Materials Science and Engineering A304306 (2001) 10501054

Crossover in the magnetic properties of nanostructured metals

J.F. Lfer a, , H.B. Braun b , W. Wagner b , G. Kostorz c , A. Wiedenmann d
Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland and California Institute of Technology, W.M. Keck Laboratory, Pasadena, CA 91125, USA b Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland c ETH Zrich, Institut fr Angewandte Physik, CH-8093 Zrich, Switzerland d Hahn-Meitner-Institut, D-14109 Berlin, Germany
a

Abstract Magnetization measurements and small-angle neutron scattering (SANS) were performed on nanostructured Fe, Co and Ni samples, produced by inert-gas condensation. The grain size, which is 1020 nm in the as-prepared state, was increased incrementally up to 100 nm by thermal annealing. The coercive eld shows a pronounced variation with grain size. In Fe, it passes a maximum at around 35 nm and shows a steep decrease towards smaller grain sizes. Small-angle neutron scattering experiments show that magnetic correlations which extend over several grains form spontaneously in zero-eld. The correlation length depends strongly on grain size and has in Fe a minimum at around 35 nm. We explain the results at low grain sizes on the basis of an extended random-anisotropy model. Within this model, we take into account that the intergrain exchange coupling constant is smaller than the intragrain exchange constant. We further demonstrate that the random-anisotropy model will break down for grain sizes exceeding a critical value Lcrit = , with approximately the bulk domain-wall width. For grain sizes above Lcrit , the coercive eld follows a 1/D behavior and the magnetic correlation length increases approximately linearly with grain size, i.e. the magnetic properties approach those of coarse-grained ferromagnetic materials. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Nanostructured ferromagnetic materials; Random-anisotropy model (RAM); Small-angle neutron scattering (SANS); Magnetic correlations

1. Introduction The interest in the investigation of nanostructured ferromagnetic materials has progressively increased in recent years owing to attractive potential applications. For magnetic storage applications, knowledge of the magnetic properties on the nanometer scale is crucial. Furthermore, FINEMET [1] or NANOPERM (FeMB, M = Zr, Hf, Nb) are examples of recently developed soft-magnetic nanocrystalline alloys, which are already used in cores of transformers. The properties of isolated ferromagnetic nanoparticles are mostly determined by the particle size. If such particles are consolidated to form a nanostructured material, the resulting magnetic properties are not only determined by the particle (grain) size, but also by the exchange interactions between the adjacent grains. In such materials, the magnetizations of neighboring grains may align with each other, such that they do not follow the randomly oriented anisotropies of the individual grains any more. As a consequence, the effective anisotropy is reduced to the statistical average of the anisotropies of the magnetically correlated grains. This is the
Corresponding author. Fax: +1-626-7956132. E-mail address: loefer@caltech.edu (J.F. fer).

idea of the random-anisotropy model (RAM), originally developed for amorphous ferromagnets [2]. Within this model, however, the grain size dependence of the magnetic properties of nanostructured materials was also explained [3,4]; combining results from different Fe based nanocrystalline alloys, the coercive eld for sufciently small grain sizes has been found to decrease with the sixth power of the grain size. Furthermore, in other studies on nanostructured materials, magnetic correlations have been observed which extend over several grains [57], and thus support the above model. In the following, we present a systematic study of the grain size dependence of the magnetic properties of nanostructured Fe, Co and Ni produced by inert-gas condensation. We chose three different ferromagnetic metals, i.e. Fe, Co and Ni, to resolve the inuences of the different bulk anisotropy constants. With the aim of relating microscopic and macroscopic magnetic properties, magnetization measurements were performed in conjunction with magnetic small-angle neutron scattering (SANS). The macroscopic magnetization was measured with a SQUID magnetometer for grain sizes between 10 and 100 nm. Magnetic SANS was used to characterize the magnetic microstructure on the scale of the grain size, which again was varied between 10 and 100 nm.

0921-5093/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 1 - 5 0 9 3 ( 0 0 ) 0 1 7 5 3 - 6

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2. Experimental procedure The nanostructured samples were produced by the inert-gas condensation technique [8] and consolidated in situ in high vacuum of 108 mbar. The consolidation was usually performed at a pressure of 2 GPa for 25 h at room temperature or elevated temperatures (up to 300 C). In order to induce grain growth, some samples were annealed additionally for 24 h in a tube furnace in vacuum of 106 mbar. The SANS measurements were carried out at the instrument V4 at the Hahn-Meitner-Institut, Berlin, using a neutron wavelength of = 8 with a wavelength spread of / = 0.1. The measurements were performed at room temperature with the samples placed between the pole pieces of an electromagnet, which allowed a homogeneous eld of up to 10 kOe to be applied horizontally, perpendicular to the incoming neutron beam and parallel to the at surfaces of the disk-shaped samples.

and Ni, measured in zero-eld and in the maximum eld of 10 kOe. For Q values above 0.2 nm1 , the scattering curves measured with or without magnetic eld lie closely together and are parallel for all three materials. For smaller Q, however, a signicant splitting is observed due to a magnetic scattering contribution in zero-eld which is suppressed in high eld. The Q range where this additional scattering occurs reects correlation lengths considerably larger than the grain size, the latter being around 10 nm in the as-prepared state. Thus, the measurements show that magnetic correlations extending over several grains form spontaneously in zero-eld. The splitting of the SANS intensity occurs at the highest Q value for (hcp) Co and shifts progressively to lower values for Fe and Ni (cf. Fig. 2). This shows that the magnetic correlation length systematically decreases with increasing bulk anisotropy constant, K (K Ni = 5.7 104 erg/cm3 ,

3. Experimental results Fig. 1 shows the coercive eld at 300 K as a function of grain size for nanostructured Fe. Even for single type of material (having one bulk anisotropy value), the coercive eld shows a pronounced variation with grain size. It passes through a maximum at around 35 nm and shows a steep decrease towards smaller grain sizes. For grain sizes D larger than 35 nm, the coercive eld follows a 1/D behavior, a relation which is generally ascribed to the pinning of domain walls at interfaces (see also [3,4]). Thus, at larger grain sizes, the grain-size dependence of the magnetic properties is comparable to that of coarse-grained ferromagnetic materials, whereas for smaller grain sizes a different behavior is observed. We further performed SANS measurements in external magnetic elds of varying strength. Fig. 2 shows the scattering cross section as a function of Q for as-prepared Fe, Co

Fig. 1. Coercive eld, Hc , as a function of grain size for nanostructured Fe, measured at a temperature of 300 K. The solid curve serves as guide for the eye, but also represents a l/D behavior for grain sizes larger than 35 nm.

Fig. 2. Scattering cross section as a function of Q for as-prepared nanostructured Fe (a), Co (b) and Ni (c), measured at H = 0 and H = 10 kOe (Q is the modulus of the scattering vector and equals 4 sin /, with = half the scattering angle and = wavelength of neutrons).

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K Fe = 4.7105 erg/cm3 , K Co = 5.2106 erg/cm3 at room temperature). For a quantitative analysis of our SANS data, we followed the data evaluation of [5]. In an external eld of 10 kOe, the common magnetic alignment is forced to extend to such large distances that it can no longer be resolved by SANS. In this case, the scattering arises merely from the (magnetic and nuclear) density contrast of the nanometer sized grains against the surrounding grain boundaries, which have a lower density and a different magnetic moment. In zero-eld, an additional scattering is superimposed, which is the contribution of magnetically correlated grains. In this case, the scattering cross section in an external eld of 10 kOe becomes d = d 1 ( bmag )2 + ( bnuc )2 ip (Q, R), 2 (1)

with ip the structure function of the particles and bmag , bnuc , the corresponding differences of magnetic and nuclear scattering lengths. In zero-magnetic eld, the scattering cross section is d = d 2 ( bmag )2 + ( bnuc )2 ip (Q, R) 3 2 + ( bmag )2 icorr (Q, Rcorr ), 3

Fig. 3. Average spatial magnetic correlation length Lmag vs. average grain size D, for nanostructured Fe. The solid line in the low grain size regime is primarily a guide for the eye, but also represents a t proportional to 1/D3 predicted by the RAM. No magnetic correlations with Lmag < Lcrit are found (gray shadowed region). Samples with D > 80 nm, leading to Lmag > 150 nm, are not shown in the gure (cf. text).

for the coercive eld, the magnetic correlation length shows a crossover at a critical length of around 35 nm.

4. Discussion (2) At grain sizes below 35 nm, we observe that the exchange coupling between adjacent grains starts to play a dominant role in the magnetization process. Following the idea of the RAM [2] and extending it to nanostructured materials as proposed in [3,4], the magnetic coupling between grains competes with the anisotropies of the individual (randomly oriented) grains. Fig. 4 gives a schematic illustration. In the subvolume V in which the grains are magnetically correlated, the effective anisotropy Keff is reduced to the statistical average of the anisotropies K of the respective grains, i.e. Keff = K/ N with N = (Lmag /D)3 the number of the magnetically coupled grains. With the effective anisotropy energy, E r K eff V, and the exchange energy, Eex AV/L2 (A = exchange constant), the minimization of the mag total energy, E r + E ex , gives Lmag (A/K)2 /D 3 .

with icorr the structure function, and Rcorr the radius, of the intergranular magnetic correlations. From the measurements at 10 kOe, using Eq. (1), we derive the parameters for the grain size distribution of our samples, assuming the shape to be a log-normal function as found in TEM investigations (see, e.g. [9]). The (volume-weighted) average grain size derived agrees well with the average grain size obtained from X-ray diffraction by evaluating the integral breadths of the Bragg peaks using the method of Klug and Alexander [10]. The matching grain sizes from the two different techniques give further support for our assumption that at 10 kOe the (nuclear and magnetic) scattering of grains is predominantly observed. By applying Eqs. (1) and (2) and subtracting the scattering at 10 kOe from the scattering in zero-eld, the length of the intergranular magnetic correlations can be extracted in an analogous way. To resolve the grain size dependence of the intergranular magnetic correlations, we investigated a series of Fe samples with different grain sizes. Quantitative data evaluation was possible up to grain sizes of 80 nm. For larger grain sizes, effects of multiple refraction occurred (see, e.g. [11]), originating from magnetically correlated regions larger than 150 nm. Fig. 3 summarizes the SANS results for all Fe samples by presenting the (volume-weighted) average magnetic correlation length, Lmag , as a function of the average grain size, D. The general trend is a continuous decrease of Lmag with decreasing grain size down to a size of about 35 nm and an increase as the grain size decreases further. Thus, as

Fig. 4. Schematic illustration of the magnetization conguration according to the RAM. The magnetizations M of the grains align parallel to each other in a subvolume V of diameter Lmag against the (random) anisotropies of the individual grains, K. This (frustrated) situation leads to a reduced effective anisotropy constant, Keff , the statistical average of the anisotropies of the grains involved.

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coupling across the interfaces is large, i.e. Ad/ID small, then Aeff = (1 + d/D)A and the effective exchange approaches that of the individual grains. In the particular case, I = A, one obtains the result of the original RAM. By minimizing the energy density of Eq. (3) with respect to Lmag , we obtain the magnetic correlation length, Lmag = 16 A2 eff , 9 K 2 D3 (5)

Fig. 5. Schematic illustration of the geometrical construction used to evaluate the magnetization congurations of nanostructured materials dominated by exchange coupling (extended RAM).

The idea outlined above results from the RAM developed for amorphous ferromagnets. However, to give a conclusive description of the magnetic properties of nanostructured ferromagnets, this model has to be generalized in two points. First, one has to consider that the anisotropy of nanostructured materials is uniform inside the nanograins, i.e. the anisotropy varies only from grain to grain (and not for individual spins as for amorphous materials). Second, the exchange across the grain boundaries differs from the exchange inside the grains, in contrast to amorphous materials where the exchange is uniform throughout the sample. Thus, for the calculation of the magnetic correlation length, Lmag , in nanostructured materials, we consider in our extended model (cubic) grains of size D with uniform intragrain exchange A, coupled via intergrain exchange I across a grain boundary of width d. Fig. 5 gives a schematic illustration of the situation. The anisotropies of the grains are randomly oriented, as indicated by the arrows ni in Fig. 5. The magnetization of volume V = L3 is assumed to be mag uniform (vector M in Fig. 5). Based on these assumptions, we can calculate the energy density e for the magnetization adjusted over a region of dimension Lmag . The detailed calculation is given in [12]. Here, we present the nal result. By introducing an effective exchange constant Aeff , the energy density has a form similar to the original RAM, i.e. e= Aeff K L2 mag D Lmag
3/2

with Aeff given by Eq. (4). For strong intergrain coupling, i.e. Ad/ID 0, the result of the RAM can be recovered, apart from a geometrical factor 1 + d/D which corrects for the nite intergrain spacing. The conditions of our experiment are best described by the case where I/A is small but nite and of the same order as d/D. In this case, Ad/ID 1, and Aeff is of the same order as A. We thus have arrived at the important result that the RAM also applies for weak intergrain coupling (as long as Ad/ID 1). In this case, Lmag is still proportional to 1/D3 , but the effective exchange constant is now smaller than the intragrain value A. Indeed, despite reduced intergrain coupling, the SANS data in the low grain size regime (Fig. 3) follow a relation Lmag 1/D 3 . As proposed in [2], the coercive eld can be estimated by equating the minimum energy density of Eq. (3) to the product of Ms Hc , with Ms the saturation magnetization. In this case, Hc = (K/4)4 D6, Ms (Aeff /3)3 (6)

(3)

The effective exchange constant, however, depends now on the intra- and intergrain exchange coupling constants as well as on the size of the grains and grain boundaries. Based on a mean-eld approximation (for details, see [12]), Aeff becomes Aeff = A 1 + d D 1+ Ad ID
1

(4)

For small interface coupling, i.e. Ad/ID large, most of the magnetization twist is absorbed by the interfaces, and Aeff = (1 + D/d)I equals, apart from a length correction, the interface exchange constant. Conversely, when the exchange

again with Aeff given by Eq. (4). In the present study, a coercivity proportional to D6 cannot be veried explicitly owing to the limited range in grain size which can be attained in our experiment. The sharp increase of Hc up to a grain size of 35 nm (Fig. 1) is, however, in general agreement with Eq. (6). Furthermore, it should be mentioned again that in the present study the grain size dependence of the coercive eld was obtained for a single type of material (Fe). Thus, we have eliminated the ambiguity that changes in the coercive eld may be caused by varying bulk anisotropies related to the use of different nanocrystalline alloys (see, e.g. [3,4]). So far, we have only considered small grain sizes, i.e. grains which are sufciently small that the exchange coupling between adjacent grains plays a dominant role in the magnetization process. As a matter of principle, the RAM cannot be applied in a range where domain walls can form within one grain. As shown in [12], however, nonuniform magnetization congurations can exist in individual grains with sizes exceeding the critical length Lcrit = , with Aeff /Knano approximately the bulk domain-wall = width; Knano is the anisotropy of the nanosized grains, which can be larger than the bulk anisotropy (see, e.g. [13]). Thus, in systems consisting of grains with D > Lcrit , the magnetization will generally match the anisotropy direction of the individual grains. The transition of the magnetization

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direction from one grain to another is then accommodated by a domain-wall type defect extending from the grain boundary into the interior of the grains. In this regime, the magnetic correlations will increase linearly with grain size D, as found experimentally (cf. Fig. 3). The existence of domain walls can also be derived from the coercivity, which is found to decrease as 1/D in this regime (Fig. 1). Using the bulk values for A and K, Lcrit is 46 nm for Fe. Since A has to be replaced by a smaller effective exchange constant Aeff and K by a (larger) anisotropy Knano , Lcrit is expected to be somewhat smaller. Indeed, the magnetization as well as the SANS measurements resolve a critical length scale of about 35 nm for Fe. In addition, to resolve the inuence of the bulk anisotropy constant, we compare the results of Fe with those of Co and Ni for the samples shown in Fig. 2, i.e. for samples with grain sizes D of around 10 nm. Using the bulk values for A and K, Lcrit = 16 nm for hexagonal Co and 120 nm for Ni. Since D Lcrit for Co, we expect the magnetic correlations to be small (cf. Fig. 3). In Ni, however, where D Lcrit , we expect, according to the RAM, large magnetic correlation lengths which extend over many individual grains. Indeed, when comparing the results of Fe with those of Co and Ni in Fig. 2, one realizes that in Co the smallest magnetic correlation lengths (down to around 20 nm (=2 /0.3 nm1 )) are found. In contrast, the magnetic correlation lengths are largest, i.e. above 100 nm, in Ni. 5. Conclusions Magnetization and SANS measurements have been performed on nanostructured Fe, Co and Ni samples of varying grain size, produced by inert-gas condensation. At low grain sizes, the SANS measurements resolve magnetic correlations, which form spontaneously in zero-eld and extend, in Fe and Ni, over many grains. Focussing on Fe, we nd that the magnetic properties, in particular coercivity and magnetic correlation lengths, vary drastically with grain size. They show a crossover at a critical length Lcrit = , with approximately the bulk domain-wall width. For grain sizes below Lcrit (35 nm in Fe), the magnetic properties can be explained by a model where the magnetic alignment, forced

by exchange interaction, between the grains competes with the anisotropies of the individual grains (random-anisotropy model). Remarkably, this model also holds if a reduced intergrain coupling I is considered, as long as Ad/ID is small (A = intragrain exchange coupling, D = grain size and d = grain-boundary width). At grain sizes above Lcrit the magnetic properties are found to be similar to those of coarse-grained magnetic materials. Comparing the results of Fe with those of Co and Ni, we nd that Lcrit = is a characteristic length scale determining the magnetic properties.

Acknowledgements This work was supported by the Swiss National Science Foundation. J. Lfer gratefully acknowledges further support by the Alexander von Humboldt Foundation via the Feodor Lynen Program. References
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