J. Phys. Chem. So/ids Vol. 56. No. 314. pp.

M-344, 1995
Copyright 0 1995 Else&r Science Ltd
Pergamon 0022~3697(94)00205-3 Printed in Great Britain. All rights reserved
0022-3697/95 $9.50 + 0.00

VALIDITY OF THE SUGANO-TANABE DIAGRAM FOR

BAND STATES IN MnO AND MnS UNDER HIGH
PRESSURE

M. KOBAYASHI,? T. NAKAI,_F§ S. MOCHIZUKIS and N. TAKAYAMAS

tDepartment of Material Physics, Faculty of Engineering Science, Osaka University. Toyonaka.
Osaka 560, Japan
IDepartment of Physics, College of Humanities and Sciences, Nihon University, Setagaya-ku.
Tokyo 156, Japan

Abstract-Optical transition between 3d bands in cubic MnO and MnS is measured upon applying
hydrostatic pressure. Pressure dependence of the Racah parameter B and the crystal field strength Dq is
determined. The pressure coefficients of transition energies from ‘A, to 4T, and 4T2 states calculated using
the Sugano-Tanabe diagram agree well with experimental values. An emission band at 1.63 eV in MnS
at I.5 K is identified to be 4T, + ‘A, transition accompanied by a large lattice relaxation.

Keywords: A. chalcogenides, A. inorganic compounds, C. high pressure, D. crystal fields, D. optical

properties.

1. INTRODUCTION MnS exhibits two strong luminescence bands with

large Stokes shifts when it undergoes the phase
It has been widely accepted that the crystal field
transition to antiferromagnets below the Nlel tem-
theory [l] offers a powerful method to analyze the
perature (TN = I52 K) [3]. We have measured the
optical transition between localized d-states of tran-
pressure dependence of the A-band [3] in order to
sition metal impurities embedded in a variety of
elucidate the emission mechanism.
insulating crystals. In Mn chalcogenides, however,
the Mn*+ ions are not localized impurities, but 2. EXPERIMENTAL PROCEDURES
constituent ions of the bulk crystal in which 3d-
In order to apply hydrostatic pressure, a diamond
orbitals overlap well with each other to form the
anvil cell was used. Absorption spectra of MnO were
electronic energy bands. It would, therefore, be im-
measured using single crystals at room temperature.
portant to check the applicability of the theory to
For MnS, only small amounts of powder sample were
such extended states. For this purpose, the appli-
available, therefore it was difficult to measure the
cation of hydrostatic pressure gives an effective way
absorption spectra. Alternatively, we have measured
to check the theory since the pressure changes the
excitation spectra for the B-band centered at I .43 eV
magnitude of the crystal field directly.
at 77 K [3]. The excitation source, light from an Xe
We report the absorption and excitation spectra in
discharge lamp, was used passing through a mono-
MnO and MnS under high pressure, which have been
chromator and being focused onto the sample.
obtained by utilizing a diamond anvil cell at low
We have measured the photoluminescence spec-
temperature. We have observed pressure dependence
trum of the A-band centered at 1.63 eV in MnS [3]
of several peaks which are ascribed to the optical
under high pressure at I.5 K. The excitation was by
transition between d bands [2]. The pressure depen-
the 488 nm line of an Ar laser.
dence has been analyzed by adopting the Sugano-
The pressure medium used was methanol and
Tanabe diagram to determine the pressure depen-
ethanol of 4: I volume ratio at room temperature,
dence of the crystal field intensity Dq and the Racah
nitrogen at 77 K and helium at 1.5 K.
parameter B.
3. RESULTS AND DISCUSSION

MnO
$ Present address: Mitsubishi Chemical Corporation.
Yokohama Research Center. Image Printing Laboratory, Figure I shows absorption spectra of MnO at given
Yokohama 227, Japan. hydrostatic pressures up to 18.6 GPa. At 0.66GPa

341
342 M. KOBAYASHI ef al.

three bands are observed: the bands whose peaks

locate at 2.01, 2.5 and 2.94 eV are ascribed to the 3d
crystal field splitting transitions from the ground state
“A, to the excited states 4T,, 4T, and 4A, (or 4E),
respectively [2]. All these bands shift toward low
energy with increasing pressure, which can be ex-
plained by the increase of the crystal field formed by
O*- ions. Peak energies are plotted as a function of
the pressure P shown by open circles in Fig. 2. A
straight line for the 4E transition in Fig. 2 gives the
energy versus P relationship as 2.94 - 0.0014P (eV),
where P is in units of GPa. According to the diagram
for the d5 configuration (Fig. 9 of Ref. [I], which we
abbreviate as the S-T diagram), the 4A, (or 4E)
transition energy E normalized by a Racah parameter
B is given by E/B = 32.5, which is a constant in a
framework of the crystal field theory. The experimen-
tal dependence of E on P means, therefore, that B
should depend on P as I I I

0 5 10 15 20
B = E/32.5 = 0.090 - 4.3 x 10e5P (eV). (1)
PRESSURE 1GPa)
Fig. 2. Pressure dependence of transition energies from “A,
to 4T,, 4T2 and 4A, (or 4E) states in MnO (open circles) and
The physical meaning for the decrease of B upon in MnS (closed circles).
application of pressure is explained as follows: when
the lattice constant decreases, the covalent character The crystal field strength Dq/B at ambient pressure
of the crystal or the spread of charge distribution can be determined by finding a position on the
becomes large, which makes the coulombic inter- abscissa in the S-T diagram at which the ratio of the
action between d-electrons or B decrease. three transition energies agrees with the experimental
ratio. The result is (Dq/B),=, = I .3. Inserting a value
of B at P=O, we obtain Dq(P=O)=O.l17eV.
Assuming six 02- ions surrounding an Mn2+ ion
placed at the origin as point charges, the electrostatic
potential is expressed in the vicinity of the origin as
follows:
35e2
v=yp x4+y4+Z4_;r4 (2)

3
( >
14.7
apart from a constant term, where six O’- ions are
placed on the three Cartesian coordinates having a
distance b from the origin. Therefore, Dq is pro-
portional to a-‘, where a is the lattice constant. In
order to obtain the pressure dependence of a, we
employ the equation of state after Murnaghan and
y+ Birch:

;=(;p+I)-“~~~‘) (3)

where u0 is a at P = 0, and B, and B; are the bulk

modulus and its pressure derivative, respectively. We
I I adopt B,, = 162 GPa and B{, = 4.8 in MnO. Combin-
2.0 3,o ing these equations, we obtain
Energy (eV 1

Fig. I. Absorption spectra of MnO under given pressures. Dq(P)=O.l17(1 +O.OIP)eV (4)
 Sugano-Tanabe diagram for band states 343

The magnitude of Dq/B does not change much under

pressure. It changes from 1.3 to 1.56 as pressure
increases from zero to 18.6 GPa which is the highest
pressure in the present experiment. In such a re-
stricted range of Dq/B, the relationship between E/B
and Dq/B for the 4T, transition given in the S-T
diagram can be replaced by a linear relationship,
without significant errors, as follows:

E/B = 35.5 - lO(Dq/B). (5)

Inserting eqns (I) and (4) for B and Dq into eqn (5).
we get
E = 2.04 -0.012P (6)

that is, a theoretical pressure coefficient of the 4T,

transition predicted by the crystal field theory is
-0.012 eV/GPa, which agrees well with an exper-
imental slope of -0.013 eV/GP as shown in Fig. 2.
Similar analysis for the 4T, transition offers a
pressure coefficient of -0.010 eV/GPa, which also
coincides well with the experimental value of
-0.01 I eV/GPa.

MnS
The excitation spectra for the 1.43 eV band under
high pressure at 77 K are shown in Fig. 3. Three
bands A, B and C whose peaks locate at 2.08, 2.45
and 2.74 eV at ambient pressure are attributed to the 2.0 2.4 2.8 3.2
transitions from 6A, to 4T,, 4T2 and 4A, (or 4E) states, PHOTON ENERGY (eV)
respectively [2]. The peak energies are shown as
closed circles in Fig. 2 as a function of P. The Fig. 3. Excitation spectra for 1.41 eV band in MnS at 77 K
under given pressures.
experimental energy of the 4A, (or 4E) transition
depends on pressure as 2.74 - O.Ol5P. Therefore, the
Racah parameter B changes as Substituting eqns (7) and (8) into eqn (9). we
obtain
B = 0.084 - 4.6 x 10-4P. (7) E = 2.082 - 0.03OP. (IO)

(Dq/B),=, is determined to be 1.07 by adopting the The theoretical value of the pressure coefficient
same procedure as in MnO. Substituting a value of B thus obtained agrees well with an experimental value
at P = 0, we get Dq(P = 0) = 0.090 eV. Kraft and of -O.O30eV/GPa for the ‘T, transition energy
Greuling [4] reported pressure dependence of the (Fig. 2). Similar calculation of the ‘T, transition
specific volume. which gives a/cro = I -0.003P. The energy based on the crystal field theory predicts
pressure dependence of the crystal field parameter Dq E = 2.444 - 0.026P. The experimental pressure co-
is determined, therefore, as efficient is -27.5 meV/GPa, which is almost equal to
the theoretical value.
Dq = 0.090(u/a,,)~5 = 0.090( 1 + 0.015P). (8) The pressure coefficient of the Racah parameter B
in MnS is about ten times larger compared with
Dq/B changes between 1.07 and 1.15, the latter MnO. On the other hand, the absolute magnitude of
corresponds to the highest pressure of 3.9 GPa. In the B in MnS is smaller than in MnO. This results from
restricted region of Dq /B, the S-T diagram for 4T, the fact that the covalency of MnS is stronger com-
transition is reduced to a linear relationship expressed pared with that of MnO.
by The pressure dependcncics of the “T, and ‘T,
E/B = 35.5 - 10 x (Dq/B). (9) transition energies in MnO are mainly determined
344 M. KOBAYASHI et al.

1.4 1.5 1.6 1.7 l-8

PHOTON ENERGY ( eV )
Fig. 4. Pressure dependence of luminescence spectrum for 1.63 eV band in MnS at 1.5 K

from the pressure dependence of Dq. However, the here. One plausible explanation is that the exciton
pressure dependence of B has a much larger role in effect between excited electron and hole makes the
MnS. For the 4T, transition, it contributes by an atomic character recover.
amount of 53% in the whole pressure coefficient, Figure 4 shows the pressure dependence of lu-
while for the 4T, transition, the contribution reaches minescence spectra of 1.63 eV band [3] in MnS at
65%. 1.5 K. The emission peak energy is expressed as
The importance of introducing the pressure depen- 1.63 - 0.033P (eV). This pressure coefficient is almost
dence of B was pointed out by Mayrhofer et al. [5] in equal to that of the lowest absorption band A
Zn, _,rMn,S. The largest value of x investigated was (-0.030 eV/GPa). This suggests that the emission
0.4. In such mixed crystals, however, there coexist originates from the reverse process of the lowest
different sizes of Mn clusters each of which feels transition from ‘A, to 4T, accompanied by a large
different strengths of the crystal field. It is difficult to lattice relaxation to produce the Stokes shift of
evaluate the crystal field in the inhomogeneous sys- 0.45 eV.
tem. Moreover, the mean field approximation is not
applicable, since the localized character of 3d is REFERENCES
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It is worthwhile to note that the crystal field theory Matter 4, 6501 (1992).
is even applicable to the transition between d bands 4. Kraft A. and Greuling B., Cr,r.rr. Res. Tedmol. 23, 605
(1988).
in MnO and MnS, since good agreement with the 5. Mayrhofer K.. Hochberger K. and Gebhardt W..
experimental pressure dependence is demonstrated J. Phys. C, Solid Stare Phys. 21, 4393 (1988).