VOLUME 33, NUMBER 13 PHYSICAL KE VIEW LETTERS 23 SEPTEMBER 1974

The authors are grateful to Professor V. Frank
and Professor A. R. Mackintosh for valuable sug-
gestions during the course of the research.
K. Pedersen assisted in the preparation of single-
crystal samples.
'For a review, see Magnetic Propeyties of Rare
Earth Metals, edited by B. J. Elliott, (Plenum, New
York, 1972).
G. Williams and L. L. Hirst, Phys. Bev. 185, 407
(1969).
L. Passell, R. Birgeneau, and
~K. C. Turberfield,
E. Bucher, Phys. Rev. Lett. 25, 752 (1970), and Phys.
Bev. B 4, 718 (1971).
4J. Jensen, J. G. Houmann, and H. Bjerrum Miler,
to be published; B. M. Nicklow, N. Wakabayashi, M. K.
Wilkinson, and B. E. Reed, Phys. Rev. Lett. 27, 334
(1971).
For a review, see A. J. Freeman, in Ref. 1.
60. Jepsen and O. K. Andersen (private communica-
tion) quote the following values for the d-conduction-
band widths in units of rydbergs: Sc, 0.28; Y, 0, 48;
Tb, 0.59; and Lu, 0.61 (obtained by the standard poten-
tial construction using superposition of atomic change
densities and full Slater exchange) .
7D. Davidov, R. Orbach, C. Rettori, L. J. Tao, and
E. P. Chock, Phys. Rev. Lett. 28, 490 (1972); B. A.
Devine, J. M. Moreti, J. Ortelli, D. Shaltiel, %. Zingg,
and M. Peter, Solid State Commun. 10, 575 (1972);
C. Rettori, D. Davidov, R. Orbach, and E. P. Chock,
Phys Bev. B 7, 1 (1973), and references therein.
S. Chikazumi, K. Tajima, and K. Toyama, J. Phys.
(Paris), Colloq. 32, Cl-180 (1971).
9T. Asada, J. Phys. Soc. Jpn. 35, 85 (1973).
'OJ. Hgg and P, Touborg, Phys. Rev. B 9, 2920 (1974).
K. A. McEwen and P. Touborg, J. Phys. F: Metal
Phys. 3, 1903 (1973).
' J. Ht(g and P. Touborg, Phys. Rev. B 9, 2920 (1974).
' A. Abragam and B. Bleaney, Electron 2-nxamagnetic
Resonance of Transition Ions (Clarendon Press, Ox-
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'~P. Touborg, J. Hying, G. J. Cock and L. W. Roeland,
Phys. Bev. B (to be published).
' O. Bathmann, J. Als-Nielsen, P. Bak, J. Hgg and
P. Touborg, Phys. Bev. 8 (to be published).
'6T. Kasuya, in Magnetism, edited by G. T. Rado and
H. Suhl (Academic, New York, 1966), Vol. IIB.
H. Aleonard, P. Boutron, and D. Bloch, J. Phys.
Chem. Solids 30, 2277 (1969); P. Touborg, S. Balling,
and K. M. Ravn, to be published.

Magnetic Properties of Ho-Co and Ho-Fe Amorphous Films

Neil Heiman and Kenneth Lee
IBM Research Labotntoxy, San Jose, Califongia 95198
(Received 6 May 1974)

Polar-Faraday-rotation and magnetization measurements on evaporated amorphous

films of Ho-Co and Ho-Fe show that the principle mechanism responsible for differences
in the T& of the crystalline and amorphous states is the altered electronic configuration
of the transition metal, rather than local anisotropy. Additionally we found that the
films possess uniaxial anisotropy.

That the technologically important" amorphous random orientation of the local anisotropy field,

can be prepared' "

rare-earth (RE) —transition-metal (TM) alloys
without the need to include
"glass-former" atoms or to maintain the sam-
ples at cryogenic temperatures presents an op-
portunity to understand the fundamentals of amor-
phous magnetism. Published experimental data
on the magnetic properties of amorphous RE-
in thai Gd is an $-state atom whereas Tb is high-
ly anisotropic. Tao et al. , '*' while not ruling out
local-anisotropy effects altogether, attribute the
differences to the fact that reduced density in-
hibits charge transfer from the RE to the d or-
bitals of the TM. Since Fe, unlike Co, has un-

""
TM alloys are confined mainly to TbFe,
GdCo, .
and"
There is considerable interest in the
fact that the Curie temperature (Tc) for TbFe, is
markedly lower in the amorphous state than in
the crystalline state, whereas Tc of GdCo, is con-
siderably higher in the amorphous state than in
the crystalline state. Harris, Plisehke, and
Zuckermann' attribute these differences to the
filled majority as well as minority spin states,
they indicate that reduced charge transfer may
produce opposite results in TbFe, and GdCo, .
Unfortunately the data on amorphous TbFe, and
GdCo, are not sufficient to resolve the question
of the relative importance of the two mechanisms.
Additionally some existing data seem to argue
against either mechanism. For example, a re-
cent Letter by Sarkar et al. ' reports Mossbauer-
VOLUME 33, +UMBER 13 PHYSI CA I. R K V I K %' I. K T
effect results which are in agreement with the
local-anisotropy model and which apparently dis-
agree with the charge-transfer model. Qn the
other hand the local-anisotropy model wouM not
seem to predict an increased Tc for GdCo, . In
view of the controversy about the mechanisms
which account for the properties of amorphous
RE- TM alloys, we have carried out a study to
help clarify the issue. %e have examined the
magnetic properties of amorphous Ho-Co and
Ho-Fe thin-film alloys over a wide composition-
al range. This is the first time that the system-
atics of both amorphous RE-Co and RE-Fe alloys
have been studied with the same RE constituent
so that the effects of the different TM can be
evaluated reliably. Also by comparing Ho-Fe
results to published TbFe, data and Ho-Co re-
sults to published GdCo, data, the importance
of the RE can be assessed. Furthermore since
we have examined the amorphous Ho- TM alloys
across a broad compositional. range, the system-
atic trends in the data provide additional insights.
%e find that our data, particularly when taken in
conjunction with the published amorphous TbFe,
and GdCo, data and with known systematics of
crystalline RE-TM alloys, demonstrate that the
amorphous state increases Tc for Co alloys, de-
creases Tc for Fe alloys, and increases the TM
moment in both the Fe and Co cases. These con-
clusions strongly support the basic features of
the charge-transfer model.
Thin films of amorphous Ho-Co and Ho-Fe al-
loys were prepared by thermal evaporation of the
bvo metals in a vacuum system with a base pres-
sure of V@10 ' Torr. Films spanned the compo-
sitional range from 17 to 60 at. % Ho. The chemi-
cal compositions were checked by electron-mi-
croprobe analysis on a number of samples, and
these measurements agreed with the evaporation-
rate-monitor determinations to within 2%. Films
were examined and found to be amorphous by
both x-ray and electron diffraction measurements.
Figure 1 shows Tc and the compensation tem-
perature T„~p as functions of composition for
amorphous Ho-Co alloys as determined by polar-
Faraday-rotation measurements at A. = 0.6328 pm.
Also plotted on the same figure for comparison
compounds obtained from the literature. "
Rre Tc Rnd T p foI seveIRl crystalline Ho Co
Tc
values for amorphous Ho-Co films with greater
than 60 at. % Co were considerably in excess of
600 K and could not even be estimated since the
saturation polar Faraday rotation shov ed no sig-
nificant decrease up to 500 K, the maximum tem-
I K RS 23 SEPTEMBER 1974
1000—
Tc (amorphous)
Tco~p (amorphous)
Tc (crystal)
TCOITlp (crystalI
800—
600—
i
C}.
E
400—
200—
0 gr I
20 60 80 100
Co (atomic percent)
FIG. 1. T(- and Tco~p for amorphous and crystalline
Ho-Co alloys. The lines are not fitted functions, but
merely indicate trends in the data. The amorphous
Ho&vco83 sample did not have T«~ p above 4.2 K (indi-
cated by arrow).
perature that could safely be used before crystal-
lization would become a consideration. One
stl lking feature of Fig. 1 is that Tc for Ho33Co87
is greater than 500 K whereas Tc for crystalline
HoCo, is only 80 K. In general it appears that
Tc and T„p of the amorphous Ho-Co alloys are
similar to Tc and T
'„p
of crystalline Ho-Co al-
loys containing 10 at. % more Co. An important
point is that the Faraday-rotation data on T p
conclusively establish the fact that the magnet-
ization is more Co dominated in the amorphous
alloys since such measurements determine the
temperature and composition at which the Ho sub-
lattice magnetization equals the Co sublattice
magnetization without regard to questions of sat-
uration, sample volume, or other technical diffi-
culties normally associated with magnetization
measurements. For completeness vibrating-
sample- magnetometer measurements were made
from 4.2 to 300 K by using a superconducting
magnet capable of VO kQe. %e had no difficulty
saturating our samples. The magnetometer mea-
surements further confirm the more Co-dominat-
ed magnetization in the amorphous samples.
Specifically the 4. 2-K saturation magnetization
values for amorphous H03 C0677 Ho„Co„, and
Ho»Co» are 765, 576, and 20 emu/cm', respec-
tively. Using either measured densities or val-
ues determined by linear extrapolation of Ho and
VOZ. UME 33, NUMBER I3
Co densities, we calculated the number of Bohr
magnetons per formula unit (pB/f. u. ) at 4. 2 K to
be (4. 8+ 0. 5) p~/f. u. , (4.3+ 0. 5)p~/f. u. , and (0.2
a 0.1)p B/f. u. , respectively compared to 7.6pB/
f.u. , 5. 6pz/f. u. , and l. lpB/f. u. for the corre-
sponding crystalline phases. The uncertainties
in the moments reflect the differences in the
measured and extrapolated densities. It should
further be noted that in crystalline HoCo„ the
moment of the Ho sublattice at 4. 2 K is greater
than that of Co, whereas the reverse is true for
the amorphous film.
T& and T„p
for Ho-Fe films obtained from
polar-Faraday-rotation measurements are plot-
compounds. "
ted in Fig. 2 along with points for the crystalline
There are striking differences be-
tween this figure and the Ho-Co plot. Tc of the
amorphous Ho-Fe films is drastically lower than
Tc of the crystalline compounds. In addition,
for the crystalline Ho-Fe compounds, Tc anom-
alously increases as more Ho is added even
though the Fe moment is known to decrease. On
the other hand T„pof the amorphous films ex-
tends further into the Ho-dominated region of the
alloy system, just as in the case of the amor-
phous Ho-Co data, demonstrating that the mag-
netizations of the amorphous samples are once
again more TM (in this case Fe) dominated. Re-
sults of magnetometer measurements are simi-
lar to those for amorphous Ho-Co in that the
magnetization of all the alloys is more Fe domi-
1000
T, (amorphous)
800— Tc Q m Ip (amOrPh OuS)
T, (crystal)
corn I, (crystal)
600—
Lo
L
Ql
Q.
E
400—
I
g~O~O—
200—
0 +/I I I
20 40 60
Fe (atomic percent)
FIG. 2. Tc and T«~ for amorphous and crystalline
Ho-Fe alloys. Ho60Fe40 was not magnetic above 77 K
(indicated by arrow). Ho25Fe&5 was approaching T«~
&
as the temperature was lowered to 77 K.
780
PHYSICAL RKVIKW LKTTKRS 23 SEPTEMBER 1974
nated. Specifically the moments for amorphous
HoFe, and HoFe, are (2. 5+ 0.3) p, z/f. u. and (2. 8
+ 0.3)yB/f. u. compared to 5. 5pB/f. u. and 4. 6gB/
f.u. for the respective crystalline material.
Amorphous Ho-Fe therefore behaves much the
same as amorphous Ho-Co except for Tc.
The facts established by the data are first that
the magnetizations in both Ho-Co and Ho-Fe
amorphous alloys are more TM dominated than
in the crystalline alloys and second that, rela-
tive to the crystalline state, Tc increases for
amorphous Ho-Co and decreases for Ho-Fe.
Since the magnetizations of both Ho-Co and Ho-
Fe amorphous alloys behave the same, and since
the same RE is involved in both series of alloys,
it is clear that the difference in the Tc behaviors
of Ho-Co and Ho-Fe must be attributed to the al-
tered state of the TM. The fact that the magnet-
izations of the amorphous samples are more TM
dominated than in the crystalline case can be ex-
plained by one of three possibilities: Either the
TM moment is increased or the Ho moment is
decreased or both. In view of the altered state
of the TM deduced from the Tc behavior, it is
reasonable to conclude that the TM moment is in-
creased. Furthermore, the systematics of crys-
talline RE- TM alloys support this conclusion in
that both the Tc and the Co m. oment increase with
increasing Co content whereas the Fe moment in-
creases but Tc decreases as the Fe content is in-
creased. Thus, the Tc behavior, the TM domina-
tion of the magnetizations, and the systematics
of RE-TM crystalline alloys support the charge-
transfer model.
Some further comments are in order. Since
the differences in Tc and magnetization between
crystalline and amorphous Ho- TM alloys span
the broad compositional range, it seems unlikely
that these differences are due only to density ef-
fects. It would appear that mere disorder plays
0 a role in altering the character of the TM. A
further consideration which may contribute to
I
the observed behavior is that nearest-neighbor
0
interactions are likely to be particularly impor-
tant in determining the properties of amorphous
materials. Co exchange interactions are ferro-
magnetic for any realistic distribution of first-
neighbor distances, whereas Fe exchange inter-
80 100 actions for first-nearest neighbors are critically
dependent upon the distribution. Finally there
may be some evidence that local-anisotropy ef-
fects alter the RE moment. If one assumes rea-
sonable maximum values for the TM moments
(1,7pB for Co, 2. 2p~ for Fe), one concludes from
VOLUME 3 3 ~ NUMBER 1 3 PHYSICAL REVIEW LETTERS
the magnetization measurements that the Ho mo-
ment is reduced by about 15%; however, as noted
earlier, a quantitative interpretation of these
measurements is not entirely reliable. It must
be stressed that mhile both charge-transfer and
local-anisotropy effects contribute to the altered
magnetizations of the amorphous RE-TM alloys,
the change in Tc must be attributed mainly to the
altered properties of the TM.
Before me conclude, we wish to point out that
all films examined had the easy direction of mag-
netization perpendicular to the film plane. In a
number of the films, cylindrical domains (i.e. ,
"magnetic bubbles" ) were detected either direct-
ly by Lorentz microscopy or inferred from the
shape of the hysteresis loop. The uniaxial aniso-
tropy constants K„ for Ho-Co alloys at 4. 2 K were
determined from the fields needed to saturate the
films in both the perpendicular and in-plane di-
rections. Values for K„were about 3 &&10' ergs/
cm'. Previously, ~™ s presumed that rf-bias
sputter-deposition techniques mere required to
produce uniaxial anisotropy. Interestingly the
values for E„ in these evaporated Ho-Co films
are about 1 order of magnitude greater than those
reported for amorphous Gd-Co" prepared by rf-
bias sputter deposition. A number of experi-
ments" had been performed to determine the ori-
gin of K„ in those Gd-Co films. The results ruled
out stress-induced and shape anisotropy, leading
to the conclusion that Co pair ordering is the re-
sponsible mechanism. The larger anisotropy in
evaporated Ho-alloy films would imply that pair
ordering is most likely not the origin of . E„ in
these films. Films prepared on carbon foils sup-
ported on Collodion-coated grids showed uniaxial
anisotropy, ruling out stress. K„values are too
large to be explained by shape anisotropy. It
would appear therefore that K„ is due to interac-
tion of the Ho with directional correlations on an
23 SEPTEMBER 1974
atomic scale. It may well be that local aniso-
tropy fields though basically random have a pre-
ference for the direction perpendicular to the
film plane.
We mould like to thank S. Lawrence for his
technical assistance, W. Parrish for x- ray re-
sults, R. Geiss for the Lorentz microscopy, and
M. Lorenz, J. Smit, J. Suits, R. Soohoo, and
C. R. Guarnieri for helpful discussions.
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