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M. Urse et al.

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

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/α-Fe
ribbons [1,3] and α-Fe/Nd2Fe14B nanocomposite [4],
Abstract - The magnetic behaviour of NdFeB thin films as a alloyed with Zr. The magnetic behavior of NdFeB thin
function of Zr content was studied and the optimum Zr
films as a function of Zr content is presented and an
concentration was determined. For this optimum composition
the evolution of structural and magnetic properties of optimum is identified. The saturation magnetization Ms of
Ta/[NdFeBZr/Fe]×n/Ta films, for a total thickness of NdFeBZr NdFeBZr samples is decreasing due to Zr addition. For an
layer of about 540 nm and individual thicknesses of Fe spacer optimum Zr content, the evolution of structural and
layer between 1 to 6 nm, is also presented. The addition of Zr is magnetic properties of [NdFeBZr/Fe]xn films when
very effective in refining the Nd2Fe14B hard and α-Fe soft thickness of the NdFeBZr and Fe layers was varied, is also
grains produced by crystallization. Simultaneous utilization of presented.
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 II. EXPERIMENTAL DETAILS
multilayer film exhibits an important increase in the coercivity
from 15.7 kOe to 21.3 kOe and in the remanence ratio from
All samples were sandwiched by using two Ta layers as
0.66 to 0.74.
buffer layer and capping layer with the thickness of 20 nm
Keywords - Nanocomposite magnet, Multilayer films, Hard and 40 nm, respectively. The samples were prepared by r.f.
magnetic properties, Zr Addition. 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
I. INTRODUCTION conventional vacuum deposition system (Laboratory
Sputtering Plant Z – 400). Compositional variation of single
and multilayer samples was achieved by modifying both the
The nanocomposite magnets have attracted considerable
surface ratio of the components on the Nd(Fe,Zr)B target
attention due to their high remanence ratio and high energy
surface and the thickness of the successive NdFeBZr and Fe
product. These performances are attributed to the intergrain
layers. The total thickness of the NdFeBZr layer was
exchange interactions between the hard and soft magnetic
maintained constant at 540 nm and the individual thickness
grains which require a homogenous and fine-grained
of the Fe spacer layer was varied from 1 to 6 nm.
microstructure [1]. After the crystallization annealing, the
All samples were deposited, at room temperature, on
nanocomposite NdFeB/M (M = α-Fe, Fe3B or FeSiB)
silicium (100) substrates, in the following experimental
samples exhibit a complex multiphase structure consisting
conditions: input power between 150 and 240 W; base
of a mixture of nanograins of metastable and stable hard and
pressure of 2x10-4 Pa; total pressure of argon (Ar) of 1 Pa.
soft magnetic phases.
The crystallographic structure was investigated using X-
Microstructure of nanocomposite magnets is strongly
ray diffraction (XRD) analysis. An X-ray diffractometer (D8
influenced by different elements used as additions. Many
Advance) with a monochromatized Cu - Kα radiation was
metallic elements can be added to the NdFeB
used, in a Bragg - Brentano arrangement. The Warren-
nanocomposite magnets with the aim to enhance the
Averbach method [5] was used to estimate the crystalline
crystallization kinetics. Generally, high melting point metals
act as nuclei for crystallization which emerge from the grain size (with an error of ± 15%). The composition of the
amorphous matrix in the primary stage of crystallization, individual layers was determined using the SEM/EDS
thus impeding grain growth on initial annealing. Among technique.
additions, it is known that Zr can prevents the formation of The magnetic characteristics were measured using a Lake
metastable Nd3Fe62B14 phase and refines the grain sizes of Shore 7410 vibrating sample magnetometer (VSM) with a
soft and hard phases [1-3]. Thus, good hard magnetic maximum magnetic field of 31 kOe.
All samples were subsequently annealed in vacuum for
different duration at temperatures between 550°C and
Manuscript received June 8, 2010 700°C.
*
Corresponding author (urse@phys-iasi.ro)
2 M. Urse et al. / Journal of Advanced Research in Physics 1(1), 011008 (2010)

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
Fig.1. The dependence of the coercivity, Hc, and remanence ratio Mr/Ms layer, while the rest remaining in the Fe layer form.
on Zr content for Ta/NdFeBZr/Ta thin films annealed at 650οC, for 20 The as-deposited samples were annealed, in vacuum, for
minutes. different periods of time, at temperatures between 550oC
and 700°C. In Fig. 2, the demagnetization curves of
III. RESULTS AND DISCUSSION Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta thin films
annealed at different temperatures for 20 minutes are
The addition of Zr is very effective in refining the presented. It can be observed that the optimum annealing
Nd2Fe14B hard grains and α-Fe soft grains produced by temperature is 650°C.
crystallization. Different compositions of the NdFeBZr In Fig. 3, the typical magnetic hysteresis loops for
targets were tested in order to obtain Ta/NdFeBZr/Ta thin multilayer Ta(20)/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]
films with hard magnetic properties. In Fig. 1, the x3/Ta(40) films annealed at 650°C for different annealing
dependence of the coercivity, Hc, and remanence ratio, duration are shown. One can see that the samples annealed
Mr/Ms, on the Zr content for Ta(20nm)/NdFeBZr/Ta(40nm) at 650°C for 20 minutes present best magnetic
thin films annealed in vacuum at the temperature of 650oC characteristics.
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. Fig.2. The demagnetization curves of Ta/[NdFeBZr(2.02at.%)(180nm)/
The control of the Fe layer thickness of the multilayer Fe(2nm)]x3/Ta films successively annealed at different temperatures for 20
minutes.
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 Fe-
layer 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 Fig.3. The hysteresis loops of Ta/[NdFeBZr(2.02at.%)(180nm)/Fe
o
remains approximately constant. It can also be observed that (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) 3

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 Coercivity Remanence Energy product


magnetization Hc (kOe) ratio (BH)max. (MGOe)
Ms (emu/g) Mr/Ms
Ta(20)/NdFeB Zr(540)/Ta(40) 69.1 20.1 0.71 3.19
Ta(20)/[NdFeBZr(180)/Fe(1)]x3/Ta(40) 66.3 19.2 0.72 2.10
Ta(20)/[NdFeBZr(180)/Fe(2)]x3/Ta(40) 75.4 21.3 0.74 3.62
Ta(20)/[NdFeBZr(180)/Fe(3)]x3/Ta(40) 80.3 18.7 0.73 2.08
Ta(20)/[NdFeBZr(180)/Fe(4)]x3/Ta(40) 82.5 18.2 0.73 2.03
Ta(20)/[NdFeBZr(180)/Fe(6)]x3/Ta(40) 84.2 17.9 0.72 1.92

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 Coercivity Remanence ratio Energy product
magnetization Hc (kOe) Mr/Ms (BH)max. (MGOe)
Ms (emu/g)
Ta(20)/NdFeB(540)/Ta(40) 83.4 15.7 0.66 5.69
Ta(20)/[NdFeB(180)/Fe(2)]x3/Ta(40) 88.6 17.2 0.70 4.68
Ta(20)/NdFeBZr(2.02at.%)(540)/Ta(40) 69.1 20.1 0.71 3.19
Ta(20)/[NdFeBZr(2.02 at.%)(180)/Fe(2)]x3/Ta(40) 75.4 21.3 0.74 3.62

In Fig. 3 it can be observed that for an annealing time of (2.02at.%)(180nm)/Fe(2nm)]x3/Ta(40nm) film (curve c),
30 minutes, a small shoulder appears on the hysteresis loop the Nd2Fe14B and Nd2(Fe,Zr)14B hard magnetic phases have
as result of the development of Fe grains near Nd2Fe14B the specific diffraction peaks shifted with 0.05 degree to
grains. lower degrees and this is probably to be due to a partial
Table II presents the main magnetic characteristics of partitioning of Zr in Nd2(Fe,Zr)14B phase. Since the Zr
Ta/NdFeB(540nm)/Ta single layer and multilayer amount of about 2.02 at.% is quite large, it may induce the
Ta/NdFeB(180nm)/Fe(2nm)]x3/Ta and Ta/[NdFeBZr formation of Fe2Zr additional phase. The average crystalline
(2.02at.%)(180nm)/Fe(2nm)]x3 /Ta thin films annealed size of grains of soft magnetic phases for
at650oC for 20 minutes. As compared to the Ta(20nm)/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta(40n
Ta/NdFeB(540nm)/Ta single layer, for the multilayer m) films is: 18 nm for Fe3B and Fe2B; 20 nm for Fe2Zr. The
Ta/NdFeB(180nm)/Fe(2nm)]x3/Ta films there is a small average crystalline size of hard magnetic phase grains are:
increase in the coercivity of about 9.5%, while for the 54 nm for Ta/[NdFeB(540nm)/Ta thin film; 30 nm for
Ta/[NdFeBZr(2.02at.%)(180nm)/Fe(2nm)]x3/Ta films there Ta/[NdFeBZr(2.02at.%)(540nm)/Ta thin film; 23 nm for
is an important increase in coercive field of about 35.6% due Ta/[NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3/Ta thin film.
to the Zr addition and stratification effect using Fe films as The refinement of the grain size by using Zr as addition
spacer layer. element is used to enhance the exchange coupling between
Due to the diffusion process the multilayer structure is the hard and soft magnetic grains in multilayer
partially or totally destroyed and a mixture consisting of Ta/[Nd(Fe,Zr)B(180nm) /Fe(2nm)]x3/Ta thin films. Fig. 5
hard magnetic and soft magnetic phases is created in shows the δM plots for Ta/[NdFeB(180nm)/ Fe(2nm)]x3/Ta
different ratios depending on the thicknesses of the and Ta/[NdFeBZr(2.02at.%)(180nm)/ Fe(2nm)]x3/Ta thin
constituent layers and annealing temperatures. The X-ray films after annealing at 650οC for 20 min.
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
Fig. 4. The XRD patterns of NdFeB(540nm) (a), NdFeBZr(2.02at.%)
and Nd2(Fe,Zr)14B hard magnetic phases, and Fe3B, Fe2B
(540nm) (b) and [NdFeBZr (2.02at.%)(180nm)/Fe(2nm)]x3 (c) thin films.
and Fe2Zr soft magnetic phases. For Ta(20nm)/ [NdFeBZr
4 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/α-Fe magnets with Zr addition”,
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[2] 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.
[3] 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.
Fig.5. The δM plots for Ta/[NdFeB(180nm)/Fe(2nm)]x3/Ta and [4] Y. Q. Wu, D. H. Ping, X. Y. Xiong, and K. Hono, “Magnetic
Ta/[NdFeBZr(2.02at.%) (180nm)/Fe(2nm)]x3/Ta thin films. properties and microstructures of α-Fe/Nd2Fe14B nanocomposite
microalloyed with Zr”, J. Appl. Phys., 91, 2002, pp. 8174-8176.
[5] H.P. Klug, L.E. Alexander, in: Diffraction Procedures for
A positive δM is observed on the whole magnetic field Polycrystalline and Amorphous Materials, Wiley, New York, 1974,
range confirming the existence of ferromagnetic exchange 665.
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.

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