57

Fe Mössbauer spectroscopy study of the magnetic properties of R2Fe14B

compounds (R=Ce, Nd, Gd, Y)
H. M. van Noort, D. B. de Mooij, and K. H. J. Buschow

Citation: Journal of Applied Physics 57, 5414 (1985); doi: 10.1063/1.334865

View online: http://dx.doi.org/10.1063/1.334865
View Table of Contents: http://aip.scitation.org/toc/jap/57/12
Published by the American Institute of Physics
57Fe M()ssbauer spectroscopy study of the magnetuc properties of R2Fe14B
compounds (R = Ce, Nd, Gd, Y)
H. M. van Noort, D. B. de Mooij, and K. H. J. Buschow
Philips Research Laboratories, 5600 fA Eindhoven, The Netherlands

(Received 27 August 1984; accepted for publication 4 January 1985)

57Fe Mossbauer spectra were taken at 25 and 293 K on four representative specimens of
compounds of the series R 2 Fe l4 B (R = Ce, Nd, Gd, and V). In all these cases it proved possible to
analyze the spectra in terms of six subspectra associated with the six crystallographically
nonequivalent Fe sites in the tetragonal R 2 Fe l4 B unit ceIl. Assuming a linear relation between the
observed hyperfine fields and magnetic moments it follows from our analysis that, although the
average Fe moment in R 2 Fe l4 B is equal to that of a-Fe, there are Fe sites that give rise to moments
much higher and much lower than the average value of 2.2/-l B IFe.

I. INTRODUCTION ;. :v
.. ....
,...;t1;". :
, '
Recently ternary compounds of the compOSitIOn ' "
,1> ",
R 2 Fe 14B have attracted considerable interest owing to their ,,
large saturation magnetization and huge magnetocrystalline '"
anisotropy, which make them suitable for permanent mag-
"
net applications. 1 A determination of the crystal structure ,,
~++
was made for the Nd zFe 14 B 2 and the same crystal structure 0,
'. ~
was found to apply for the remainder of the R 2 Fe l4 B com-
pounds. 3 This crystal structure is of tetragonal symmetry
and its unit cell is composed of 56 Fe atoms residing at six
different sites. Measurements of magnetic properties at tem-
.....
0, I
..r;,
' 4. :
:t""'*
! + f: +\+
peratures equal to or higher than room temperature were ! • <;'
o I + !~
made on bulk material by Sagawa et al. I In a more detailed
... .
o ,

study also the low-temperature magnetic properties were de- o

'
termined as well, using field strengths up to 20 T. 3 It was , '
..
0,

derived from the latter measurements that the average Fe 0'

• 0'
moment in R 2 Fe l4 B compounds is fairly high and equals
that in a-Fe. In the present investigation we have used the
.
o·
57Fe Mossbauer effect as a local probe of the magnetic mo-
ments in order to determine to what extent the magnetic
• '0

moments of the Fe atoms at the various sites are different.

::
Four different compounds of R 2 Fe 14 B were selected for this
purpose: Y 2Fe14B, Nd 2 Fe I4 B, Gd 2 Fe I4 B, and Ce 1 Fe 14 B. The
R component is trivalent in the first three compounds, the "
:
only variable being the 4jspin, which is zero in Y 2 Fe 14 B, of 0," .'
moderate size in Nd 2 Fe ,4 B, and rather large in Gd 2 Fe ,4 B.
The R component is tetravalent in Ce2 Fe 14 B. 3 This latter
compound was included to reveal possible effects due to a
changed valence electron concentration.
...
II. EXPEIRIMENTAL PIROCEDURES AND IRESUlTS
'\
The alloys were prepared by arc melting in purified ar- , ,
"
gon gas from starting materials of 99.9% purity. Subse-
quently the aJ.loy buttons were wrapped in Ta foil and vacu- "
. '
um annealed at 900 ·C for two weeks. After arc melting the ":
samples were examined by means of x-ray diffraction (CuKa
radiation). The x-ray diagrams were found to be composed of
a single set oflines, all belonging to the tetragonal Nd 1 Fe l4 B
structure type. -5 o -5 mmlsec
The 57Fe Mossbauer spectra of several R 2 Fe l4 B com- FIG. 1. 57Fe Mbssbauer spectra obtained at 25 K for various ternary inter·
pounds were obtained at 25 and 293 K on a conventional metallic compounds of the type R 2Fe 14 B.

5414 J. Appl. Phys. 57 (12). 15 June 1985 0021 ·8979/85/1 25414·06$02.40 @ 1985 American Institute of Physics 5414
 f
• +
+
420 K
FIG. 2. "Fe Miissbauer spectrum
Ce,Fe'4B at 420 K.
of

+ +
+ +
+
\. .If
+ +
\~
-+t

-5 o +5 mm/sec

show that the presence of elemental Fe as an impurity phase

constant acceleration spectrometer. The source, 10 mCi
can be excluded. Another impurity phase that might inter-
57CO in Pd, was moved while the absorber was kept in a fixed
fere with the interpretation of the spectra is R 2Fe 17 • These
position. For Ce 2Fe I4 B, Mossbauer spectra were also taken
phases have Curie temperatures in the vicinity of room tem-
at 420 K, which is close to the Curie temperature of this
perature and for Ce 2 Fe 17 the value of Tc is even below room
compound. For obtaining the Mossbauer spectra a small
temperature. (Tc = 238 K.) In the room-temperature spec-
part of the samples R 2 Fe l4 B was pulverized. In order to re-
trum of Ce 2Fe l4 B the presence of some Ce2 Fe 17 would be
duce effects due to self-absorption as far as possible only a
revealed by the presence of some additional intensity near
thin layer of pulverized material was used as an absorber.
zero velocity when comparing with the low-temperature
The linewidth for all subspectra equals 0.33 mmls, which is
spectrum. From the absence of this additional intensity we
slightly larger than the 0.23 mmls obtained for our a-Fe
conclude that the phase Ce 2 Fe 17 is not present as an impurity
standard (30-,u-m-thick foil). This may be due to some self·
phase. Similar considerations hold for the other compounds
absorption of the R 2 Fe 14 B samples. On the other hand this
investigated.
larger linewidth may be an intrinsic effect. In favor of this
latter interpretation is the observation of a linewidth of only
0.26 mmls in a sample of Th 2 Fe l4 B prepared in a similar
iii. INTERPRETATION OF THE SPECTRA
way to the R 2 Fe l4 B samples mentioned above. (The crystal
structure of Th 2 Fe 14B is isotypic with that of the R 2 Fe 14 B Before attempting to interpret the spectra it is desirable
compounds. A report dealing with the description of its to give a brief account of the crystal structure of the R 2 Fe l4B
magnetic properties and 57Fe Mossbauer spectra is in pro- compounds. The unit cell of these compounds is tetragonal
gress.) (space group P 42/mmm, No. 136) and is composed of 56 Fe
The low-temperature Mossbauer spectra of the com- atoms distributed over six crystallographically nonequiva-
pounds investigated are shown in Fig. 1. The relative trans- lent Fe sites. 2 The preferred direction of magnetization is
mission for all these spectra is the same and equals 0.97 for parallel to the c axis in all of the compounds considered in
the line of highest intensity (see also Fig. 3). Visual inspection this investigation. 3 Crystallographic details regarding the six
of the spectra makes it clear that the spectra are composed of different Fe sites have been given in Table L The first column
several subspectra having strongly different hyperfine fields. lists the Wyckoff symbols corresponding to these sites and
From the position of the outermost lines one may also de- provides information on their relative number. The second
duce that there are Fe sites in R 2 Fe 14B for which the atomic column lists the number of Fe neighbors. The corresponding
moment exceeds that of elemental Fe. intervals of near-neighbor Fe-Fe distances are given in par-
No lines are found in aU the spectra at positions corre· entheses. The second and third columns list similar data re-
sponding to the Mossbauer spectrum of elemental Fe. For garding R atom and B atom neighbors, respectively. Based
Ce 2 Fe l4 B this follows more clearly from the Mossbauer on Goldschmidt radii the normal Fe-Fe, Fe-R, and Fe-B
spectrum recorded at 420 K. Since this is close to the Curie distances are equal to 0.248,0.304, and 0.20 nm, respective-
temperature (Tc = 425 K), almost all of the magnetic split- ly. Atoms located at distances to Fe, R, or B neighbors that
tings are seen in Fig. 2 to have become drastically reduced. are more than 25% off these values were not considered to be
These results are in keeping with the x-ray data in that they near neighbors.

5415 J. Appl. Phys., Vol. 57, No. 12, 15 June 1985 van Noort, de Mooii, and Buschow 5415
TABLE I. Crystallographic properties associated with the various Fe sites in the tetragonal R 2 Fe '4B unit cell. The numbers in parentheses indicate the ranges
of distances in which the various types of neighbor atoms are found.

Fe site Fe neighbors R neighbors B neighbors

8j2 12 (0.263-0.280 run) 2 (0.307-0.313 nm) 0

16k2 10 (0.239-0.266 nm) 2 (0.304--0.328 nm) 0
16k] 9 (0.247-0.276 run) 2 (0.31Onm) 1(0.218 nm)
8j, 9 (0.239--0.280 nm) 3 (0.327-0.313 nm) 0
4e 9 (0.251-0.279 run) 2 (0.322 nm) 2 (0.214nm)
4c 8 (0.250--0.258 nm) 4 (0.311-0.340 nm) 0

Guided by the results listed in Table I we fitted the
Mossbauer spectra observed with six different subspectra of
relative intensity ratios 8: 16: 16:8:4:4, assuming that the re-
coil free fraction for the various sites is the same. For this fit
we used a Lorentzian shape of the various lines of the sub-
spectra. It soon became evident that good fits for each ofthe
spectra could be obtained for more than one set ofhyperfine
parameters. In order to decide between the various possibili-
ties we applied the following additional constraints to the
fitting procedure:
(i) The set of effective hyperfine fields Bhf able to pro-
duce a good fit for the Nd 2 Fe l4 B spectrum had to lead to an
equally good fit for the spectra of the other R 2 Fe 14 B com-
pounds in which R is trivalent, without major changes in
these parameters. Only for the site having a relatively high R
coordination (site 4c, see below) a lower value for Bhf was
tolerated when the R component is nonmagnetic, as in the
compound Y2Fe14B. Also for the fitting of the Ce 2 Fe 14 B
spectrum somewhat lower values of Bhf were considered as
acceptable in view of the tetravalent character of Ceo
(ii) A description of the isomer shift in Fe-base metal
systems was recently given 4 in terms of the model of Mie-
dema and van der Woude. 5 In this model the IS (relative to
a-Fe) of a given Fe atom is detennined by the effective frac-
tional area of contact of the Fe atom with its dissimilar near-
est-neighbor atoms. This area of contact is bigger the larger
the cross-sectional area of the dissimilar neighbor atoms. In
view ofthe fact that V213 (V = atomic volume) is much larger
for the rare earths than for B, the changes in IS is the com-
pounds R 2 Fe 14 B relative to a-Fe are mainly due to the pres-
ence of the rare-earth component, although a quantitative
description seems not yet possible at the moment. Experi-
mentally as well as from model calculations it follows that
combination of Fe with R leads to changes ofIS in the nega-
tive direction. 4 This led us to assume another constraint,
namely that for the various Fe sites in R 2 Fe 14B the isomer
shift (relative to a-Fe) should satisfy the rdation IS<O.
(iii) In view of the similarity in crystal structure one does
not expect large differences in QS for comparable sites in the
spectra of the various R 2 Fe 14 B compounds considered.
A representative example of a fit satisfying the require-
ments mentioned above is shown in Fig. 3. The three rel-
evant hyperfine parameters (effective hyperfine field Bhf , iso-
mer shift IS, and quadrupoJ.e splitting QS) corresponding to

I ISi2
---,I--,-----,--------.------,!16k
r-I

Il I
I Si 1
4c
.-----,------.----~----~--~~I 4e
1-0
FIG. 3. 57Fe Mossbauer spectrum of
1.00
Nd 2 Fe,.B at 25 K and correspond-
ing fit (full line through the data
points).

relative
transmission

0.97

-5 o +5 mm/sec

5416 J. Appl. Phys .• Vol. 57, No. 12, 15 June 1985 van Noort, de Mooij, and Buschow 5416
TABLE II. Hyperfine parameters (effective hyperfine field Bh ,; isomer shift relative to a-Fe at 300 K, IS; quadrupole splitting, QS) associated with the
different Fe sites in R2Fe'4B, obtained by fitting the 25-K Mossbauer spectra. The accuracy of the data listed equals ± 0.2 T for Dh , and ± 0.03 mmls for IS
andQS.

D h , (T) IS (mm/s) QS(mm/s)

Site Nd Gd Y Ce Nd Gd Y Ce Nd Gd Y Ce

8j2 40.0 37.8 38.1 36.4 0.0 0.0 0.0 0.0 0.3 0.2 0.3 0.3
16k 2 35.7 34.8 34.3 32.7 -0.2 -0.2 -0.2 -0.2 0.1 0.1 0.1 0.1
16k, 33.7 32.7 32.9 30.7 -0.1 -0.1 -0.1 -0.1 0.2 0.2 0.1 0.1
8j, 32.5 31.9 31.1 28.8 -0.1 -0.0 -0.1 -0.1 0.2 0.2 0.1 0.1
4e 32.7 32.3 30.1 28.6 -0.2 -0.3 -0.1 -0.2 0.0 0.0 0.0 0.1
4c 31.2 33.0 18.4 17.9 -0.2 -0.2 -0.0 -0.0 -0.3 - 0.4 -0.3 -0.3

those fits have been listed in Table II. The errors involved in (4e). However, if the R component has a magnetic moment of
the fitting procedure are ± 0.03 mmis for IS and QS and its own, the 4fspin may enhance the 3d moment of neighbor-
± 0.2 T for B hf . ing Fe atoms. In addition one may expect there to be a trans-
Since there are two subspectra of relative intensity 8 we ferred hyperfine field contribution arising primarily through
had to make a choice as to which of these two subspectra s-conduction electron polarization. It follows from these
would correspond to sites 8il and 8i2' respectively. In the considerations that for the site with the higher R coordina-
data listed in Table II we have assigned the subspectrum tion one expects a stronger dependence on the R component
with the higher hyperfine field to the 8i2 site. This assign- in the sense that the hyperfine fields decrease in the order
ment is based on the larger number of Fe neighbors for the R = Gd, Nd, Y, Ceo The last two rare-earth atoms are non-
8i2 site than for the 8il site (see Table I). magnetic. Since Ce is tetravalent it may be expected to lower
The fact that both R atoms and B atoms tend to lower the Fe moment more effectively than Y. Inspection of the
the magnetic moment of neighboring Fe atoms has also been results shown in Fig. 4 suggests that the dependence on the R
used to make the assignment of the two subspectra with rel- component is stronger in the lower of the two broken lines.
tive intensity 16, the higher hyperfine field corresponding to For this reason we have assigned the subspectra correspond-
the higher Fe coordination. ing to this line to the 4c site. The fact that the hyperfine fields
In order to make the assignment for the two subspectra of the 4c sites are generally lower than that of the 4e site is in
of the lowest intensity we have plotted the various hyperfine agreement with the slightly lower Fe coordination of the
fields versus R component in Fig. 4. In the first place we note former site compared with that of the latter (see Table I).
that it is difficult to decide between the moment-reducing In this point it is desirable to investigate whether the
effect of 4R neighbors (4c) or 2R neighbors and 2B neighbors differences in Bhf observed for different crystallographic Fe

40
8j2

;::-----i-\\ . .~:-------16k2
FIG. 4. Variation of the absolute value of the
effective hyperfine fields (25 KI and the corre-
sponding Fe moments of the different Fe sites
" ----- __ •• 16k, in R2Fe'4B when R is varied. A correction of
30 . . _-.-._------- -- :!, 2 the IB..,. I values due to dipolar fields will affect
I- primarily the position of the 4c data points,
......
IX)
-G)
\
\ '.
'.
which will be shifted in downward direction
by about I T. For the other sites the dipolar
corrections are negligibly small (see main
" '. text).
,
20 \.
..... ---- .. ~- ..... ---.. -.. -* 4c

25 K

Nd Gd y Ce

5417 J. Appl. Phys., Vol. 57, No. 12, 15 June 1985 van Noort, de Mooij, and Buschow 5417
sites might partially originate from differences in dipolar
fields experienced by the Fe nuclei present at these sites. ... Sc-Fe -/
Dipolar fields for the various Fe sites in Nd 2 Fe l4 B and
Y2Fel4B were calculated on the assumption of point dipoles • V-Fe /*
oriented along the c directions4 (within a sphere of 4O-A radi- 30
... Th-Fe •
us) using Fe moments equal to 21lB' On the basis of magnetic
measurements a moment equal to 21l B was also adopted for • Lu-Fe
Nd. 4 Numerical values for the dipolar field in Nd 2 Fe l4 B are
- 0.33 T (8jl)' - 0.41 T (8j2)' - 0.06 T (16k l), - 0.11 T
(16k 2 ), - 0.03 T (4e), and 0.56 (4c). Also at the Fe sites in
Y zFe l4 B the dipolar fields are small and range from - 0.03
T (16k l) to 0.78 T (4c). Excepting the 4c sites, the corrections
of Bbf due to dipolar contributions are not much larger than 20
the experimental error ( ± 0.2 T) and in some cases are
smaller than this. But even for the 4c sites the corrections are
small compared to the large differences in Bbf found for the
4c sites and, for instance, the 8jz sites.
Finally we comment on the fact that in all the Moss-
bauer spectra analyzed we had to assume that about 2% of
the Fe is present in the form of a paramagnetic compound
(Bbf = 0). This is indicated in Fig. 3 by means of a small
iOL-----~----~------~----~
doublet near zero velocity. We believe that the origin of this 2.0
is a trace of a ternary intermetallic compound of relatively
low Fe content which has escaped detection by x-ray diffrac- FIG. 5. Average hyperfine fields in various Fe-base interrnetallics vs the
tion. corresponding average Fe moments. The data obtained in the course of the
present investigation on Y 2Fel4B are represented by a star; the data point
corresponding to a-Fe is indicated by a full square. The full line passes
through the origin and represents a behavior where the average hyperfine
field values are proportional to the corresponding moment values.
IV. CONCLUSIONS
derived from the high-field magnetic measurements men-
In a previous study of the magnetic properties of
tioned above. The same factor has been used to calibrate the
R 2 Fe l4 B compounds it was derived from high-field magneti-
right-hand scale in Fig. 4. Under the assumption that for all
zation measurements that the average Fe moment in these
the R 2 Fe l4 B compounds in Fig. 4 a linear relation exists
compounds is equal to 2.2Il B IFe, which is similar to that between the observed hyperfine fields and the corresponding
found in a-Fe. 3 The hyperfine field data obtained in the
magnetic moments, our results would show that the magnet-
course of the present investigation suggest that there may be
ic moments of the R 2Fe l4 B compounds are composed of con-
significant differences in Fe moment associate<! with the Fe
tributions due to different sites where the Fe atoms have
atoms residing at different sites. In order to transform the
magnetic moments that are considerably above (8j2) and be-
values found for Bbf into values of the corresponding FI!
low (4c) the atomic moments found in a-Fe. It would also
moments (flFe) a relation between Bbf and IlFe is required. It
follow from the analysis presented above that the magnetic
was already suggested by Gubbens et al. I> that the average
moments are relatively insensitive to moment enhancement
hyperfine field is proportional to the average Fe moments in
due to the rare-earth spin, the Fe atoms occupying the 4c and
intermetallic compounds in which Fe is combined with Y.
4e site forming an exception.
We checked on the validity of this relation by including com-
pounds in which Fe is combined with other metals of the
third row of the periodic table. Values of the average hyper-
fine field and the corresponding Fe moment were derived ACKNOWLEDGMENT
from data reported in the literature. 7- 12 It can be seen from We wish to thank R. P. van Stapele for his stimulating
the data plotted in Fig. 5 that the proportionality mentioned interest and fruitful discussions.
is comparatively general and includes compounds with
widely different crystal structures such as the cubic Laves
phases and the hexagonal PuNi 3 and Th 2 Ni 17-type com-
pounds. The results in Fig. 5 suggest that the hyperfine fields 1M. Sagawa, S. Fujimura, M. Togawa, H. Yamamoto, and Y. Matsuura, J.
App!. Phys. 55, 2083 (1983).
in these materials are mainly determined by the core polar- 2J. Herbst, J. Croat, F. E. Pinkerton, and W. Yellon. Phys. Rev. B 29, 4176
ization and that the transferred hyperfine fields do not play (1984).
an important role. The conversion factor corresponding to 3S. Sinnema, R. J. Radwanski,J. J. M. Franse, D. B. de Mooij. and K. H. J.
the straight line in Fig. 5 is equal to 14.8 Tills. In fact, a Buschow, J. Magn. Magn. Mater. 44, 333 (1984).
'A. M. van der Kraan and K. H. J. Buschow, Phys. Rev. 27, 2693 (1983).
factor equal to 14.8 T/IlB is obtained when the value 32.5 T 'A. R. Miedema and F. van der Woude, Physica l00B, 145 (1980).
found by us for the weighted mean of the Fe hyperfine field "P. C. M. Gubbens, J. H. J. van Apeldoom, A. M. van der Kraan, and K. H.
in Y 2Fe l4 B is used in conjunction with the value 2.21l BlFe J. Buschow, J. Phys. F 4,921 (1.974).

5418 J. Appl. Phys., Vol. 57, No. 12, 15 June 1985 van Noort, de Mooij. and Buschow 5418
7A. M. vander Kraan,J. N. J. van derVelden, J. H. F. van Apeldoorn, P. C.
M. Gubbens, and K. H. J. Buschow, Phys. Status Solidi A 35, 137 (1976).
RK. H. J. Buschow, J. AppJ. Phys. 42,3433 (1971).
?n. Niarchos. P. J. Viccaro, G. K. Shenoy, B. D. Dunlap and A. T. Aldred,
Proceedings of the 5th International Conference Hyperfine Interactions,
Berlin, July (1980) (unpublished).
5419 J. Appl. Phys., Vol. 57, No. 12, 15 June 1985
lOS. Blow, 1. Phys. C3, 158 (1972); P. C. M. Gubbens, A. M. van der Kraan.
and K. H. 1. Buschow, J. Appl. Phys. 56,2547 (1984).
lip. C. M. Gubbens, A. M. van der Kraan, and K. H. 1. Buschow, Solid
State Commun. 37, 635 (1981).
12K. H. J. Buschow, P. H. Smit, and R. M. van Essen, J. Magn. Magn.
Mater. 15·18, 1261 (1980).
van Noort, de Mooij, and Buschow 5419