SUSCEPTIBILITY MEASUREMENTS IN GdZn, (*)

by D. DEBRAY and E. RYBA (**)

Service d e Physique d u Solide et de Resonance Magnttique Centre d'Etudes NuclCaires d e Saclay

BP no 2, 91, Gif-sur-Yvette, France

R6sumb. - On etudie en fonction de la temperature la resonance paramagnetique et la susceptibilite statique de GdZnz. Le moment magnetique effectif de GdZnn est egal a 8,48 magnktons de Bohr ; les temperatures de Cur~e para- magnktiquc ct ferromagnktique sont respectivement tgales k +-- 70 OK et 68 OK. Le spectre de rksonance est constituk d'une raie large unique, sans structure. Le facteur g ne depend pas de la temperature et vaut 2,029 + 0,005. On interprhte les resultats experimentaux it l'aide de la theorie RKKY des interactions d'echange s-f en tenant compte des effets de corrtlation inter6lectroniques. On obtient de cette manikre un paramttre d'echange effectif (J) &gal a -1- 0,018 eV.

Abstract. - Paramagnetic spin resonance has been observed in GdZnz, supplemented by static susceptibility measurements, over a range of temperatures. GdZnz has an effective magnetic moment 8.48 Bohr magnetons, paramagnetic and ferromagnetic Curie temperatures, respectively, equal to -1.- 70 OK and 68 O K . The resonance pattern is a single smooth, broad line. The g-value, independent of temperature, is 2.029 1 0.005. The experimental data are interpreted using the R K K Y theory of s-f exchange interaction taking into account correlation effects. The effective exchange parameter (J)

so obtained is + 0.018 eV.

I. Introduction. - One of the ways to study the interaction of local moments with the conduction electrons in a metallic host is by observation of paramagnetic resonance supplemented by static susceptibility measurements. In this paper, we report on such measurements in GdZn, over a range of temperatures.

The compound GdZn, has the CeCu,-type [I] crystal structure. This work was undertaken a s part of a broader program to understand the occurrence of the CeCu,-type structure in rare earth intermetallics as against the Laves phases and other competing structure types.

11. Experimental. - GdZn, was prepared by melt- ing together stoichiometric amounts of 99.9

+

"/, G d with 99.999 "/, Z n in tantalum crucibles sealed under an inert atmosphere. Bulk susceptibility measurements were made through the use of a modified Faraday technique [2] over the temperature range 4.2O-303 OK.

Resonance measurements were made by the usual reflection technique at 9.2 kMc on powdered samples

(< 44 microns) sealed in standard EPR tubes under an inert atmosphere t o prevent oxidation. Measurements were made over the temperature range 1530-303OK which is well within the paramagnetic region.

111.1 Experimental results. - The susceptibility of GdZn, obeys the Curie-Weiss law with an effective magnetic moment 8.48 Bohr magnetons and a paramagnetic Curie temperature (Op)

+

70 OK. The compound undergoes ferromagnetic ordering below 68 OK.

T h e resonance pattern is a single smooth (no fine structure), broad peak with the line shape typical of that expected within the skin-depth region of metallic particles. The spectra were analyzed by the method of Peter et al. [3] and due demagnetization

(*) Experimental part of this work was done, respectively, at the Pennsylvania State University and University of Pitts- burgh, U. S. A. Analysis of experimental data was done at the first author's present laboratory.

(**) Pennsylvania State University, U. S. A.

corrections were made. The g-value is independent of temperature within the limits of experimental error and equal to 2.029 f 0.005. We thus observe a g-shift, Ag =

+

^0.037^f0.005. T h e linewidth DH (half- power half-width of the absorption part of resonance) increases linearly with temperature with

DHIT

-

4 . 4 gauss/OK

(Fig. I). The shape factor A / B [4] decreases with

FIG. 1. - Temperature dependence of linewidth DHand shape factor AIB.

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19711404

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PARAMAGNETIC RESONANCE A N D STATIC SUSCEPTIBILITY MEASUREMENTS C I - 1131

falling temperature and appears to level off at a value of about 2.6.

111.2 Analysis of results. - 111 the simplest form of RKKY exchange interaction, - J.S.s, between spins of the local moments and the conduction electrons, A g [5], DN [6] and Op [7] are, respectively, given by,

where X: is Pauli volume susceptibility of theconduc- tion electrons, ^nodensity of lattice sites, Z the electron/

atom ratio and F(x) = x - ~ (X cos x - sin x). The in (3) is over all the local-moment sites. Other notations have their usual meanings.

Using lattice parameters of GdZn, [8] and assuming Gd and Zn atoms contribute 3 and 2 electrons, respectively, to the conduction band, 7 and D H were com- puted from (1) and (2). = + 0.18 eV and DHJT = 32.2 gauss/OK.

1

F as a function of k,, the Fermi wave vector, is shown in figure 2. It is seen that

FIG. 2. - Dependence of F(2 k~ R o n ) on k ~ . Summation is n

over all rare earth ions.

for the free-electron value k t ⁼1.50 A - 1 ,

1

F is positive. However, F must be negative since 8p for GdZn, is positive. Also, GdCu, (CeCu2-type struc-

ture, kF 0 = 1.34 ^{A - l )}has a small positive Op [9]. Such considerations indicate that a value of Fcorrespond- ing to k , = 0.8 k: is reasonable. Similar conclusions have also been reached by other workers [lo] for various rare earth intermetallics. Use of (3) then gives

I J I = 0.44 eV, twice the magnitude as obtained from g-shift. It should be noted that the sign of observed g-shift as well as its temperature independence is consistent with the observed enhanced effective magnetic moment and strict obeyance of Curie-Weiss law.

Howcver, the magnitudes of Jobtained above are about an order larger than the values reported by most workers [ l l , 12, 131 for G d + 3 and E u + ~ in a metallic host. Also, the observed linewidth is about an order of magnitude less than the Korringa value (2). We believe that these discrepancies are a result of neglecting inter- electron correlation and exchange effects.

It is known that the inter-electron interactions enhance the host Pauli spin susceptibility [I41 and at the same time pushes out the first zero of the RKKY oscillations [15] due to selective enhancement. The inter-electron interactions also alter the Korringa relation and give a linewidth K(d times [I61 the Kor- ringa value. As a mattcr of check, the susceptibility of LaZn, (crystal structure same as GdZn, and practi- cally same conduction electron concentration) was measurcd. The value so obtained after correction due to core demagnetization and possible impurities is

--

lo-' e. ^m.u./cc. This value is about tentimes the Pauli value and gives K(m) = 0.1. The corrected J

and DH/T are, respectively, + 0.018 eV and 3.2 gauss/

OK. Above considerations will also alter de Gennes relation (3) and are likely to bring in line the value of I J I obtained from it.

The temperature dependence of A / B is puzzling and not understood. In GdZn,, the ionic susceptibility is a t least 100 times larger than the conduction electron susceptibility and since the particle size is much larger than the skin-depth (a few microns), A / B should be = 2.6 [4]. The observation of a smooth resonance line without any trace of fine structure combined with a low observed linewidth indicates negligible, if any, effect of crystal field. This is not surprising in view of the fact that the 4 f 7 configuration is very stable and there is additional screening by conduction electrons in a metallic host.

IV. Concluding remarks. - The observation of a positive g-shift indicates the dominance of true exchange (J,,,, always positive) over that due to inter- band 4f-conduction electron mixing (J,,,,, always negative) [17]. However, since the interband contri- bution to 7 i s sensitive to conduction electron charac- ter [I 71, the sign of J may be different for the same paramagnetic ion in different host metals. It is impor- tant to consider the effect of inter-electron interactions in interpreting paramagnetic resonance results and also when de Gznnes relation (3) is used. The crystal field effect on G d + 3 in GdZn, is negligible, if any.

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D. DEBRAY AND E. RYBA

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