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Acta Materialia 59 (2011) 7768–7775


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Microstructure optimization to achieve high coercivity in


anisotropic Nd–Fe–B thin films
W.B. Cui, Y.K. Takahashi, K. Hono ⇑
National Institute for Material Science, Tsukuba 305-0047, Japan

Received 1 August 2011; received in revised form 3 September 2011; accepted 4 September 2011
Available online 20 October 2011

Abstract

A high coercivity of 2.35 MA m1 (29.5 kOe) is demonstrated using perpendicular anisotropy Nd–Fe–B films. Single layer columnar
grown Nd–Fe–B thin films with a coercivity comparable with that of sintered magnets (1.11 MA m1, 14.0 kOe) were used as the starting
film. The coercivity was doubled by annealing films capped with Nd, Nd/Cu, and Nd/Ag layers. Transmission electron microscopy indi-
cated that the Nd2Fe14B columnar grains were isolated by a Nd-rich grain boundary phase formed by diffusion of the capped layers into
the grain boundaries of the polycrystalline Nd–Fe–B films. The temperature dependence of coercivity was lower than that of commercial
sintered magnets. The coercivity of the Nd/Cu diffusion processed sample at 473 K was 0.979 MA m1 (12.3 kOe), which is higher than
that of Nd10Dy4Fe80B6 sintered magnets.
Ó 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Permanent magnets; Nd–Fe–B thin films; Coercivity; Transmission electron microscopy

1. Introduction earth elements there is a need to develop high coercivity


Dy-free Nd–Fe–B sintered magnets.
Nd–Fe–B-based sintered magnets show the highest max- One well-known approach to increasing the Hcj of sin-
imum energy product BHmax among all permanent mag- tered magnets is to refine the crystal grain size of the
nets and are widely used in applications where high Nd2Fe14B phase [1,2]. However, Nothnagel reported that
BHmax are required. The relatively low coercivity (iHc) of there is a critical grain size of around 3 lm at which Hcj
about 0.96 MA m1 (12 kOe) of Nd–Fe–B-based commer- decreases dramatically with further refinement of the grain
cial sintered magnets is a major practical obstacle for cer- size [2]. Li et al. reported that sintered magnets with a
tain applications, such as traction motors in (hybrid) decreased Hcj contain a large fraction of neodymium oxides
electric vehicles (HEV) and wind power generators. The in the so-called Nd-rich phases, including dhcp Nd, fcc
current solution is to partly substitute heavy rare earth ele- NdO and hcp Nd2O3 [3]. These reports suggest that refine-
ments such as Dy for Nd in Nd2Fe14B, thereby increasing ment of the crystal grain size is not sufficient to enhance
the room temperature coercivity to about 2.4 MA m1 Hcj. Since the crystal grains of sintered magnets are
(30 kOe) to suppress demagnetization at an operating strongly textured along the c-axis, which is an easy axis
temperature of 473 K. Since the partial substitution of for magnetization, high coercivity cannot be expected if
Dy for Nd increases the magneto-crystalline anisotropy the grain boundaries (GB) are simply structural boundaries
of Nd2Fe14B the coercivity of the Nd–Dy–Fe–B alloy that do not differ in chemistry. Hence, the chemistry of the
increases by a factor of 2–3 at the expense of BHmax. GB in sintered magnets has been of interest for many years
However, due to the scarcity and high cost of heavy rare since the first development of Nd–Fe–B sintered magnets
by Sagawa et al. in 1982 [4]. A high resolution back-scat-
⇑ Corresponding author. tered electron (BSE) scanning electron microscopy (SEM)
E-mail address: kazuhiro.hono@nims.go.jp (K. Hono). investigation by Vial et al. indicated that a continuous

1359-6454/$36.00 Ó 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2011.09.006
W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775 7769

GB layer was formed in post-sintering annealed commer- at 1.3 Pa. Nd15Fe75B10 single layer films of various thick-
cial magnets [5]. Recently the chemical composition of nesses were initially sputtered. Nd(20 nm), Nd(20 nm)/
the GB phase in sintered magnets has been investigated Cu(3 nm) (Nd70Cu30) and Nd(20 nm)/Ag(3 nm) (Nd80
more quantitatively using the three-dimensional atom Ag20) layers comparable to the eutectic compositions were
probe (3-DAP) technique [3]. The current understanding deposited onto the Nd15Fe75B10 base films. Hereafter these
is that the increase in Hcj on post-sintering annealing is samples are denoted Nd(t), Nd(t)/Nd, Nd(t)/Nd/Ag, Nd(t)/
due to the formation of thin Nd-rich amorphous GB layers Nd/Cu, respectively, where t denotes the thickness of the
as a result of partial melting of the Nd–Cu eutectic in the initial Nd–Fe–B thin film in nm. The substrate temperature
Nd-rich phase grains. This liquid Nd-rich phase is consid- was kept at 823 K during the sputtering process, and then
ered to infiltrate the GB and envelop the Nd2Fe14B grains, increased to 873 K for in-situ post-deposition annealing
which weakens intergrain exchange coupling. Based on this for 30 min. The hysteresis loops along the perpendicular
assumption, Sepehri-Amin et al. demonstrated that the and parallel directions were measured using SQUID vibrat-
coercivity of an hydrogenation disproportionation desorp- ing sample magnetometer (VSM) with a maximum applied
tion recombination (HDDR) powder can be enhanced to field of 7 T. The constituent phases were characterized by
about 1.6 MA m1 (20 kOe) using the GB diffusion of X-ray diffraction (XRD) using CuKa radiation. The micro-
Nd–Cu hypereutectic alloy powders [6]. structures were characterized by transmission electron
The microstructure of thin films can be controlled more microscopy (TEM). The energy filtered TEM images were
easily than that of sintered magnets. Highly anisotropic acquired using a Gatan Tridium energy filter in a Technai
Nd–Fe–B thin films with columnar grains can be achieved G2 F30 microscope using the Nd N edge (118 eV), Cu L
by depositing the films directly onto heated substrates [7] or edge (931 eV) and Ag M edge (367 eV).
depositing them at low temperature followed by post-depo-
sition annealing [8–13]. By directly depositing the films 3. Results
onto heated substrates systematic investigations were car-
ried out on the effect of buffer layers (Cr, Mo, Nb, Ta, Ti 3.1. Magnetic properties of single layer Nd–Fe–B films
and V), and a coercivity of 1.6 MA m1 (20 kOe) was
reported in thin films with Nb buffer layers [7]. Nd–Fe–B As a model system, single layer Nd15Fe75B10 films of var-
films interbeded with M layers (M = Nb [10], Ta [11], ious thicknesses were prepared. Fig. 1 shows the XRD pat-
NdCu [12], or W [13]), i.e. [NdFeB/M]n thin films, have terns of the films with thicknesses of t = 30, 50, 80 and
also been reported. The coercivities of these films were only 100 nm. The major observed peaks are 00l, indicating that
around 1.6 MA m1 (20 kOe). More recently Dempsey the films grew with a strong (001) texture. The magnetiza-
et al. reported a coercivity of 2.2 MA m1 (27 kOe) in sput- tion curves for the single layer films with t = 30, 50, 80
ter deposited Nd–Fe–B thick films (Dempsey NM, Wood- and 100 nm are shown in Fig. 2. Perpendicular and in-plane
cock TG, Sepehri-Amin H, Zhang Y, Kennedy H, Givord magnetization curves of the films indicate that all the films
D, Hono K, Gutfleisch O, unpublished). However, the have perpendicular anisotropy with iHc = 1.11 MA m1
structure–coercivity relationships in these films have not (14 kOe) for t = 80 nm. This value is comparable with
been investigated thoroughly. The aim of this work is to
explore how high coercivity can be obtained by optimizing
the microstructure of anisotropic Nd–Fe–B polycrystals
without using Dy. We used thin films as a model case for
sintered magnets because the microstructure of the films
can be more readily controlled. The microstructure–coer-
civity relationships are analyzed using the micromagnetic
model. Based on the results we discuss the optimum micro-
structure to achieve the highest coercivity in Nd–Fe–B iso-
tropic poloycrystalline magnets without using Dy.

2. Experimental procedure

All Nd–Fe–B films were prepared by magnetron sputter-


ing onto thermally oxidized silicon substrates with a Ta
underlayer. A Ta underlayer of 50 nm and a coverlayer of
10 nm were sputtered at room temperature to suppress oxi-
dation of the Nd–Fe–B films and to align the c-axis of the
Nd2Fe14B grains perpendicular to the film planes. An alloy
target with a composition of Nd15Fe75B10 was used to grow
the Nd–Fe–B layers. The base pressure was better than 10 Fig. 1. X-ray diffraction of Nd15Fe75B10(t nm) (t = 100, 80, 50, and
6
Pa, and the Ar pressure for sputtering was maintained 30 nm) single layer thin films.
7770 W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775

(27.1 kOe) by the Nd diffusion process. The coercivity


increases slightly on Cu addition for all the Nd–Fe–B films,
with the highest coercivity of 2.16 MA m1 (27.5 kOe)
obtained for Nd15Fe75B10(80 nm)/Nd/Cu. Minor Ag addi-
tion can enhance the coercivity even further. In particular,
the highest coercivity obtained by the diffusion process is
2.35 MA m1 (29.5 kOe) in the Nd15Fe75B10(50 nm)/Nd/
Ag thin film.
Magnetic hysteresis loops of diffusion processed Nd15
Fe75B10(80 nm)/Nd, Nd15Fe75B10(80 nm)/Nd/Cu, Nd15
Fe75B10(80 nm)/Nd/Ag and Nd15Fe75B10(50 nm)/Nd/Ag
films are compared in Fig. 4. Good squareness and a high
remanence ratio are shown in the perpendicular direction
to the film planes. The in-plane magnetization curves are
Fig. 2. Perpendicular (perp) and in-plane or parallel (para) magnetic
hysteresis loops of Nd15Fe75B10(t nm) (t = 100 (a), 80 (b), 50 (c), and
very difficult to saturate. Compared with Fig. 2b, the perpen-
30 nm (d)) single layer thin films. dicular coercivities are larger, indicating that intergrain
exchange coupling is reduced in the diffusion processed
films.
the coercivity expected from a sintered magnet with a grain
3.3. Microstructure of diffusion processed films
size of about 3.5 lm [14]. The highest perpendicular anisot-
ropy can be seen in the Nd–Fe–B single layer film with
Fig. 5 compares the cross-sectional microstructures of
t = 100 nm, with a slightly reduced coercivity, indicating
the Nd15Fe75B10(80 nm), Nd15Fe75B10(80 nm)/Nd, Nd15
columnar growth of the Nd2Fe14B grains. The thickness
Fe75B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/Nd/Ag
dependence of the single layer Nd15Fe75B10 films is summa-
thin films with Nd, Cu and Ag jump ratio images. The single
rized in Fig. 3 by black squares.
layer film (Fig. 5a) and the Nd diffusion processed thin film
(Fig. 5b) show a granular microstructure comprising
3.2. Magnetic properties of diffusion processed films
Nd2Fe14B and Nd-rich phase grains. The Nd-rich phase
grains appear as a bright contrast in the Nd jump ratio
On annealing the films capped with Nd, Nd/Cu and Nd/
image. Due to Nd/Cu and Nd/Ag diffusion the Nd2Fe14B
Ag layers at 873 K for 30 min Nd–Cu and N–Ag eutectic
grains show a columnar shape separated by a bright Nd-
alloys melt and diffuse into the magnetic Nd–Fe–B layer
rich GB phase. This suggests that recrystallization occurs
along the grain boundaries to form Nd-enriched layers
among the Nd2Fe14B grains. The coercivities are signifi-
cantly enhanced by more than 0.80 MA m1 (10 kOe)
by this diffusion process. For t = 100 nm the coercivity is
enhanced from 1.08 (13.5) to 1.9 MA m1 (24 kOe), as
shown in Fig. 3. When the Nd15Fe75B10 layer is decreased
to 80 nm the coercivity reaches a maximum of 2.16 MA m1

Fig. 3. Coercivities of Nd15Fe75B10(t nm), Nd15Fe75B10(t nm)/Nd(20 nm), Fig. 4. Perpendicular (perp) and in-plane or parallel (para) magnetic
Nd15Fe75B10(t nm)/Nd(20 nm)/Cu(3 nm) and Nd15Fe75B10(t nm)/ hysteresis loops of (a) Nd15Fe75B10(80 nm)/Nd(20 nm), (b) Nd15Fe75-
Nd(20 nm)/Ag(3 nm) thin films as a function of the thickness of the base B10(80 nm)/Nd(20 nm)/Cu(3 nm), (c) Nd15Fe75B10(80 nm)/Nd(20 nm)/
films. Ag(3 nm) and (d) Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm) thin films.
W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775 7771

Fig. 5. Cross-sectional TEM images of (a) Nd15Fe75B10(80 nm), (b) Nd15Fe75B10(80 nm)/Nd(20 nm), (c) Nd15Fe75B10(80 nm)/Nd(20 nm)/Cu(3 nm) (d)
and Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm) thin films and corresponding Nd, Cu and Ag jump ratio images.

in the Nd/Cu and Nd/Ag capped films. The formation of region are brighter than in the Nd2Fe14B phase, showing
columnar Nd2Fe14B grains isolated by a Nd-rich GB phase that Cu and Ag are not dissolved in the Nd2Fe14B phase.
appears to result in enhanced coercivity. Cu and Ag are To check the possibility of Ag and Cu being distributed in
also enriched in the GB region, as indicated in the Cu and the Nd2Fe14B phase the temperature dependence of magne-
Ag jump ratio images. Fig. 6 shows in-plane TEM images tization was measured for the Nd15Fe75B10(80 nm)/Nd,
of the Nd15Fe75B10(80 nm), Nd15Fe75B10(80 nm)/Nd, Nd15Fe75B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/Nd/
Nd15Fe75B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/Nd/ Ag films. The results are shown in Fig. 8. Humps due to spin
Ag thin films along with the Nd, Cu and Ag jump ratio reorientation are shown, indicated by the arrows. Spin reori-
images. Round or equiaxed Nd2Fe14B phase grains with entation is an intrinsic feature of the Nd2Fe14B phase that
an average diameter of about 40 nm can be observed in occurs due to a decrease in the first order anisotropy con-
Fig. 6a. The Nd jump ratio image shows that the Nd-rich stant (K1) with decreasing temperature and tilting of the easy
phase forms equiaxed grains along with Nd2Fe14B grains. magnetization direction from the c-axis to a cone configura-
The low coercivity can be attributed to the Nd2Fe14B grains tion with a cone angle of 30° at 4.2 K [15]. Fig. 8 shows the
being in contact with each other, as shown in Fig. 2. The spin reorientation at 135 K in the Nd15Fe75B10(80 nm)/Nd
microstructural features are similar to those of sintered film as previously reported [15]. The spin reorientation tem-
magnets [3]. After Nd diffusion the equiaxed Nd2Fe14B perature TSR increases only slightly to 137 K due to Ag dif-
phase grains are enveloped by the Nd-rich phase and the fusion and to 144 K on Cu addition. The slight shift in TSR
grains appear to be separated from one another. Compared indicates that there is only a slight dissolution of Ag and
with the single layer film, the Nd-rich phase appears to Cu in the Nd2Fe14B phase, which is in agreement with the
envelop the Nd2Fe14B grains. Many Nd2Fe14B phase grains corresponding jump ratio images.
are isolated by the Nd-rich phase, as indicated in the Nd
jump ratio image in Fig. 4b. The grain size is estimated to 3.4. Temperature dependence of coercivity
be about 40 nm, which is nearly the same size as that in
the single layer film. After Nd/Cu or Nd/Ag diffusion the Since high coercivities were obtained for diffusion
grain sizes had grown to about 90 and 70 nm, respectively. processed Nd–Fe–B thin films it is worth investigating how
However, some large rectangular grains of more than a a high coercivity can be sustained at elevated temperatures.
100 nm coexist with small grains of 20–30 nm. The size The temperature coefficient of coercivity b describes the
distribution in the NdCu and NdAg diffusion processed thermal stability of coercivity, which is defined as
thin films is not as homogeneous as that in the Nd diffusion b = [iHc(T)  iHc(300)]/[iHc(300)  (T  300)], where,
processed thin films. The Nd2Fe14B phase grains are dis- H
i c (300) and H
i c(T) represent the coercivity at 300 K (room
persed in a Nd-rich phase matrix, resulting in a higher temperature) and temperature T, respectively. The
coercivity. coercivities are measured from 300 to 573 K. Fig. 9 compares
Fig. 7 shows high magnification TEM images of Nd/Cu the temperature dependence of coercivity in the
and Nd/Ag diffusion processed thin films. From the Nd Nd15Fe75B10(80 nm)/Nd, Nd15Fe75B10(80 nm)/Nd/Cu and
jump ratio it can be observed that the Nd-rich phase infil- Nd15Fe75B10(50 nm)/Nd/Ag thin films. As a reference, the
trates into the GB and envelops the Nd2Fe14B phase grains, temperature dependence of a Nd10Dy4Fe80B6-based com-
seen as white regions in Fig. 7b and e. Cu and Ag are also mercial magnet with iHc = 2.37 MA m1 (29.8 kOe) and
enriched in the same region, as shown by their jump ratio BHmax = 250 kJ m3 and a Nd14Fe80B6 commercial magnet
images (Fig. 7c and f). The Cu and Ag contrasts in the GB with iHc = 0.88 MA m1 (11 kOe) and BHmax = 432 kJ m3
7772 W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775

Fig. 6. In-plane energy filtered TEM images of (a) Nd15Fe75B10(80 nm), (b) Nd15Fe75B10(80 nm)/Nd(20 nm), (c) Nd15Fe75B10(80 nm)/Nd(20 nm)/
Cu(3 nm) and (d) Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm) thin films. Zero loss images and Nd, Cu and Ag jump ratio images are shown.

are also shown (http://www.hitachi-metals.co.jp/prod/ magnets [15]. This means that the temperature dependence
prod03/pdf/nmx.pdf). The coercivities decrease in all films of coercivity in diffusion processed thin films is significantly
with increasing temperature. The coercivities of the thin films lower than that of commercial magnets. Moreover, at 473 K,
decrease more slowly than those of commercial sintered which is the working temperature of the traction motors of
magnets with temperature. The temperature coefficient of HEV, the coercivities of the Nd15Fe75B10(80 nm)/Nd/Cu
the coercivity of the Nd/Cu diffusion processed thin film is and Nd15Fe75B10(50 nm)/Nd/Ag thin films are 0.96 (12.1)
lower than that of the Nd and Nd/Ag diffusion processed and 0.92 MA m1 (11.6 kOe), respectively, which are much
thin films. The value of b obtained for the Nd/Cu diffusion higher than those of Nd-Dy-Fe-B sintered magnets. The high
processed thin film (0.32% K1) is also lower than that coercivities of the Nd/Cu and Nd/Ag diffusion processed
for the Nd diffusion processed thin film (0.40% K1, 300– thin films are able to satisfy the requirements for application
573 K) and for the Nd/Ag diffusion processed thin film in traction motors for HEV, indicating beneficial effects of a
(0.35% K1, 300–473 K). b is usually between 0.6 and magnetically isolated nanograin structure for high tempera-
0.45% K1 (300–433 K) in sintered magnets or hot pressed ture applications.
W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775 7773

Fig. 7. High magnification in-plane (a) zero loss image, (b) Nd jump ratio image, and (c) Ag jump ratio image for Nd15Fe75B10(80 nm)/Nd(20 nm)/
Ag(3 nm) and (d) zero loss image, (e) Nd jump ratio image and (f) Cu jump ratio image for Nd15Fe75B10(50 nm)/Nd(20 nm)/Cu(3 nm) thin films.

Fig. 8. Comparisons of M–T curves for Nd15Fe75B10(80 nm)/Nd(20 nm), Fig. 10. Initial magnetization curves of Nd15Fe75B10(80 nm), Nd15Fe75-
Nd15Fe75B10(80 nm)/Nd(20 nm)/Cu(3 nm) and Nd15Fe75B10(50 nm)/ B10(80 nm)/Nd(20 nm), Nd15Fe75B10 (80 nm)/Nd(20 nm)/Cu(3 nm) and
Nd(20 nm)/Ag(3 nm) thin films. Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm) thin films.

4. Discussion

A high coercivity of 2.35 MA m1 (29.5 kOe) was found


for Nd–Fe–B thin films, in which Nd2Fe14B grains with an
average grain size of 70 nm were isolated by a Nd-rich
phase. It would be interesting to investigate the underlying
coercivity mechanism as a model for achieving high coer-
civity in Nd–Fe–B sintered magnets. Many approaches
have been applied to investigate the coercivity mechanism,
such as initial magnetization, minor hysteresis loops, rem-
anence curves [16–18] and the micromagnetic model [19].
Fig. 10 shows the initial magnetization curves for the
Nd15Fe75B10(80 nm), Nd15Fe75B10(80 nm)/Nd, Nd15Fe75
Fig. 9. Temperature dependence of the coercivities of Nd15Fe75- B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/Nd/Ag thin
B10(80 nm)/Nd(20 nm), Nd15Fe75B10(80 nm)/Nd(20 nm)/Cu(3 nm) and
Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm) thin films. As a reference, the
films. The slope of the initial magnetization curve of the
temperature dependence of the coercivities of Nd10Dy4Fe80B6 and single layer film is steep and saturates at 0.60 MA m1
Nd14Fe80B6 commercial sintered magnets are also shown. (7.5 kOe), which is close to that of a typical sintered magnet
7774 W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775

[20]. However, the saturation field for the Nd, Nd/Cu and
Nd/Ag diffusion processed samples increased to
1.5 MA m1, indicating that magnetization reversal is not
only by magnetic domain wall displacement, but also by
the moment rotation of small isolated grains of approxi-
mately 40–90 nm, as shown in Fig. 6. Note that the single
domain size of the Nd2Fe14B phase is approximately
200 nm, therefore, all the grains in the thin films are smaller
than the single domain size.
Minor hysteresis loops measure the coercivity after
applying different magnetic fields. Fig. 11 compares the
ambient coercivity as a function of the external maximum
applied field in the Nd15Fe75B10(80 nm)/Nd, Fig. 11. Ambient coercivity dependence on the external maximum applied
Nd15Fe75B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/Nd/ field in Nd15Fe75B10(80 nm), Nd15Fe75B10(80 nm)/Nd(20 nm), Nd15Fe75-
Ag thin films with that in the Nd15Fe75B10(80 nm) single B10(80 nm)/Nd(20 nm)/Cu(3 nm) and Nd15Fe75B10(50 nm)/Nd(20 nm)/
layer thin film. Coercivity increases linearly with increasing Ag(3 nm) thin films.
external applied field and then saturates at an external field
of 1.5 MA m1 for the single layer film. However, in the
diffusion processed thin films magnetization saturates at
3 MA m1, which is independent of the type of capping
layer. Thus, saturation is more difficult in the diffusion pro-
cessed thin films. This difference observed in the minor hys-
teresis loops indicates that the mechanism of coercivity in
single layer films is different from that in diffusion pro-
cessed thin films.
The micromagnetic model was applied to further clarify
such differences and the mechanisms of coercivity in these
thin films. Coercivity has the following relationship from
a micromagnetic point of view [19]:
iH c ¼ aH A  N eff M s ð1Þ
Fig. 12. The dependence of iHc/Ms on HA/Ms in Nd15Fe75B10(80 nm),
where HA is the anisotropy field, HA = 2K1/Ms, For Nd15Fe75B10(80 nm)/Nd(20 nm), Nd15Fe75B10(80 nm)/Nd(20 nm)/Cu(3 nm)
Nd2Fe14B ambient HA  5.89 MA m1 (74 kOe), which is and Nd15Fe75B10(50 nm)/Nd(20 nm)/Ag(3 nm)/Ta thin films. The inset
the ideal coercivity for the coherent rotation of magneti- shows the temperature dependence of saturation magnetization of these
cally isolated single domain particles. Ms is the saturation four thin films.
magnetization and a and Neff are microstructure-dependent
parameters. The parameter a describes the reduction in the value increases to 0.4 for the Nd, Nd/Cu and Nd/Ag diffu-
anisotropy field due to the presence of crystallographic de- sion processed films. Since the parameter describes the
fects in the magnetically inhomogeneous region (aK) on the reduction in anisotropy field due to the presence of crystal-
grain surface and misalignment of the grains (au). The lographic defects and magnetically inhomogeneous re-
parameter Neff describes the local demagnetization field, gions, e.g. GB and other interfaces, such an increment in
which assists nucleation of the reversed domain under the a indicates that magnetic anisotropy can be restored at
action of the applied inverse field. The value of coercivity interfaces by the Nd, Nd/Cu and Nd/Ag diffusion process.
iHc strongly depends on the anisotropy and the demagneti- Neff is correspondingly decreased by the diffusion process,
zation field. For Nd2Fe14B, since high coercivity magnets indicating a reduction in the self-demagnetization field of
are designed for motor working temperatures of around the particles.
473 K, the ideal nucleation field HA would be HA = 2K1/ Fig. 13 summarizes the dependence of the structure
Ms. The temperature dependence of K1 is obtained from parameters a and Neff on the Nd–Fe–B thickness in the
Durst and Kronmüller [21]. Fig. 12 shows the dependence Nd15Fe75B10(t), Nd15Fe75B10(t)/Nd, Nd15Fe75B10(t)/Nd/
of iHc/Ms on HA/Ms for the single layer and diffusion pro- Cu and Nd15Fe75B10(t)/Nd/Ag thin films. Compared with
cessed films, i.e. Nd15Fe75B10(80 nm), Nd15Fe75B10(80 nm)/ the diffusion processed thin films the parameter a for the
Nd, Nd15Fe75B10(80 nm)/Nd/Cu and Nd15Fe75B10(50 nm)/ Nd2Fe14B single layer films of various thicknesses are less
Nd/Ag films. The experimentally measured temperature than those in the diffusion processed thin films. Since we
dependence of Ms of the films is also shown in the inset know that a describes the reduction in local magneto-crys-
to Fig. 12. The micromagnetic parameters a and Neff were talline anisotropy due to crystallographic defects near the
fitted by the least squares method and are indicated in the GB, such a low a in single layer films indicates the presence
figure. Note that a for the single layer film is 0.26, while the of locally low magneto-crystalline regions at Nd2Fe14B
W.B. Cui et al. / Acta Materialia 59 (2011) 7768–7775 7775

TEM images indicate that Nd2Fe14B grains are isolated


by a Nd-rich GB phase after the diffusion process. After
Nd/Cu and Nd/Ag diffusion Cu and Ag are mainly distrib-
uted in the Nd-rich GB regions, and the coercivity–temper-
ature coefficients are much better than those of commercial
magnets. The coercivities at 473 K of 0.98 MA m1
(12.3 kOe) in Nd/Cu and 0.92 MA m1 (11.6 kOe) in Nd/
Ag diffusion processed thin films are noteworthy. Micro-
magnetic analysis of the films before and after the diffusion
process indicated that the crystallographic defects causing
the local reduction in magneto-crystalline anisotropy were
significantly reduced, as suggested by the increase in a from
0.25 to 0.4, and the demagnetization effect Neff was also
decreased. This work suggests that if an ideal microstruc-
ture comprising magnetically isolated elongated grains of
a single domain size is realized in bulk magnets they will
exhibit a high coercivity and low temperature coefficient,
which is sufficient at an operating temperature of 473 K
without using Dy.

Acknowledgements

Fig. 13. The dependence of structural parameters (a) a and (b) Neff on the This work was supported by NEDO through the Rare
thickness of Nd15Fe75B10(t nm), Nd15Fe75B10(t nm)/Nd(20 nm), Nd15- Metal Substitute Materials Development Project on the
Fe75B10(t nm)/Nd(20 nm)/Cu(3 nm) and Nd15Fe75B10(t nm)/Nd(20 nm)/ “Development of technology for reducing dysprosium
Ag(3 nm) thin films. usage in a rare-earth magnet” and Toyota Motor Co. Ltd.

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model single layer strongly textured polycrystalline films.