M. Urse et al.

/ Journal of Advanced Research in Physics 1(1), 011008 (2010)

Effect of Additions on the Exchange Coupling and Magnetic Properties of Nd2Fe14B Thin Films
Maria Urse *, Marian Grigoras, Nicoleta Lupu, and Horia Chiriac National Institute of Research & Development for Technical Physics, 47 Mangeron Blvd., 700050 Iasi, ROMANIA
properties were obtained for melt-spun (Nd,Pr)2Fe14B/-Fe ribbons [1,3] and -Fe/Nd2Fe14B nanocomposite [4], alloyed with Zr. The magnetic behavior of NdFeB thin films as a function of Zr content is presented and an optimum is identified. The saturation magnetization Ms of NdFeBZr samples is decreasing due to Zr addition. For an optimum Zr content, the evolution of structural and magnetic properties of [NdFeBZr/Fe]xn films when thickness of the NdFeBZr and Fe layers was varied, is also presented.

Abstract - The magnetic behaviour of NdFeB thin films as a function of Zr content was studied and the optimum Zr concentration was determined. For this optimum composition the evolution of structural and magnetic properties of Ta/[NdFeBZr/Fe]n/Ta films, for a total thickness of NdFeBZr layer of about 540 nm and individual thicknesses of Fe spacer layer between 1 to 6 nm, is also presented. The addition of Zr is very effective in refining the Nd2Fe14B hard and -Fe soft grains produced by crystallization. Simultaneous utilization of Zr as addition and Fe thin films as spacer layer is important in enhancing the coercivity (Hc) and remanence ratio (Mr/Ms) of NdFeB films. As compared to Ta/NdFeB(540nm)/Ta single layer, the Ta/NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3/Ta multilayer film exhibits an important increase in the coercivity from 15.7 kOe to 21.3 kOe and in the remanence ratio from 0.66 to 0.74. Keywords - Nanocomposite magnet, Multilayer films, Hard magnetic properties, Zr Addition.

II.

EXPERIMENTAL DETAILS

I. INTRODUCTION The nanocomposite magnets have attracted considerable attention due to their high remanence ratio and high energy product. These performances are attributed to the intergrain exchange interactions between the hard and soft magnetic grains which require a homogenous and fine-grained microstructure [1]. After the crystallization annealing, the nanocomposite NdFeB/M (M = -Fe, Fe3B or FeSiB) samples exhibit a complex multiphase structure consisting of a mixture of nanograins of metastable and stable hard and soft magnetic phases. Microstructure of nanocomposite magnets is strongly influenced by different elements used as additions. Many metallic elements can be added to the NdFeB nanocomposite magnets with the aim to enhance the crystallization kinetics. Generally, high melting point metals act as nuclei for crystallization which emerge from the amorphous matrix in the primary stage of crystallization, thus impeding grain growth on initial annealing. Among additions, it is known that Zr can prevents the formation of metastable Nd3Fe62B14 phase and refines the grain sizes of soft and hard phases [1-3]. Thus, good hard magnetic
Manuscript received June 8, 2010 * Corresponding author (urse@phys-iasi.ro)

All samples were sandwiched by using two Ta layers as buffer layer and capping layer with the thickness of 20 nm and 40 nm, respectively. The samples were prepared by r.f. sputtering from two targets (disc of Nd12Fe82B6 alloy with Nd and Zr chips on its surface and disc of Ta) and by electron beam evaporation (i.e. Fe films), using a conventional vacuum deposition system (Laboratory Sputtering Plant Z 400). Compositional variation of single and multilayer samples was achieved by modifying both the surface ratio of the components on the Nd(Fe,Zr)B target surface and the thickness of the successive NdFeBZr and Fe layers. The total thickness of the NdFeBZr layer was maintained constant at 540 nm and the individual thickness of the Fe spacer layer was varied from 1 to 6 nm. All samples were deposited, at room temperature, on silicium (100) substrates, in the following experimental conditions: input power between 150 and 240 W; base pressure of 2x10-4 Pa; total pressure of argon (Ar) of 1 Pa. The crystallographic structure was investigated using Xray diffraction (XRD) analysis. An X-ray diffractometer (D8 Advance) with a monochromatized Cu - K radiation was used, in a Bragg - Brentano arrangement. The WarrenAverbach method [5] was used to estimate the crystalline grain size (with an error of 15%). The composition of the individual layers was determined using the SEM/EDS technique. The magnetic characteristics were measured using a Lake Shore 7410 vibrating sample magnetometer (VSM) with a maximum magnetic field of 31 kOe. All samples were subsequently annealed in vacuum for different duration at temperatures between 550C and 700C.

M. Urse et al. / Journal of Advanced Research in Physics 1(1), 011008 (2010)

Fig.1. The dependence of the coercivity, Hc, and remanence ratio Mr/Ms on Zr content for Ta/NdFeBZr/Ta thin films annealed at 650C, for 20 minutes.

III. RESULTS AND DISCUSSION The addition of Zr is very effective in refining the Nd2Fe14B hard grains and -Fe soft grains produced by crystallization. Different compositions of the NdFeBZr targets were tested in order to obtain Ta/NdFeBZr/Ta thin films with hard magnetic properties. In Fig. 1, the dependence of the coercivity, Hc, and remanence ratio, Mr/Ms, on the Zr content for Ta(20nm)/NdFeBZr/Ta(40nm) thin films annealed in vacuum at the temperature of 650oC for 20 minutes is presented. One can see an important increase in the coercivity and remanence ratio with increasing the Zr content up to about 2.02 at.% followed by an abrupt decrease for a content of about 3.5 at.%. As compared to the Zr-free samples, the important increase of coercivity from 15.7 kOe to 20.1 kOe for Zr-doped samples is due to the domain wall pinning effect within the intergranular region. The composition of Ta/NdFeBZr(2.02at.%)(540nm)/Ta layer, determined by EDS technique, is as follows: Fe 68.57 at.%, Zr 2.02 at.%, Nd 12.23 at.%, Ta 10.03 at.% and B up to 100 at.%. The coercivity is one of the key factors controlling the properties of nanocomposite materials. For multilayer [NdFeBZr/Fe]xn samples, the soft Fe grains act as nuclei for the magnetic domains during the magnetization reversal. The control of the Fe layer thickness of the multilayer NdFeBZr/Fe films is essential for obtaining of the nanocomposite samples with hard magnetic properties. In Table I, the comparative results on the magnetic characteristics for annealed Ta(20nm)/NdFeBZr(2.02at.%) (540nm)/Ta(40nm) and Ta(20nm)/[NdFeBZr(2.02at.%) (180nm)/Fe(t)]x3/Ta(40nm) thin films with different thicknesses (t) of Fe layers are presented. It can be observed that the value of the coercivity, Hc, increases when the Felayer thickness increases from 1 nm to 2 nm, and decrease and remains approximately constant for higher thicknesses of the Fe-layer. The saturation magnetization, Ms, increases with increasing the Fe-layer thickness for the entire range investigated, from 1 to 6 nm. The remanence ratio, Mr/Ms, slightly increases with increasing Fe-layer thickness up to 2 nm while, for a higher thickness, the remanence ratio remains approximately constant. It can also be observed that

the value of the maximum energy product, (BH)max. increases with increasing the Fe-layer thickness up to 2 nm and decreases afterwards. For the Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta multilayer films, a supplemental increase in the coercivity of about 6% and in the remanence ratio of about 4% can be observed as compared to single Ta/NdFeBZr thin films. The decrease of the coercivity as a result of stratification of NdFeBZr(2.02at.%) film by using of the Fe layer of about 1 nm as spacer layer, can be ascribed to the total diffusion of Fe atoms in the NdFeBZr layer volume during the crystallization treatment. For thicknesses of 2 nm and larger than 2 nm it is quite possible that only a part of the Fe atoms from the spacer layer diffuse in the volume of NdFeBZr layer, while the rest remaining in the Fe layer form. The as-deposited samples were annealed, in vacuum, for different periods of time, at temperatures between 550oC and 700C. In Fig. 2, the demagnetization curves of Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta thin films annealed at different temperatures for 20 minutes are presented. It can be observed that the optimum annealing temperature is 650C. In Fig. 3, the typical magnetic hysteresis loops for multilayer Ta(20)/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)] x3/Ta(40) films annealed at 650C for different annealing duration are shown. One can see that the samples annealed at 650C for 20 minutes present best magnetic characteristics.

Fig.2. The demagnetization curves of Ta/[NdFeBZr(2.02at.%)(180nm)/ Fe(2nm)]x3/Ta films successively annealed at different temperatures for 20 minutes.

Fig.3. The hysteresis loops of Ta/[NdFeBZr(2.02at.%)(180nm)/Fe o (2nm)]x3/Ta films annealed at 650 C for different annealing time.

M. Urse et al. / Journal of Advanced Research in Physics 1(1), 011008 (2010)

TABLE I MAGNETIC CHARACTERISTICS OF Ta(20nm)/NdFeBZr(2.02at.%)(540nm)/Ta(40nm) AND Ta(20nm)/[NdFeBZr(2.02at.%) (180nm)/Fe(tnm)]x3/Ta(40nm) THIN FILMS ANNEALED AT 650oC FOR 20 MINUTES. Samples / (all thicknesses in nm) Saturation magnetization Ms (emu/g) 69.1 66.3 75.4 80.3 82.5 84.2 Coercivity Hc (kOe) 20.1 19.2 21.3 18.7 18.2 17.9 Remanence ratio Mr/Ms 0.71 0.72 0.74 0.73 0.73 0.72 Energy product (BH)max. (MGOe) 3.19 2.10 3.62 2.08 2.03 1.92

Ta(20)/NdFeB Zr(540)/Ta(40) Ta(20)/[NdFeBZr(180)/Fe(1)]x3/Ta(40) Ta(20)/[NdFeBZr(180)/Fe(2)]x3/Ta(40) Ta(20)/[NdFeBZr(180)/Fe(3)]x3/Ta(40) Ta(20)/[NdFeBZr(180)/Fe(4)]x3/Ta(40) Ta(20)/[NdFeBZr(180)/Fe(6)]x3/Ta(40)

TABLE II MAGNETIC CHARACTERISTICS OF Ta/NdFeB(540nm)/Ta SINGLE LAYER, Ta/NdFeB(180nm)/Fe(2nm)]x3/Ta AND Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta MULTILAYER FILMS ANNEALED AT 650oC FOR 20 MINUTES. Samples / (all thicknesses in nm) Saturation magnetization Ms (emu/g) 83.4 88.6 69.1 75.4 Coercivity Hc (kOe) 15.7 17.2 20.1 21.3 Remanence ratio Mr/Ms 0.66 0.70 0.71 0.74 Energy product (BH)max. (MGOe) 5.69 4.68 3.19 3.62

Ta(20)/NdFeB(540)/Ta(40) Ta(20)/[NdFeB(180)/Fe(2)]x3/Ta(40) Ta(20)/NdFeBZr(2.02at.%)(540)/Ta(40) Ta(20)/[NdFeBZr(2.02 at.%)(180)/Fe(2)]x3/Ta(40)

In Fig. 3 it can be observed that for an annealing time of 30 minutes, a small shoulder appears on the hysteresis loop as result of the development of Fe grains near Nd2Fe14B grains. Table II presents the main magnetic characteristics of Ta/NdFeB(540nm)/Ta single layer and multilayer Ta/NdFeB(180nm)/Fe(2nm)]x3/Ta and Ta/[NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3 /Ta thin films annealed at650oC for 20 minutes. As compared to the Ta/NdFeB(540nm)/Ta single layer, for the multilayer Ta/NdFeB(180nm)/Fe(2nm)]x3/Ta films there is a small increase in the coercivity of about 9.5%, while for the Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta films there is an important increase in coercive field of about 35.6% due to the Zr addition and stratification effect using Fe films as spacer layer. Due to the diffusion process the multilayer structure is partially or totally destroyed and a mixture consisting of hard magnetic and soft magnetic phases is created in different ratios depending on the thicknesses of the constituent layers and annealing temperatures. The X-ray diffraction investigations indicate that Ta/[NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]xn/Ta thin films, in as deposited state and after thermal treatments at temperatures below 570oC, have amorphous structure. At annealing temperatures between 570oC and 600oC the microstructure of the samples consists of a small number of Fe3B nanograins which are embedded in the amorphous matrix. Samples annealed at temperatures higher than 600oC exhibit a complex multiphase structure of tens of nanometers. Figure 4 shows the X-ray diffraction patterns for selected samples annealed at 650oC for 20 min., as follows: Ta/[NdFeB(540nm)/Ta film (a); Ta/[NdFeBZr (2.02at.%) (540nm)/Ta film (b); multilayer Ta/[NdFeBZr (2.02at.%)(180nm)/ Fe(2nm)]x3/Ta film (c). It can be observed that the samples which contains Zr as addition presents a complex multiphase structure consisting of a mixture of nanograins of Nd2Fe14B or a mixture of Nd2Fe14B and Nd2(Fe,Zr)14B hard magnetic phases, and Fe3B, Fe2B and Fe2Zr soft magnetic phases. For Ta(20nm)/ [NdFeBZr

(2.02at.%)(180nm)/Fe(2nm)]x3/Ta(40nm) film (curve c), the Nd2Fe14B and Nd2(Fe,Zr)14B hard magnetic phases have the specific diffraction peaks shifted with 0.05 degree to lower degrees and this is probably to be due to a partial partitioning of Zr in Nd2(Fe,Zr)14B phase. Since the Zr amount of about 2.02 at.% is quite large, it may induce the formation of Fe2Zr additional phase. The average crystalline size of grains of soft magnetic phases for Ta(20nm)/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta(40n m) films is: 18 nm for Fe3B and Fe2B; 20 nm for Fe2Zr. The average crystalline size of hard magnetic phase grains are: 54 nm for Ta/[NdFeB(540nm)/Ta thin film; 30 nm for Ta/[NdFeBZr(2.02at.%)(540nm)/Ta thin film; 23 nm for Ta/[NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3/Ta thin film. The refinement of the grain size by using Zr as addition element is used to enhance the exchange coupling between the hard and soft magnetic grains in multilayer Ta/[Nd(Fe,Zr)B(180nm) /Fe(2nm)]x3/Ta thin films. Fig. 5 shows the M plots for Ta/[NdFeB(180nm)/ Fe(2nm)]x3/Ta and Ta/[NdFeBZr(2.02at.%)(180nm)/ Fe(2nm)]x3/Ta thin films after annealing at 650C for 20 min.

Fig. 4. The XRD patterns of NdFeB(540nm) (a), NdFeBZr(2.02at.%) (540nm) (b) and [NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3 (c) thin films.

M. Urse et al. / Journal of Advanced Research in Physics 1(1), 011008 (2010)

ACKNOWLEDGMENT Support from the Romanian NUCLEU Program (Project PN 09-43 02 01) is highly acknowledged. REFERENCES
[1] C.Wang, M.Yan and Q. Li, Crystallization kinetics, microstructure and magnetic properties of Nd2Fe14B/-Fe magnets with Zr addition, J. Phys. D: Appl. Phys., 40, 2007, pp. 3551-3556. H. W. Chang, Y. T. Cheng, C. W. Chang, C. C. Hsieh, Z. H. Guo, W. C. Chang and A. C. Sun, Improvement of size and magnetic properties of Nd9.5Fe72.5Ti3B15 bulk magnets by Zr or Nb substitution for Ti, J. Appl. Phys., 105, 2009, pp. 07A742. C. Wang, M. Yan, W.Y. Zhang, Significant changes in the microstructure, phase transformation and magnetic properties of (Nd,Pr)(2)Fe14B/alpha-Fe magnets induced by Nb and Zr additions, Materials Science and Engineering B, 123, 2005, pp. 80-83. Y. Q. Wu, D. H. Ping, X. Y. Xiong, and K. Hono, Magnetic properties and microstructures of -Fe/Nd2Fe14B nanocomposite microalloyed with Zr, J. Appl. Phys., 91, 2002, pp. 8174-8176. H.P. Klug, L.E. Alexander, in: Diffraction Procedures for Polycrystalline and Amorphous Materials, Wiley, New York, 1974, 665.

[2]

[3]

Fig.5. The M plots for Ta/[NdFeB(180nm)/Fe(2nm)]x3/Ta Ta/[NdFeBZr(2.02at.%) (180nm)/Fe(2nm)]x3/Ta thin films.

and

[4]

A positive M is observed on the whole magnetic field range confirming the existence of ferromagnetic exchange interactions between soft and hard magnetic grains. An increase in the exchange interactions between the soft and hard magnetic grains with the addition of Zr can be also observed. IV. CONCLUSIONS The addition of Zr is very effective in refining the Nd2Fe14B hard grains produced by crystallization. As compared to the Ta/NdFeB/Ta thin film, for Ta/[NdFeBZr (2.02at.%) thin film there is an important increase in the coercivity of about 28%. Simultaneous use of Zr as addition and Fe film as spacer layer are important, especially for the enhancement of the coercivity and remanence ratio of NdFeB film. In comparison with Ta/NdFeB/Ta thin film, the Ta/NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta multilayer exhibits an important increase in the coercivity from 15.7 kOe to 21.3 kOe, an increase in the remanence ratio from 0.66 to 0.74 and a small decrease of the maximum energy product from 5.69 to 3.62 MGOe.

[5]