Diluted magnetic semiconductors

J. K. Furdyna

Citation: J. Appl. Phys. 64, R29 (1988); doi: 10.1063/1.341700

View online: http://dx.doi.org/10.1063/1.341700
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Diluted magnetic semiconductors
J. K. Furdyna
Department of Physics, University oJNotre Dame, Notre Dame, Indiana 46556
(Received 20 October 1987; accepted for publication 21 March 1988)
We review the physical properties of diluted magnetic semiconductors (DMS) of the type
Ail_xMnxBvI (e.g., Cd1_xMnxSe, Hg! _ .. Mnx Te). Crystallographic properties are discussed
first, with emphasis on the common structural features which these materials have as a result of
tetrahedral bonding. We then describe the band structure of the A~l __ xMnxBV! alloys in the
absence of an external magnetic field, stressing the close relationship of the sp electron bands in
these materials to the band structure of the nonmagnetic ABB vl "parent" semiconductors. In
addition, the characteristics of the narrow (nearly localized) band arising from the half-filled
Mn 3d 5 shells are described, along with their profound effect on the optical properties of DMS.
We then describe our present understanding of the magnetic properties of the A~'_ xMnxBv'
alloys. In particular, we discuss the mechanism of the Mn t- +-Mn+ +- exchange, which
underlies the magnetism of these materials; we present an analytic formulation for the
magnetic susceptibility of DMS in the paramagnetic range; we describe a somewhat empirical
picture of the spin-glass-like freezing in the Ail_ xMnxBvI alloys, and its relationship to the
short range antiferromagnetic order revealed by neutron scattering; and we point out some not
yet fully understood qnestions concerning spin dynamics in DMS revealed by electron
paramagnetic resonance. We then discuss the sp-d exchange interaction between the sp band
electrons of the A;'_ xMnxBv' alloy and the 3d 5 electrons associated with the Mn atoms. Here
we present a general formulation of the exchange problem, fonowed by the most representative
examples of its physical consequences, such as the giant Faraday rotation, the magnetic-field-
induced metal-to-insulator transition in DMS, and the properties of the bound magnetic
polaron. Next, we give considerable attention to the extremely exciting physics of quantum
wells and superlattices involving DMS. We begin by describing the properties of the two-
dimensional gas existing at a DMS interface. We then briefly describe the current status of the
A~I _x Mn, B VI layers and superlattices (systems already successfully grown; methods of
preparation; and basic nonmagnetic properties of the layered structures). We then describe
new features observed in the magnetic behavior of the quasi-two-dimensional ultrathin DMS
layers; and we discuss the exciting possibilities which the sp-d exchange interaction offers in
the quantum-well situation. Finally. we list a number of topics which involve DMS but which
have not been explicitly covered in this review-such as elastic properties of DMS, DMS-based
devices, and the emerging work on diluted magnetic semiconductors other than the
A~l_ xMnxBvI alloys-and we provide relevant literature references to these omitted topics.

I. INTRODUCTION Semiconductors and Semimetals series has been devoted in

Diluted magnetic semiconductors (DMS)-also re-
ferred to as semimagnetic semiconductors-are semicon-
ducting alloys whose lattice is made up in part of substitu-
tional magnetic atoms. The most extensively studied and
most thoroughly understood materials of this type are the
A;I __ xMnxBvI alloys in which a fraction of the group n sub-
lattice is replaced at random by Mn. The worldwide scientif-
ic interest and intense research activity which this group of
materials enjoys is evidenced by over one thousand papers
published on DMS to date, by an exceptionally large number
ofinvited papers devoted to this subject at international con-
ferences, \-20 and by the survey articles 21 - 25 and compendia26
which have appeared in the last decade. Furthermore, sever-
al international symposia devoted specifically to DMS have
recently been held (e.g., Bad Honnef, 1984; Aussois, 1985;
Boston, 1986; and Jablonna, 1987), the Boston meeting re-
sulting in a published proceedings. 27 Finally, Vol. 25 of the
its entirety to DMS.2B
Diluted magnetic semiconductors of the A~! _ x Mn" B VI
type are of interest for several distinct reasons. 29 Their ter-
nary nature gives us the possibility of "tuning" the lattice
constant and band parameters by varying the composition of
the material. The random distribution of magnetic ions over
the cation sublattice leads to important magnetic effects,
e.g., the fonnation of the spin-glass-like phase at low tem-
peratures. The su.bstitu.tional Mn atoms in the AllB vr lattice
are also characterized by highly efficient electrolumines-
cence, whi.ch makes dilute A ~I_ x Mn x BVI alloys important in
the context of optical fiat panel display applications. Fur-
thermore, the presence of localized magnetic ions in these
semiconductor alloys leads to an exchange interaction be-
tween the sp band electrons and the d electrons associated
with Mn +- +, resulting in extremely large Zeeman spHUings
of electronic (band and impurity) levels. This selective "am-
plification" of spin-dependent properties leads to dramatic

R29 J. App\. Phys. 64 (4),15 August 1988 0021-8979/88/160R29-36$02.40 @ 1988 American Institute of Physics R29

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new effects, such as the giant Faraday rotation, the magnet-
ic-field-induced metal-insulator transition, and the forma-
tion of bound magnetic polarons.
Because of the tunability of their lattice parameters and
their energy gaps, theA~I_ xMnxBvI alloys are excellent can-
didates for the preparation of quantum wells, superlattices,
and other configurations that involve band-gap engineering.
The presence ofMn in these alloys brings new physics (mag-
netic properties, optical transitions specific to Mn + + ions,
and the sp-d exchange interaction) into the multiple quan-
tum-well context, extending the already rich and exciting
spectrum of phenomena which take place in layered hetero-
structures by yet another dimension.
In this review we shall focus primarily on the
A~I_ xMnxBvI alloys. We shaH first describe the structural
properties of these materials. We shall then discuss their
band properties and electrical and optical effects in the ab-
sence of an external magnetic field, including the effects of
the narrow d electron bands which give rise to optical prop-
erties specific to Mn + + ions. Next we shall describe the
magnetic properties of DMS. We will then formulate the
principal concepts of exchange interaction between the sp
band electrons and the d electrons associated with Mn + + .
Finally, to underscore the unique opportunities of the rapid-
ly growing field of DMS superlattices and heterostructures,
we shall devote a separate section to review the physical
properties of two-dimensional structures, including the
physics of DMS quantum wells, superlattices, and inter-
faces.
II. CRYSTAL STRUCTURE AND COMPOSITION OF DMS
A.Overview
The entire family of ternary Ai! _ xMnxBvI alloys, along
with their crystal structures and corresponding ranges of
composition,30 is listed in Table 1. One can see from the table,
for example, that Cd\._ "Mnx Te forms a ternary alloy of
zinc-blende structure with x up to 0.77, whileZn 1 _. xMuxSe
exhibits zinc-blende structure for x < 0.30 and wurtzite
structure for 0.30 <x <0.55. Given the fact that the stable
crystal structures of MnTe, MnSe, and MnS are neither
TABLE I. A{I_xMn,Bvl diluted magnetic semiconductors.
Crystal
Materials structure Range of composition
Zn,_ ,MnxS zincblende
wurtzite O.1O<x<OA5
Zn, _ xMnxSe zincblende
wurtzite O.}O<x.;:O.57
Zn,_.,MnxTe
Cd, _xMnxS
zincblende
wurtzite
wurtzite
Cd' .. xMnx Se
Cd, _xMnxTe zinc blende
Hg, _xMnxS zinc blende
Hg'_xMnx Se zincblellde
Hg,._ ,MD, Te zincblende
R30 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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zinc blende nor wurtzite; 21 it is remarkable that the
Ail _ x Mn" BVI solid solutions shown in Table I can reach
such high values of x. For example, MnTe itself crystallizes
in the NiAs structure, yet in the case of Cd l _ x Mn" Te the
zinc-blende structure of the "parent" CdTe survives for x as
high as 0.77, and even higher for Zn l __ "Mn" Te. 2 !
The two crystal structures in which the A~I__ xMrixBvI
alloys form-zinc blende and wurtzite-are very closely re-
lated, in spite of the difference in symmetry, in that they are
both formed with tetrahedral (S_p3) bonding, involving the
two valence s electrons of the group II element and the six
valence p electrons of the group VI element. Manganese is a
transition metal with valence electrons corresponding to the
4s2 orbital, Although manganese differs from the group II
elements by the fact that its 3d shell is only half-filled, it can
contribute its 4s2 electrons to the S_p 3 bonding, and can
therefore substitutionally replace the group II elements in
the AIlBvI tetrahedra! structures.
These properties of manganese are apparently a neces-
sary but not a sufficient condition for forming stable phases
over a wide range of compositions, since other transition-
metal elements, even those which readily form divalent ions,
are not nearly as miscible with the ABB vl compounds. It
would appear that the ease with which Mn atoms substitute
for the group II elements in the zinc-blende and wurtzite
structures results from the fact that the 3d orbitals ofMn are
exactly half-filled. By Hund's rule aU five spins are parallel in
this orbital, and it would require considerable energy (about
6-7 eV) to add an electron with opposite spin to the Mn
atom. 20 In this sense the 3d 5 orbit acts as a complete shell
(like, say, the 4d 10 shell in Cd), and the Mn atom is thus
more likely to resemble a group n element in its behavior
than are other transition-metal elements.
B. Crystal structure and lattice parameters of
v,
AL"MnxB alloys
One can see from Table I that, as a rule, ternary alloys
formed by substituting Mn for the group II element in the
AHB vl lattice retain the crystal structure of the "parent"
AIiB Y [ compound. Exceptions to this rule are Zn 1 _ xMnxS
and Zn,._ ",MnxSe, which exhibit the structure of the cubic
A lIB VI host for low Mn content, but above a certain value of
x form in the wurtzite structure. A natural upper limit on the
Mn mole fraction x in the A~I_xMnxBvI crystals is imposed
by the fact that, as was already pointed out, the MnBvI
binary compounds do not naturally crystallize in the zinc-
blende or wurtzite structures.
O<x<O.1O
It is interesting to note that, although the stable phase of
HgS itself is the cinnabar structure (HgS is the only N1B vi
O<x<O.30 compound to crystallize in this form), the presence of Mn in
Hg 1_ x Mnx S appears to stabilize the zinc-blende structure
°
<x.;;O.86
O<x<O.45
of this system. 21 At the present time relatively little is known
about this alloy.
O<x<O.50
<l<x,O.77 The lattice parameters of all DMS ternary alloys obey
O<x,O.37 Vegard's law very closely. This is illustrated by Fig. 1, show-
O<x<O.38 ing the dependence of the lattice parameter of the three cubic
O<x<O.75 tellurides on composition. 32 It is gratifying that the extrapo-
lation to x = 1, which indicates the lattice parameter for the
J. K. Furdyna R30
 4.7 r--~---.-----,--.,--..,
6.50

6.40 0<1:
MnTe

00:{
6.30
c

6.20
MnSe

,
6.10 6
0 1,0 ~
u
)( (Mo!e fraction) Z
<t -- ---- Mn S

~ 3.9 - 'l.""""S
FIG. 1. Lattice parameter as a function ofMn mole fraction x for telluride
DMS. Note the Vegard law behavior and the convergence of the extrapoh~t­ 3.8
ed lines at a single point (6.334 A), which determines the lattice parameter
for the zinc-blende phase of MnTe [after Ref. 31, with Hg, _ xMux Te data
3.7 0
taken from Delves and Lewis, J. Phys. Chern. Solids 24, 549 (1963)]. O. 1.0
Mn CONCENTRATION x

hypothetical zinc-blende MuTe, is the same for the three
alloys. Thus, in spite of the fact that zinc-blende MnTe does
not exist in nature, one may regard the telluride
A~[_ .. MnxBvl materials as true pseudobinary alloys of
AIlTe and MnTe, and one can express the lattice parameter
for any composition in the form
FIG. 2. Mean cation-cation distances d as a function ofMn mole fraction x
for A~'. xMnxBvl alloys. Analytic expressions corresponding to the figures
are given in Table III (after Ref. 32).
The actual lattice parameters can be obtained from the
parameter d listed in Table II as follows:

a = (1 - x ) aU_VI + xaMn_VI' (1) zinc blende: a= lid, (2)

where an_VI and GMn- vr are lattice parameters of the binary wurtzite: a = d, c = (V l!2d. (3)
constituents (e.g., of CdTe and of the "hypothetical" zinc- Further discussion of the lattice structure of the
blende MnTe). A~I __ xMnxBvI alloys from this unified point of view can be
The behavior illustrated in Fig. 1 for the cubic lattice found in Ref. 32, including useful considerations of the role
parameter a is actually true for the distance d between near- of the tetrahedral radius of the constituent atoms in deter-
est like atoms independent of structure, so that the Vegard mining the lattice dimensions (see also Furdyna and Kos-
law behavior can be presented in a unified picture for the sut 33 ) •
entire A~I_xMnxBYI family, wurtzite and zinc blende It should be noted that, apart from its fundamental im-
alike. 32 We show this in Fig. 2. The usefulness of such a plot portance, the precise know ledge of the lattice parameter is of
is made clear by considering, for example, the linear behav- considerable practical interest in that it provides a conven-
ior of d observed for the selenides. Note that Hg! __ x Mn.. Se ient determination of crystal composition in ternary alloys.
is cubic, Cdl __ xMnxSe is hexagonal, and Zn l _ xMn"Se It is a fortunate circumstance in this respect that in the case
changes its crystal structure "in stride" as x increases. Thus, of all A~I__ xMnxBY' alloys the linear variati.on of the lattice
once having established the parameter d for MnSe by extra-
polating, e.g., the lattice constant data for the hexagonal
TABLE n. Mean C<'ttion-cation distance d in A:'. xMnxBY[ alloys.
Cd 1 _ xMnxSe to x = 1, we can predict the lattice constant
for the cubic Hg 1 _ x Mn~ Se, or for either of the two phases of Upperjimit Mean cation-cation
Zn, _ x Mn" Se. Two additional points are worthy of note in Material ofx distance, d (A)
Fig. 2. First, it is interesting that the mutual relationship of d
for HgSe, CdSe, and ZnSe in this figure closely resembles Znl"_xMn,S 0.45 3.8300 + 0.1391 x
Zn, _xMnxSe 0,57 4.0090 + 0.1645 x
that for HgTe, CdTe, and ZnTe, despite the differences in
Zu, _xMnxTe 0.86 4.315+0.168x
structure. We also note that the value of d for Zn 1 _ x Mnx Se
Cd, _xMnxS 0.45 4.123 - 0.151 x
increases smoothly through the cubic-to-hexagonal transi- Cd, _ .,Mn,Se 0.50 4.296 - 0.123 x
tion,32 suggesting that it is the increase in the lattice spacing Cd'_xMnx Te 0.77 4.587 -- 0.105 x
that forces the onset of the hexagonal structure, rather than Hg,_ ,Mn"S 0.37 4.09 - 0.167 x
the other way around. Analytical expressions for the cation- Hg,_ xMuxSe Q.38 4.301 -·0.123 x
cation distances d are listed in Table n for all A~I_ xMnx BY' Hg,_ xMnxTe 0.75 4.5678 - O.OBOO x
alloys (after Ref. 32).

R31 J. Appl. Phys., Vol. 64, No.4, i5 August 1988 J. K. Furdyna R31

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parameter with x is very large (contrast this with, e.g.,
Hg 1 ~ xCdx Te), making this approach to the determination
of composition quite reliable. Typical x-ray techniques yield
the lattice parameter with precision of one part in 104 or
better, thus giving the composition within 1% for most
A~r~xMnxBVI ternaries,
C. Microscopic (local) structure of the OMS lattice
In view of the very consistent adherence of the
A1i_xMnxBV! lattice to Vegard's law obtained from x~ray
diffraction data, one might automatically assume that the
crystal structure of a ternary "zinc-blende" or "wurtzite"
alloy is strictly zinc blende or wurtzite, I.e., that the anions
and the cations are distributed over two interpenetrating,
geometrically perfect fcc or hcp sublattices, each with a lat-
tice constant varying linearly with x. Under this assumption
the picture would be identical to the microscopic structure of
the parent ABB YI binary compound, with the cation lattice
sites occupied randomly by two kinds of ions, and only the
scale adjusted by the Vegard law behavior. This picture is
analogous to the virtual crystal approximation, frequently
used in interpreting the band properties of ternary alloys.
In reality the microscopic situation is considerably more
complicated. Recent extended x-ray absorption fine struc-
ture (EXAFS) studies of DMS by Balzarotti et af.3 4 and
Bunker and co-workers35 •36 shed important light on the de-
tailed microscopic structure of the A~I__ xMnxBV( lattice
(and, by extension, on other tetrahedrally bonded ternary
alloys), and we shall examine this in some detail.
The EXAFS technique provides detailed information
on the immediate atomic environment of a given lattice site,
In the case at hand, it is therefore sensitive, e.g., to the local
spatial distribution of the four cations tetrahedrally bound to
a given anion. In reporting the results and conclusions which
follow from the EXAFS data we shall, for specificity, refer to
Zn l _ "Mn" Se investigated by Bunker and co-workers. 35,36
Briefly, the EXAFS results carried out on
Zn i _ xMn"Se for 0 <x < 0.55 indicate that the Zn-Se and
Mn-Se bond lengths in this material remain practically con-
stant throughout the entire range of compositions studied,
The Zn-Se bond length is approximately unchanged from its
value in pure ZnSe, and the Mn-Se bond length is approxi~
mately that predicted for the hypothetical tetrahedrally
bonded (i.e., zinc blende or wurtzite) MnSe, for which the
lattice parameter is obtained by extrapolation in Fig. 2. The
actual bond length values are shown as a function of x in Fig,
3. Note that, like the parameter d plotted in Fig. 2, the bond
lengths in Fig. 3 are also insensitive to the transition from the
zinc-blende to the wurtzite structure.
These results are not in contradiction to the x-ray dif-
fraction data which predict Vegard's law behavior for the
ternary lattice. X~ray diffraction is not sensitive to the topo-
logical details surrounding an indiuidual lattice point, but
determines the lattice parameter aueraged over many anion
and cation sites. It is this averaged a(x) which varies linearly
with x, as illustrated in Figs. 1 and 2. The EXAFS results,
however, cannot be reconciled with the interpretation that
Vegard's law is obeyed on the microscopic scale by each of
the two interpenetrating geometrically perfect fcc or hcp
R32 J. Appl. Phys., Vol. 64, No.4. 15 August 1988
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..-~.---t
0.13 1
Mn Concentration (x)
FIG. 3. Actual Mn-Se and Zn-Se bond lengths as a function of composi.
tion, determined by EXAFS (after Ref. 35). The space-averaged bond
length (i.e., that extracted from the lattice parameter as measured by x-ray
diffraction) is also shown. Note that Zn,. xMnxSe transforms from zinc-
bJellde to wurtzite at x:::;O.3, but this has no observable effect on either the
bond length or the Vegard law behavior of the lattice parameter.
Bravais lattices (the one occupied by Se atoms, the other by a
random distribution of Zn and Mn in the chosen example of
Znl_xMnxSe). Rather, the two sublattices are distorted by
adjusting locally to accommodate the requirement of keep-
ing the respective Zn-Se and Mn-Se bond lengths as nearly
constant as possible.
While important from a directly crystallographic point
of view, these results are also expected to bear on a number of
other physical phenomena. For example, in light of these
results, the microscopic environments of atoms in the zinc-
blende and wurtzite ternaries are no longer strictly cubic and
hexagonal, respectively, and it is possible that many optical
transitions, particularly those involving local mode excita-
tions, which are forbidden by the type of ideal symmetry
manifested by the binary "parent" compound, may be re-
laxed in these ternary random aHoys. Furthermore, it has
been recently demonstrated that the magnetic properties of
DMS are dominated by superexchange interaction, Le., by
Mn + + ~ Mn + + interactions that are mediated through the
intervening anion. 37-39 The anion-Mn distance, as wen as the
angle subtended by the Mn-anion-Mn triangle, are expected
to bear directly on this exchange process, and thus the new
insights into the local atomic configuration provided by
EXAFS are likely to play an important role in the under-
standing of the magnetic properties of DMS.
Additional details and references on crystal structure,
bond lengths, and covalent radii, as well as on materials
preparation procedures of the A~I_xMnxBY[ alloys, can be
found in Refs. 21, 30, and 32, explicitly devoted to these
SUbjects.
D. Pressureainduced crystalline transformations
Although only a few investigations have been devoted to
the effect of high pressure on the AII_ xMn"Bv1 systems,40.4!
they clearly indicate, as might be expected, that the crystal
structures of these alloys undergo pressure-induced trans~
formations similar to those occurring in the parent AIIB v1
compounds. Thus, e.g., Cd1 __ xMn" Te transforms at high
J. K. Furdyna R32
pressure from the semiconducting zinc-blende to the metal-
lic rock salt structure, similarly to CdTe. The pressures at
which transformations occur are shown in Fig. 4.
This is yet another manifestation that, structurally, the
A~l_ x MnxBvI alloys are extremely close to the AIlB v1 com-
ponds. With this in mind, one would also expect that at high
pressure the Hg I _ x Mn" BVI family should transform to the
cinnabar phase, as happens in the case of the parent HgTe
and HgSe compounds themselves. 42 This, however, has not
yet been established experimentally.
m. ELECTRONIC PROPERTIES OF DMS IN THE
ABSENCE OF A MAGNETIC FIELD
A. General band structure features
The band structure of the A~I_xMnxBV! DMS alloys
can be presented in a unified way by stressing four underly-
ing features:
(1) Qualitatively, the band structure of the
A~[_xMnxBvI alloys closely resembles that of the AllB vI
materials having the same crystal structure, In particular,
these alloys are direct-gap semiconductors, with the band
extrema occurring at the r point. This is illustrated by Fig. 5,
where the curves show the characteristic E vs k dispersion
typical for a A HBVI semiconductor. These bands, common to
the AEB v , compounds and to the Ai I _ x Mn"B Y1 alloys alike,
originate from the sand p orbitals of the constituent atoms,
and we shan refer to them as sp bands.
(2) Quantitatively, the band structure of the
A~I _ x Mnx BVI material transforms in a smooth manner from
that of the parent A HB VI compound to the band structure of
the tetrahedrally bonded MnB YI alloy. Although this evolu-
tion is not strictly linear with x, a linear variation (as would
be predicted by the virtual crystal approximation) is an ex-
cellent first-order approximation for a quantitative descrip-
Cd/..:xMnle
x·a.oo.
0.10 a
0.12 +
0.30 t>
0.45 II
0.60 '!'
0.90 0.70 0
o.eo
0.70 '--_-'-_ _-'-_--"_ _J.-_ _' - - _ - '
o 2,0 4.0 6.0
P (GPo)
FIG. 4. Pressure dependence of the fractional volume change for
Cd,_ xMnx Te (x = 0,0.10,0.12,0.30,0045,0.60, and 0.70), showing the
abrupt zinc-b1ende/rock salt transition near 3.3 GP (after Ref. 40).
RS3 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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5
-<r
ell
>
~
>- 0
(!) E.,. Ueff
0::
W
Z
e:"" ~
W
-5
L r x
FIG. S. Schematic band structure for a zinc-blende Ali_.xMnxBvI alloy.
The behavior of the sp bands is qualitatively the same as in zinc-blende
AlIBV! semiconductors. The Mn levels ej (occupied) and e:J" (unoccu-
q
pied) are split at each site by the energy V.1f C::::; 7 eV). The elfect of pod
hybridization and of the tetrahedral crystal field on the Mn levels is neglect-
ed in this schematic presentation, since the elfect is small on the scale of the
figure. For wurtzite Ai' .., Mn x BVI alloys the band stmcture would be qual-
itatively the same, except that the degeneracy seen at [', in the figure would
be removed, resulting in a slight valence-band splitting ( ::::: 20 me V) at the r
point.
tion of the dependence of the energy gap and other band
parameters on x. The band structures of the parent AIIB VI
binary compounds are wen known. Although tetrahedrally
bonded MnBvI alloys either do not exist in nature (e.g.,
MnTe) , or are of such poor quality that electronic measure-
ments on these compounds are not reliable, band structures
of zinc-hlende or wurtzite MnS, MnSe, and MnTe can be
established by the various computational schemes common-
ly used in band structure calculations, such as the virtual
crystal approximation (VeA), coherent potential approxi-
mation (CPA), and others. 20,31,43-46 The band structures so
obtained can then serve as the x = 1 limit for interpolation
between the A uB VI and MnB VI. This procedure, although
not always precise, nevertheless serves as a very useful guide
for estimating the properties of A ~I_ x Mnx BVI alloys for
O<x< l.
(3) Superimposed on the above band structure charac-
teristic of the A HB VI semiconductors is the effect of the 3d :;
shell of Mn. In Fig. 5 we introduce the presence of Mn as
enegy levels marked e;t <7 and ei CT, corresponding to the ma-
jority (occupied) and minority (unoccupied) states of the
3d orbital. In reality, these levels will be further split by the
tetrahedral field, and broadened into narrow bands by hybri-
dization with the p orbitals. The location of the e;t level is (f
about 3.5 eV below the top of the valence band, as deter-
mined by photoemission experiments47- SO (i.e., by an experi-
ment which involves removing an electron from a fully occu-
pied 3d 5 orbital at a Mn site). This value (about 3.5 eV)
appears to be the same for aU A;I_ x Mnx B VI alloys studied so
far. 51 The location of ed- a band is less certain, but inverse
photoemission experiments 52 (Le., adding a sixth electron to
a given Mn site) indicate that it lies some 3.5 eV above the
top of the valence band in Cd I _ x Mnx Te.
J. K. Furdyna R33
 (4) While the knowledge of the positions of both e/ <7 zinc blende zinc blende wurtzite
and ed- bands, described above, is extremely important for
(T open gap (zero gap)

W \U
formulating p-d hybridization (which underlies both sp-d
and d-d exchange interactions, to be discussed later), it must
be emphasized that these levels are determined in the context
of a removal of an electron (3d 5 -> 3d 4) or of an addition of I
an electron (3d 5 -> 3d 6) to a given Mn site. These transitions I
should not be confused with intra-ion transitions, involving a I
I
:7f\ I
spin flip within the 3d 5 level itself. The latter transitions,
occurring at energies around 2.2 eV, are offundamental im- o
portance in the optical properties of the AiI_xMnxBV! al-
loys, particularly those where the energy gap exceeds 2 eV.
In the remainder of this section we shall focus on the I
direct-gap and on the intra-Mn transitions, since these fea- k" 0
tures are of primary importance in determining the optical
and electrical properties ofDMS in zero magnetic field. For FIG. 6. Band structure near the r point for three cases of interest: an open-
a discussion of the general band structure, induding points gap zinc-blende semiconductor (e.g., Cd, _xMnx Te, or Hgl_xMn xTe for
far from the r point and deep lying bands, we refer the read- x> 0.07}; a zero-gap zinc-blende semiconductor (e.g., Hg,_ x Mn. Te for
,X < 0.05); and a wurtzitesemiconducwr (e.g., Cd t _xMnxSe). In thewurt-
er to the theoretical 20 •37 ,43-46 and experimental 53-55 papers
zite case, the r 9 - r/ C ) and r,tV) - r/ C)transitiolls determine the optical
dealing explicitly with the subject. absorption edge for the Elc and the Ellc polarizations, respectively. where
E is the electric field of incident light and c is the hexagonal axis. This is the
B. The energy gap and its dependence on composition basis of dichroism observed in wurtzite crystals.

AU A~r _ x Mnx B VI alloys are direct-gap semiconductors,

like their AllBvl parent materials, as is shown in Fig. 6 for
three groups of alloys: wurtzite, zinc-blende open gap, and
zinc-blende zero gap. The effect on the energy gap of rep!ac-
ing the atoms of the group II element by Mn is illustrated by
the case of Cd I _ xMnx Te. As Mn is substituted for Cd in the
CdTe lattice, the energy gap increases, to the point that the
originally opaque material eventually becomes transparent
to visible light,56,57 The variation of Eg in Cd l _ xMnx Te is
found to be linear in composition (as suggested above), and
can be expressed as57
Eg(300 K} = (1.528 + 1.316x) eV,
E g (4.2 K) = (1,606 + l.592x) eV,
for the available composition range (x < 0,77). The energy
gap for the hypothetical zinc-blende MnTe can thus be ob-
tained by extrapolating this result to x = 1. The value so
obtained (2.85 eVat 300 K; 3.18 for 4.2 K) can then be used
in the spirit of virtual crystal approximation (VCA) to ob-
tain Eg (x) for Hgj __ xMn" Te and Zn! _ xMn~ Te, This is
shown graphically in Fig. 7 for the telluride family of DMS
because of potential applications of variable narrow-gap
semiconductors as infrared detectors.
As is apparent from Eq. (4), there is a significant tem-
perature dependence of E g' such that the energy gap tends to
open wider as the temperature decreases. 60 This behavior is
similar to that characteristic of the parent AIIBvI com-
pounds, with the result that in the genera! vicinity of the
optical cutoff the A~r_ xMnxBvI alloys tend to be more trans-
parent to shorter and shorter wavelengths as the tempera-
(4a) ture is decreased. The temperature variation for Cd" Mnx Te
is illustrated in Fig. 8. As can be seen, the variation is roughly
(4b)
4
Telluride OMS
402 K
3
>Q)

at 4,2 K. While departures from VCA are known to exist in

the form of"howing," the above linear approximation serves w'" Z
!l.
as a useful guide for the overan behavior of Eg (x). Available
data for Znl_xMn~ Te (Ref. 58) and Hg1_xMu x Te (Ref.
<t
~

>-
,,0
59) confirm the reliability of this approach. Cl ~<:-"r
Il:
Such "tunability" of the energy gap by composition has W ,,\,,"r
Z ~
an especially profound effect in the case of Hg compounds. W
Consider Hg1 __ xMn x Te as an example. 59 In this case the 0 - ------
role of Mn is similar to that of Cd in Hg 1 _ x Cd" Te. For low
values of x this aHoy is a zero-gap semiconductor, like the
-I
"parent" HgTe. At several atomic percent ofMn (x;::::O.07 0.0 0.2 0.4 0.6 O.S 1.0
at 4.2 K; x;::::O.05 at room temperature) the energy gap of Mn CONCENTRATION x
Hg 1 __ ",Mnx Te "opens," and for larger values of x the alloy
becomes an ordinary (i.e., positive gap) semiconductor, the FIG. 7, Energy gap Eg vs Mn concentration x for telluride DMS at low
gap being extremely sensitive to x, very much like in temperatures. A linear extrapolation of E. to x = 1 gives an energy gap of
Hg 1 __ x Cd" T e. A great deal of interest exists in this feature 3.18 eV for zinc-blende MnTe.

R34 J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna R34

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 may be further extended to quarternary compounds, such as
Cdl_..~_yMnxZny Te. 6 ! Noting that the chemical composi-
tion of this alloy can be written as
+
N
0---0 300 K
c:
~ 2.6
0-'-" 80 K (CdTe)! _ x~y (MnTe)x (ZnTe)y,
£ - .. 10K
o we may then estimate the energy gap as
Z
<C 2.4
Eg(x,y) = (1-x-y)Eg (CdTe)
+xEg(MnTe) +yEg(ZnTe), (6)
and similarly for other quaternaries.
There are two qualifications to the approach ofEq. (5).
The first is that wurtzite crystals, such as CdSe and its DMS
derivatives, are birefringent, and there exists a smail differ-
ence between the energy gap for incident light polarized par-
allel and perpendicular to the c axis. 60 However, since the
effect is small (of the order of 20 meV) , Eq. (5) still provides
1.4 '-----'---'---'---'---'--'----'
0.0 0.2 0.4 0.6 a good guide to the behavior of Eg even in materials which
MANGANESE MOLE FRACTION (xl undergo a phase transitions from zinc blende to wurtzite as x
is increased.
FIG. 8. The energy gap (obtained from the free exciton transition, marked The second qualification has to do with a new type of
"A" in the figure) and the 6A,_ 4T, intra-Mn transition (marked "Mn.2+") bowing, which is particularly striking in the cases of
as a function of Mn concentration x for Cd! __ xMnx Te for three tempera-
tures. Note the qualitative similarity in the temperature dependence of both
Cd! ~xMn"S (Ref. 62) and Zn\ ~xMnxSe (Refs. 63 and
types of transitions (after Ref. 57). 64), the latter shown in Fig. 9. The dip in E g , seen at small
values of x in the figure, is probably a consequence of the sp-d
exchange interaction64 which will be described in the subse-
linear between 77 and 300 K, a rather useful fact for making quent sections, and which is uniquely characteristic ofDMS.
interpolations to intermediate values of T. Although the exchange interaction is especially important
In Table III we summarize the energy gap values for the when an external magnetic field H is present, in certain cases
x = a and 1 limits of the A~I_ x MnxBvl alloys for three tem- it can mainifest itself at H = 0, as in the behavior of Eg
peratures. In most of these the effect of bowing is rather shown in Fig. 9. This effect is strongly temperature depen-
small, so that the virtual crystal approximation approach., dent. It is in principle present in other DMS, but to a much
lesser degree.
Eg(x) = (l-x)Eg(O) +xEg(1) =Eg(O) +xAEg,
(5)
C. Intra~d-shell transitions
can be used to estimate the energy gap for a given composi-
tion and temperature. Here Eg (0) and Eg (1) are the energy The AiI __ xMnxBvI systems differ from the AnB v1 com-
gaps for x = 0 and x = 1, respectively, and pounds, and from "orthodox" II-VI ternaries such as
/lEg = Eg(l) - Eg(O). This linear interpolation procedure
3.40 r-r----,--,-----r---r-~

TABLE III. Energy gaps for x = oand I limits oftheA\I_xMnxB vl alloys 3.30
for liquid-helium (LHe), liquid-nitrogen (LN2), and room (RT) tempera-
tures. ,,
3.20
,,
,,
/
Compound T Eg (eV) Compound T Eg (eV)
3.!0
ZnS LHe 3.84 HgS LHe <0
LNz 3.78 LN2 -0 "'3.00
RT 3.68 RT >0 ILl
ZnSe LHe 2.82 HgSe LHe -0.27
LN2 2.80 LNz -0.205 2.90
RT 2.71 RT +0.10
ZnTe LHe 2.40 HgTe LHe -0.300 2.80
LN, 2.38 LN z -0.252
RT 2.28 RT - 0.146
CdS LHe 2.56 MnS LHe .-3.6 2.70
LN2 2.55 LN2 -3.5 o 0.2. 0.4 0.6 0.8 1.0
RT 2.45 RT -3.4 l! Mn FRACTION
edSe LHe 1.83 MuSe LHe 3.3
LN, 1.82 LN2 3.14 FIG. 9. Energy gap as a function ofMn concentration x for Zn, _xMnxSe
RT 1.75 RT 2.9 for two temperatures. Open circles are for bulk crystals (after Ref. 143); full
CdTe LHe 1.606 MuTe LHe 3.2 circles are for MBE grown zinc-blende Zn, _xMn"Se [L. A. Kolodziejski,
LN. L596 LNz 3.05 R. L. Gunshor, R. Venkatasubramanian, T. C. Sonsett, R. Frolme, S.
RT 1.528 RT 2.9 Datta, N. Otsuka, R. B. Bylsma, W. M. Becker, and A. V. Nurmikko, J.
Vac. Sci. Techno!' B 4,583 (l986)}.

RS5 J. AppL Phys., Vol. 64, No.4, 15 August i 988 J. K. Furdyns R35

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Cd! __ xZnx Te, in that the 3d shell of the Mn + + ion is only
half-filled. This leads to new intra-Mn -+- + electronic transi-
tions, generally in the vicinity of2.2 eV, which dominate the
optical properties of the A~I._ xMnxBvI alloys at high values
of x, and are responsible for their characteristic deep red
color in that range of composition. Furthermore, these tran-
sitions within the 3d shell make wide-gap A ~i __ x Mn~ B VI ma-
terials, such as Zn t _ x Mnx Se and Zn I _ x Mn" S, of consider-
able interest in the context of electroluminescent display
devices.
Although the Mn + + d levels shown in Fig. 5 hybridize
with the sp bands, and thus broaden into d bands, the degree
of such broadening is in fact quite small. We may thus gain a
fairly complete understanding of the intra-Mn transitions by
considering first a free Mn atom, and then an isolated
Mn + r ion occupying a cation site in a ABBV! host lattice.
A free Mn atom has the 3d 54s2 configuration, with the
spins of the five 3d electrons aligned in the ground state ac-
cording to Hund's rule ( i i r t i). In this state the atom has a
total spin quantum number S = ~ and a total angular mo-
mentum L = 0 (since according to the Pauli exclusion prin-
ciple the angular momenta of the five electrons must each be
different, ranging over aU five possible values from - 2 to
+ 2). The lowest excited states of the atom correspond to
L = 1,2,3, and 4. To make a transition to one of these L rfO
states requires flipping of at least one of the d electron spins
( i j t t ~ ), i.e., a change to the spin quantum number S = ~. In
spectroscopic notation, the states are identified by the label
(2S+ I) L. Thus, the ground (S =~, L = 0) state of the Mn
atom is labeled 6S, and the L = 1, 2, 3, and 4 excited states
corresponding to S = ~ are 4p, 4D, 4F, and 4G, respectively.
Of these, the 4G level (S = ~,L = 4) has the lowest ener-
gy, as shown in Fig. 10. We shaH be primarily interested in
this state, si.nce transitions from the ground state involving
the lowest energy (6S_ 4G) will dominate the optical prop-
erties of the AiI_ xMnxBvl alloyso For this reason, we shall
4F _ _ _ ! approximately 2.2 eV, and constitutes in effect an optical
4 ___
0 ___
I absorption edge in crystals which contain a relatively high
4p
i concentration ofMn (x> 00 I ). This accounts for the charac-
46 _ _ _ <;:~::_:: 4 A,.4 E
4
- 4_2
r energy gap of the system is well above 2.2 eV.
'I
I
6
5
_________ I SA,
Free atom Mil ..... in
crystal field
I energy gap and the intra-Mn++ transitions has the same
FIG. 10. A schematic diagram of the splitting of the lowest excited state of
the 3d 5 level (4G) relative to the ground state (6S) for a Mn + + ion in the
presence of a tetrahedral crystal field. The arrows indicate possible intra-
Mn transitions.
R36 J. Appl. Phys., Vol. 64, No.4, 15 Augusl1988
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also not consider here states with S = ~ (t tit 1 ), etc., aU of
which lie at higher energies than 4G. For an exhaustive ex-
amination of the hierarchy of excited states, the reader is
referred to the classical papers by Tanabe and Sugano,65
McClure,66 or Griffith.67
When the Mn Atom is placed substitutionally in a ca-
tion site of a A HB VI host lattice, it is acted upon by the crystal
fieldo The dominant crystal field interaction arises from the
four surrounding anions, and in this sense the effect of the
crystal field is the same in zinc-blende and wurtzite OMS
systems. The free-atomic states are degenerate, the degener-
acy being 2L + 1. This degeneracy is removed by the crystal
field, which splits the degenerate levels in accordance with
the symmetry of the Mn + + orbitals and of the surrounding
crystal field configuration. The resulting levels are then la-
beled according to their group theoretical transformation
properties. We review the notation here, since it has become
the standard vocabulary ofintra-Mn+ + optical transitions.
The ground state 6S is spherically symmetric and nonde-
generate, and in the crystal field notation is labeled 6AI. The
ninefold degenerate 4G state of the free atom is split into four
levels, labeled in group theoretical notation 4TJ (itself three-
fold degenerate), 4T2 (threefold generate, 4E (twofold de-
generate), and 4A j (nondegenerate). It has been shown by
extensive calculations65-67 that the effect of the crystal field
is to pun the 4T\ and 4T2levels closer to the ground state, and
that the 4AI and 4E levels are almost coincident and practi-
cally unaffected by the tetrahedral field, as illustrated sche-
matically in Figo 10.
Transitions between the 6 S level (S = l' L = 0) and any
of the excited states (8 = ~, L #0) in the free Mn atom are in
principle forbidden by the llS = 0 and parity selection rules.
For a Mn + + ion in the AIlB vI host these selection rules are,
respectively, relaxed by spin-orbit interaction and by the
lack of inversion symmetry of the crystal environment.
Transitions from the 6A I level to any of the excited states
originating from the 4G level thus become possible, as shown
in Fig. 10. Ofthese, the 6A 1 - 4 T j is the lowest energy (and
therefore the most important) transitions. It corresponds to
teristic red color of the AiI_.xMnxBvl alloys even when the
The energy of the 6A]_ 4T] transitions in relation to the
energy gap is shown for Cd l __ x Mu x Te in Fig. 8, illustrating
that either the energy gap or the 6A 1 __ 4T j transitions deter-
mine the absorption edge, depending on which is smaller.
The data points shown in the figure are obtained by piezore-
fiectance experiments, which permit detection of valence-to-
conduction-band transitions even in the presence of consid-
erable opacity resulting from the 6AI .... 4 T] excitationso 68 It is
interesting to note that the temperature dependence of the
qualitative character.
It should be mentioned that, although the earliest inves-
tigations of the strong absorption occurring at 2.2 eV cor-
rectly ascribed it to the 6A I -+ 4 T] transition,69 the origin of
this absorption has nevertheless been the subject of some
J. K. Furdyna R3S
controversy. In particular, several authors 7\). 71 have ascribed
it to a transition from the top of the valence band to the e;;
level shown in Fig. 5. Such participation of the valence band
has, however, been ruled out by reflectance experiments car-
ried out in the presence of an external magnetic field, as
follows. 72 As will be shown in Sec. V, the Zeeman splitting of
the valence band is enormous (of the order of 100 meV at
low temperatures), while Zeeman splitting of the d electron
levels themselves is at least two orders of magnitude smaner.
Thus, if the 2.2-e V excitation involved the valence-band edge
as the initial or final stage, this transition would manifest
strong, easily observed spUttings when a magnetic field is
applied. In the reflectance study referred to above, such
splittings are unmistakable in those features identified with
the energy gap, but are definitely not present in the 2.2-e V
transition. This experiment constitutes definitive evidence
that the transition occurring at the energy marked Mn 2 + in
Fig. 8 originates from the intra-Mn (i.e., bAl·.... 4Tj ) excita-
tion.
As might be intuitively expected. the transitions indicat-
ed by arrows in Fig. 10 should broaden as the Mn content of
the sample increases, so that the °A 1-> 4TI line may in fact
overlap the 6A 1 --> 4 T2 and other possible transitions. The var-
ious transitions shown in Fig. 10 by arrows should, however,
be resolvable in very dilute systems. Indeed, optical absorp-
tion experiments in Zn 1 _xMn"Bv1 alloys [where intra-
Mn + + absorption may be investigated in the limit as x 0,
since Eg (x = 0) > 2.2 eV in this material] do show a broad
structure 73 •74 that has been ascribed to transitions from 6AI
to 4T1, 4Tz, and 4A l' 4E levels, respectively.
It is, finally, important to point out that the 6A I and the
4T! levels are of principal importance in photo- and electro-
luminescence of wide-gap DMS. As is wen known, e1ectrolu-
minescence involving Mn in dilute Zu1_xMuxSe and
Zn, _ xMnxS systems is particularly efficient, and finds ap-
plication in flat panel display devices. 75. 76 The mechanism of
electroluminescence is understood as follows. When a vol-
tage is applied to the material, hot electrons are injected into
the bulk. These cause excitation ofthe Mn + + ions to the 4T[
state (whether by direct impact ionization of the Mn + + or
by some form of resonant excitation transfer), which then
return to the ground state by emitting the characteristic yel-
low light. The most efficient performance of electrolumines-
cence appears to be in rather dilute samples (x ~ 0.03). The
literature on this technologically important aspect of Zn-
based A~I_ xMnxBV[ alloys is quite vast (much ofit concern-
ing identification of the excitation transfer mechanism be-
tween the injected ballistic electrons and the Mn -+ + ion),
and the interested reader will find a thorough discussion of
this subject in several excellent reviews, especially those de-
voted to electro luminescence in Zn 1 _xMnx S.75.76
D. Itt final comment on nonmagnetic properties of OMS
Although the properties of the energy bands arising
from the sp electrons are necessarily intertwined with the d
electrons, the picture which emerges from the above presen-
tation is that, in describing optical properties, the two elec-
tronic systems (the sp bands and the d electrons) may, as a
very good approximation, be considered independently. The
R37 J. Appl. Phys., Vol. 64, No.4. 15 August 1988
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behavior of both systems is remarkably systematic, and our
(T understanding of them rather complete. 6!l It is this thorough
quantitative understanding ofthe sp band picture which per-
mits us to formulate and identify with confidence the new
contributions arising form the sp-d interaction, which be-
come strikingly manifest in DMS in the presence of finite
magnetization, as will be discussed in Sec. V.
IVo MAGNETiC PROPERTIES OF DMS
We now present an overview of the magnetic properties
of the A~I__ x Mn"B v1 alloys as they are presently understood.
While the magnetic properties are interesting in their own
right, they also bear on the electrical and optical properties
of these DMS materials through the mechanism of the sp-d
exchange, as will become evident in Sec. V. This gives addi-
tional impetus for the need of obtaining a clear picture of
magnetism in DMS at both microscopic and macroscopic
levels.
A. The exchange interaction between Mn + +- ions
Underlying the static and dynamic magnetic properties
of the A~l _xMllxBvr alloys is the exchange interaction be-
tween Mn+ + ions. We therefore begin by reviewing the re-
sults of recent studies, both theoretical and experimental,
concerning the Mn -t + - Mn + + exchange.
-Jo
A major achievement in the recent past has been the
demonstration of the role played by the anion in mediating
the interaction between Mn + -t ions. This is borne out by the
theoretical calculations of Larson et at.,37 who have em-
ployed a perturbative approach to determine the exchange
integrals in DMS. They find that both the nearest-neighbor
exchange process (described by the integral J) and the next-
nearest-neighbor exchange (described by J NNN ) are antifer-
romagnetic, and that J is approximately five times larger
than J NNN • More importantly, it is possible to determine the
hierarchy of mechanisms constituting the Mn + + - Mn + +
exchange interaction. The type of exchange processes are
found to faU into three categories: two-hole processes, one-
hole--one-electron processes, and two-electron processes,
The overwhelming contribution is from the two-hole pro-
cesses: this is the superexchange mechani.sm, which can be
viewed as an indirect exchange interaction mediated by the
anion (and thus it involves the valence band, since the anions
dominate the properties of the valence band in AIlBvl-based
semiconductors). The one-hole-one-eIectron processes (the
Bloembergen-Rowland interaction) account for only 5% of
the exchange interaction,77 while the two-electron processes
are negligible. 37
Experimental measurements of the exchange integral
have been made using a wide variety of techniques-high
field magnetization,78-80 neutron scattering,81-83 Raman
scattering,84 and low field magnetic susceptibility.38 The
first three techniques provide the most direct and reliable
measurements of J, and we briefly discuss the results of one
of these methods, Le., the high field magnetization, as an
iUustrative example.
As we shall show later, the high field (B> 10 T) mag-
netization shows a striking steplike behavior as a function of
J. K. Furdyna R3?
magnetic field. This can be observed either in direct magneti- 60
zation experiments78,80 or in the optical splitting of the band- o Znl_X MnxTe
edge exciton. 79 The fields at which these steps occur give a • COI-X MnxTe
direct measure of the nearest-neighbor exchange integral J. 40
Larson, Hass, and Aggarwa1 85 have performed a thorough
analysis of high field magneto-optical and magnetization :;c
data in Cdl_xMn x Te and Cd1_xMnxSe, taking into ac-
~
count the effects of distant neighbor interactions. They find 20
values of J = - 6.3 and - 7.9 K for the telluride and the
selenide, respectively. and the values of JNNNIJ to be
around 0.2 for Cd1_xMn x Te and 0.3 for Cdl_xMnx~k Ob-~~~ __-L__ ~ __L -__ L-~ __-J
The results of the available measurements of J are sum- 0.0 0.2 0.4 0.6 0.8
marized in Table IV. Some trends are worth pointing out: )(

For alloys with the same cation, the exchange integral in-
creases with decreasing anion size (namely, in the order tel-
luride, selenide, sulfide). Also, for the same anion, the value
ofJ for the cadmium alloys is comparable to that of mercury
alloys, but is lower than J for the zinc alloys. To a large
extent this behavior of J probably reflects the changes in the
lattice constant. An interesting physical explanation for
these trends has been proposed by Spalek et al. 38 on the basis
of the distortion of the tetrahedral bond geometry and its
effect on the mediation of the Mn++ -Mn+ + interaction by
the intervening anion.
FIG. 11. Magnetic phase diagram for Zn'_xMuxTe and Cd' .. xMuxTe
(Cd,. x Mnx Te data points are from Ref. 85; Zu'_xMllxTe points for
x> 0.3 are from Ref. 84, and for x<0.2 from Ref. 87; some authors, e.g., Ref.
89, observe higher T. values for Cd, _ xMn, Te than those reported in Ref.
85, but always below Tg for Zn, _ "Mn" Te). (after Ref. 16).
ceptibility corresponds to a genuine phase transition, we
have to conclude that the low-temperature phase is a disor-
dered but "frozen" state, such as a spin glass.
We shall now proceed to discuss the susceptibility and
magnetization behavior in the two phases shown in Fig. 11.

B. Static magnetic properties 1. The paramagnetic phase

Low field static magnetic susceptibility measurements Despite extensive magnetization measurements on the
indicate that the AlI_ x MnxBV1 alloys exist in different mag- A~I_xMnxBvI alloys, the analytic formulation of this prob-
netic phases, depending on the Mn concentration x and on lem is still limited to the special cases onow Mn concentra~
the temperature T. Figure 11 shows the magnetic phase dia- tion or of high temperatures. We will discuss the various
gram for Zn,_xMnxTe (Ref. 86) and Cd 1 _ x Mn x Te,87 analytic and empirical expressions which describe the sus~
which is qualitatively typical of all DMS. The phase diagram ceptibility in quantitative terms in various limits.
consists of two regions: a high-temperature paramagnetic a. The dilute limit. When the concentration ofMn++ is
phase and a low-temperature frozen phase, The latter phase small (x < 0,01), the Mn + + spins can be regarded as isolat-
generally occurs when x> 0.2 (as suggested by the major ed, i.e., independent from one another. The magnetization M
portion of Fig. 11). but recent work has shown that spin is then described by the Brillouin function, and we can write
freezing can also occur for lower values of x at very low M = - xN~Mn J.ln(Sz)
temperatures. 24,88-90
In mapping this diagram, the phase boundary is based = xN0f5Mn J.lsSBs [gMIl f.i.n SH l(kBT) J ' (7)
solely upon the occurrence of a cusp in the temperature vari- where (Sz) is the average spin per Mn site, No is the number
ation of the low field static magnetic susceptibility.86,87,91 of cations per unit volume, Bs is the standard Brillouin func~
Neutron diffraction measurements show that the low-tem- tion, H is the applied field, and S = ~ for Mn + +. The sign
perature phase does not exhibit any long range magnetic difference between M and (Sz), and between <Sz) and B s' is
order.92.93 Assuming that the anomaly observed in the sus- a consequence of the relation between the magnetic moment
and the spin of the electron,
TABLE IV. Nearest-neighbor Mn+ +- -Mn" .. exchange integrals J for !J.= -gJ.lnS,
Al'_xMnxBV( alloys.
In the low field or high-temperature limit [I.e.,
gp. eSH( k B T) « 1], Mis linear in H, and the static magnetic
Alloy J(K) Source
susceptibility X, defined by M = XH, is of the Curie form
Zn, _ ,MnxS - 16.1 Ref. 83 X = C,;xIT, (8)
Zn, _xMnxSe - 12.3,-13 Refs. 83,78
Zn'_xfv1nx Te - 9.5, - 10.0 Refs. 83,80 where
Cd'_xMnx S - 10.6 Ref. 84
Cd'_xMnx Se -7.9, - 8.3 Refs. 85,78 (9)
Cd1_,MnxTe - 6.3, - 6.9 Refs. 85, 38
Hg'_xMnx S h. High-temperature expansion ofX for arbitrary x. For
Hg,. xMnxSe -10.9 Ref. 38 OMS of arbitrary x, the magnetization M cannot be ex-
Hg,_xMnxTe -7.15 Ref. 38 pressed by the standard Brillouin function because of the
Mn-Mn interactions. At low fields, however, 1~1 is found to

R3S J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna RSS

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be linear in H, as in the dilute case, again allowing us to
define the static susceptibility X. As shown in Fig. 12, experi-
mental measurements of magnetic susceptibility indicate
that at high temperatures X displays a Curie-Weiss behav-
ior,9!
x = C(x)/[T - B(x)J.
The Curie-Weiss temperature 8(x) obtained from experi-
ment is negative, indicating antiferromagnetic interactions
between the spins.
The high-temperature expression for X can be analyti-
cally derived by representing A~I_. "MnxBvl alloys as ran-
domly dilute magnetic systems with antiferromagnetic Hei-
senberg interactions. The calculation of X in the
high-temperature limit yields 38
X = CoX/(T + BoX),
where Co is the Curie constant already defined in Eq. (9),
and B(x) is expressed as BoX. By considering nearest-neigh-
bor interactions only, the parameter go can be calculated,
with the result
where Z is the number of nearest neighbors (Z = 12 for
zinc-blende and wurtzite DMS), and J is the nearest-neigh-
bor exchange integral. Note, then, that J can be estimated
from experimental measurements of (I(x) = BoX; and, con-
versely, that the high-temperature X can be calculated ana-
lytically for any x if J is known for the given alloy family.
For higher values of x at low temperatures, experimen-
tal results show a departure from the Curie-Weiss law, in the
form ofadownturnin the plot ofX-I vs T, as seen in Fig. 12.
This downturn is observed in aU A~I_ xMnxBvl alloys. There
has been no quantitative analysis made of this behavior.
However, it can be qualitatively understood36 by induding
higher-order expansion terms in the calculation of X.
c. A general phenomenological formulation of magneti-
zation The two cases discussed earlier (i.e., the dilute limit
~?]'
. ..
CdMnSe " ,
, .'
" . " ~.
to" " ,,"
45, , , . " also shown in the figure. The magnetic fields at which these
3~.· '
.'
"
, ,. 25.'"
40
0
0 ..
.
0
5
. 0'
0 100 200
T(K)
FIG. 12. Inverse magnetic susceptibility as a function of temperature for
Cd,.o xMuxSe of various mole fraction (given in atomic percent in the fig-
ure). Note the linear Curie-Weiss behavior above 40 K, the characteristic
downturn of x·-
1 at lower temperatures. and the cusp seen in all but the
x = 0.05 data, signaling the spin-glass transition (after Ref. 91).
R39 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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and the low field, high-temperature limit) allow an analyti-
cal description of the magnetization, or at least of the low
field susceptibility. As we mentioned earlier, for arbitrary
values of x and T the standard Brillouin function is inade-
quate for explaining the magnetization data. However, there
( 10) still is a qualitative similarity between the observedM vs H
behavior and the Brillouin function. Based upon this resem-
blance, Gaj, Planel, and Fishman94 proposed an empirical
but very useful expression by replacing the magnetic ion
mole fraction x and temperature T in Eq. (7) by effective
values X etr and Telf , i.e.,
M=XeffNoftJ.lllSBs([gf-LeSH/(koTctr)]) , (13)
where Xeff and Telf are phenomenological fitting parameters.
The profile ofthe M vs H curve is determined by Telf , which
is a function of both x and T; and the correct magnitude of M
(11 )
is obtained by adjusting x etf • While there has been no rigor-
ous justification of Eq. (13) on analytical grounds, it is ex-
pected to follow from the mean field theory. The usefulness
of Eq. (13) lies simply in the fact that Xeff' and Teff can be
tabulated as a function of x and T for each family of DMS.
(12) d. Highfield magnetization. At very high fields (B> 10
T) even the empirical expression fails, and the magnetiza-
tion shows a steplike behavior as a function of field. 78-80 This
is a direct consequence of the existence of antiferromagneti-
cally coupled nearest-neighbor pairs, and is easily explained
as foHows. The energy level scheme for a pair of Mn + + ions
is
E= -J[Sy(Sy+ 1) -¥] +gpBmH, (14)
where J is the nearest-neighbor Mn + + -Mn + + exchange in-
tegral; the parameter S1 is the total spin for a pair, which can
take integral values from 0 to 5; and for each value of ST' m
takes values - ST' - Sy + 1,,,,,ST' For J < 0, the ground
state is nonmagnetic at zero field, with S1 = 0, and it re-
mains the ground state as long asgj.LBH IJ! -1 < 2. While this
condition holds, pairs do not contribute to the total magneti-
zation. However, once the value of gil EH IJ I-· J exceeds 2,
the energy for Sy = m = - 1 becomes the ground state, as
shown in the upper part of Fig. 13. Suddenly there is a contri-
bution to the magnetization from all the pairs, and this re-
sults in a step in the magnetization (lower part of Fig. 13).
Other such steps are similarly predicted for higher fields, as
steps occur hence provide a direct measure of J .
2. The spinaglass phase
As we remarked earlier, the low field magnetic suscepti-
bility of the A~I_ "Mn,;B VI DMS shows a well-defined cusp at
a critical temperature Til (as seen in Fig. 12), signaling a
possible phase transition. This serves to define a magnetic
phase diagram, showing the boundary between the high-
temperature paramagnetic phase and the low-temperature
300
frozen phase, shown in Fig. 11. The low-temperature phase
is macroscopically disordered and displays many of the
characteristics of a spin-glass state. In particular, the low-
temperature specific heat has a linear temperature depend-
ence and, at least in samples with x < 0.65, does not show any
anomaly at T g • 87 Furthermore, remanence effects and irre-
J. K. Furdyna R39

"-
w
4 6
9/-LeH/IJI
FIG. 13. Energy level scheme for a pair of Mn + + ions, showing how steps
occurin the magnetization at high fields. The relative size ofthe steps in Mis
exaggerated for clarity (after Ref. 16).
versible phenomena are clearly observed in magnetization
studies below Tg (Refs. 86, 87, and 91) as illustrated, for
example, by the difference between field-cooled and zero-
field-cooled susceptibility data shown in Fig. 14. Although
the precise nature of this phase remains a subject of some
controversy (for example, recent work l8 suggests that the
low-temperature behavior of the A~I__ x Mnx B VI alloys is clos-
er to that of a random field magnet) we wiU for the present
adhere to the tradition of calling it a spin glass, with the
understanding that the rigorous magnetic classification of
DMS alloys is yet to come.
The spin-glass behavior in DMS has frequently been at-
tributed to frustration of the antiferromagnetic interactions
between the Mn + -;- ions, arising from the lattice topology of
the A~I_ x Mn" BVI alloys.95 This i.s based on theoretical argu-
ments which show that, for a diluted magnetic fcc lattice
with nearest-neighbor interactions only, a spin-glass state be-
comes possible when the magnetic ion concentration exceeds
a percolation threshold of x~O.19.96 Indeed, an extrapola-
tion in Fig. 11 of an experimental results obtained for tem-
peratures above -4.2 K tends toward x:::::O.2. This feature
has been traditionally taken as evidence that frustation is the
underlying mechanism of spin-glass formation in DMS.
However, it is now clear that the spin-glass phase can form
for arbitrarily sman x at sufficiently low temperatures (see
Fig. 11), as has indeed been observed for Cd! _ x Mn.. Se,8M
Zn1_xMn x Te,89,90 Zn 1 _ x Mn"Se,89,9() and Hg1 __ xMnx Te. 24
For this reason, and because fcc and hcp lattices do in fact
anow for antiferromagnetic order of the third kind (see be-
R40 J. Appl. Phys., Vol. 64, No.4, 15 August 1968
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• CdMnSe
aCdMnTe
1L-_-L_-----L..............-
o 4 8 12 16 20
T(K)
FIG. 14. Irreversible thermoremanence effects observed in the magnetic
susceptibility X in Cd, _xMnx Te and Cd 1 _ xMnxSe of various concentra-
tion below the spin-glass transition cusp. Arrow pointing to the right indi-
cates zero-field-cooled data, arrow to the left corresponds to field-cooled
data (after Ref. 91).
low), we shall deemphasize the role of frustration as a pri-
mary mechanism of the spin-glass formation (see Sec. IV C,
below).
Some authors 87 further divide the low-temperature
phase into an "antiferromagnetic" region for x > 0.65. This
is based on specific heat measurements on a sample of
Cd! _xMux Te with x = 0.68, which showed an anomaly in
the specific heat at the same temperature as the cusp in X We
will resist fonowing this description, arguing that there is no
convincing evidence that the system tends to iong range or-
der. There may, however, be other, as yet not identified, rea-
sons for making a distinction between what have originally
been labeled "spin-glass" and "antiferromagnetic" regimes.
A more systematic exploration of magnetic properties in the
x> 0.7 region, with a view of identifying the nature of mag-
netic interactions in this range, is to be strongly encouraged.
For a further discussion of magnetic susceptibility as
wen as specific-heat studies in A~I_.xMnxBvl alloys, the
reader may wish to refer to the thorough and extensive re-
view article by Oseroff and Keesom. 97
3. Neutron diffraction
Neutron diffraction has been used to probe the
magnetic order in Zn j _ x Mnx Te, 93 Zn 1 _ x Mnx Se,98 and
Cd l _ xMnx Te. 99. 1OO We discuss the Zn 1 __ xMnx Te results as
an illustrative example. The powder diffraction patterns for
this case consist of zinc-blende nuclear Bragg peaks, super-
imposed on a diffuse background. 93 The main feature of the
diffuse scattering is broad magnetic peaks, shown in Fig. 15,
which are most intense at low temperatures and which
J. K. Furdyna R40
 tion e- KR , from which one can estimate a "correlation
SOOr
length" K-- 1 (see Fig. 3inRef. 93). The temperature depend-
400
ence of the correlation length is a universal function for all
, the Zn 1 _ x Mn x Te samples studied,'B.lOo and flattens off at
~

(J) 0----+ -----+----+-----+--

illl)
-~
(lOa)

2.0 .:; low temperatures, as illustrated in Fig. 17.

!-
2:
~ 400
t)
0----'-- --;----il-i-------+----- ---+------ +
~----------------------------------------
o L-.b (0 I'S 20
i
25 30
SCATTERING ANGLE (DEGREES)
FIG. 15. Neutron counts as a function of scattering angle observed on a
powder sample ofZu 1 _ xMnx Te (x = 0.594) at three temperatures. Only
the diffuse magnetic peaks are shown; the labels (Ill) and (200) mark the
location of the corresponding nuclear Bragg peaks, which have been re-
moved for darity. The continuous lines are fits to a model described in Ref.
93. The dashed lines show the background count intensity. Note that the
diffuse peaks broaden as the temperature rises, indicating that the size of the
AFM-HI clusters decreases with increasi!lg temperature (after Ref. 7).
broaden and weaken with increasing temperature. As dem-
onstrated in the references cited above, the positions of the
diffuse peaks are a signature of type III anti/erromagnetic
order (AFM-III), which is illustrated for zinc-blende crys-
tals in Fig. 16.
The widths of the diffuse magnetic peaks are always
much greater than those of the Bragg peaks, implying that
the above antiferromagnetic order is only short range (i.e.,
confined to small clusters). The angular dependence of the
magnetic diffuse scattering can be fitted theoretically to ob-
tain magnetic correlations between a given spin and succes-
sive shells of neighbors comprising such clusters. It is then
found that the sign sequence of correlations is again consis-
tent with the AFM-III order. 93 The spatial decay of correla-
tions 100 can be described by an exponentially decaying func-
Neutron diffraction studies of Cd1_xMn" Te and
1.0 ~ Zn I _ x Mnx Se yield much the same results as for
;- Zn1_xMnx Te, showing spin cluster formation, AFM-III
u
2.0 ~ short range order, and saturation of the diffuse magnetic
(fl peak widths at low temperatures.92.9S.99 Here the case of
1.0 Ul
o Zn 1 _ x Mnx Se is especially interesting in that for x> 0.30 this
a::
(.,) material crystallizes in the wurtzite structure. Low-tempera-
ture data then reveal the existence of spin clusters correlated
in the wurtzite version of the AFM-III antiferromagnetic
order98 (i.e., that displayed by wurtzite .8-MnS), as shown
in Fig. 18.
It is interesting to observe that, if we view the Mn ions
with opposite spins as different atoms, the AFM-III order in
zinc-blende crystals (Fig. 16) is crystallographically identi-
cal to the chalcopyrite structure, i.e., a tetrahedrally bonded
structure which accommodates two types of cation, e.g.,
CuFeSz or CdGeAs 2 • Similarly, the wurtzite form of AFM-
III shown in Fig. 18 is identical to the wurtzite-chalcopyrite
crystallographic structure, such as BeSiN2 • These two struc-
tures appear to be the only naturally occurring tetrahedral
structures with the chemical formula ABel' accommodat-
ing two types of cation (Aand B) and one anion (C).tol This
observation may provide a clue as to why, of the various
antiferromagnetic structures possible for fcc and hcp crys-
tals (type I, II, and III), 102 the tetrahedrally bonded zinc-
blende and wurtzite DMS are predisposed to form the AFM-
III order.
ZOI_XMn)(Te
x -0.565
1.2 '-
,;'

1.0- /
Jf
,;'
/
Zinc Blende Type - ill
Structure AFMorder 0.8-
,V
z , r/
~ ¢'
-v."" 0.6- //
o
-0- -0-1
I
041- I

I
0.21- ITg
I
I
J_ It: I I I I I I
0.° '---'--20"':0-'--"'--4"'0---'-60-'---'--9'-0--'--'
0
TEMPERATURE (K)
• M n (1') 0 M n (-t) 0 S1!I
FIG. 17. Inverse magnetic correlation length If/ as a function of tempera-
ture, determined by neutron diffraction for Zn1_xMnx Te, x = 0.565; Gr."
FIG. 16. A unit cell for the AFM-III structure of zinc-blende crystals, denotes the nearest-neighbol" Mn-Mn distance (after Ref. 100). The spin-
shown side-by-side with two zinc-blende unit cells. Note that the AFM-IH glass transition temperature 1~ for this value of x is also indicated. Note
is tetragonal rather than cubic. that If, levels off below this temperature.

R41 J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna R41

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FIG. 18. An orthohexagonal unit cel! for the AFM-HI structure for wurt-
zite crystals, shown side-by-side with two wurtzitc orthohexagonal cells.
C. Empirical picture of magnetic ordering
While we still lack a detailed microscopic picture of the
spin correlations in the A~l_ x Mnx B VI alloys at low tempera-
tures, it is useful to develop a plausible, although admittedly
very empirical, scenario. OUf model is similar to that pro-
posed by Mydosh 103 in a discussion of metallic spin glasses.
The key insight on which this picture rests is derived
from the neutron diffraction studies, which reveal that the
antiferromagnetic interaction between neighboring spins
leads to the formation of clusters of short range AFM-III
order. Little is known about the process of nucleation of
these clusters. A diluted magnetic system, even when it is
ideally random, must display local fluctuations in the spin
distribution, and one can only guess that it is these spatial
fluctuations which determine where the clusters actually be-
gin to form. The clusters grow in size with decreasing tem-
perature, which is directly inferred from the steady sharpen-
ing of the linewidth of the diffuse magnetic peaks (Figs. 15
and 17). As this process continues, it is reasonable to expect
that a temperature will eventually be reached at which the
cluster size is sufficiently large for the correlated regions to
"touch." This leads to two consequences: the clusters, while
retaining their original identity, must interlock, which af-
fects their ability to respond to an external field; and they
must cease to grow. The latter is consistent with the leveling
off of the correlation length revealed by neutron scatter-
. 9199Th'
mg. -. is process 0 f custer
I growt h and subsequent inter-
locking is illustrating schematically in Fig. 19.
We believe that this interlocking process of different
clusters (with short range intracIuster order, but no long
range order) can be approximately equated with the spin
freezing indicated by the cusp in the magnetic susceptibility.
Experiments show that the spin-glass transition temperature
Tg is an increasing function of x and J. This is easily ex-
plained by the above picture. It is intuitively evident that for
higher x the number of clusters per unit volume will be larg-
er, i.e., that they will be closer together. It is also to be expect-
R42 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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. Type-ill AFM .
. cluster . '..:...,
··~lHf··~: .
'. ~ '.'
~ .' fez?-
~.
T »Tg 1
:3 4
FIG. 19. An empirical picture of clusters having internal short range AFM-
III order. The clusters grow with decreasing temperature, and eventually
interlock, as shown schematically for four successively decreasing tempera-
tures. III the picture proposed here, (3) would roughly correspond to the
spin-glass transition temperature.
ed that at any given temperature the size ofthe clusters is an
increasing function of J and of x. Hence, for higher J and
higher x the "locking" will occur at higher temperatures,
consistent with the observed behavior of Tg • This increase in
Tg with x should be particularly rapid in the high x limit,
where the small cluster separation and their expected larger
size cooperate to bring about the locking process. This is
consistent with the rapid up-tum in the plot of Tg vs x seen
for x > 0.6 in Fig. 11.
In the low x limit, below the nearest-neighbor percola-
tion value of x:::::; 0.19, the process shouId be qualitatively the
same, the interlocking occurring at considerably lower tem-
peratures, commensurate with the lower values of the
further-neighbor exchange integrals. This is indeed consis-
tent with the "tailing" of the phase diagram observed below
x = 0.19 at very low temperatures,88-90 shown in Fig. 11.
The above picture-starting from independent individ-
ual clusters and ending with an interlocked cluster
network-also survives a more detailed examination of the
immediate vicinity of the locking temperature, where clus-
ters and loose spins coexist, as revealed by recent experi-
ments on the relaxation of thermoremanent magnetization
in Cd I _ x Mnx Te. 104 This was discussed in some detail in the
article of Furdyna and Samarth, where this picture was first
proposed. 16
D. Dynamic magnetic properties of DMS
While the static magnetic properties of DMS are now
reasonably wen in hand (with the possible exception of the
J. K. Furdyna R42
........ ·····························::r·:·················
microscopic nature ofthe freezing process), dynamic mag-
netic behavior of these alloys is at this point not well under~
stood. This void in our knowledge is particularly important,
since any attempt to understand the low-temperature frozen
phase in DMS must necessarily deal with the problem of spin
dynamics. Furthermore, the dynamical magnetic properties % 1
<l
bear directly on several practical applications of DMS: for
instance, magneto-optical devices depend on the ability of
magnetization to respond to a driving field, and the speed of
l"O.3!1
such a device ultimately depends on the spin dynamics. 105 So Jt-O.!i3
far, most of the information about the dynamics of the !
.\:,.;0.25

Mn + + spin system comes from electron paramagnetic reso-
nance (EPR),106-11O some recent muon spin relaxation
(,uSR) measurements, III and studies on the relaxation of the
thermoremanent magnetization. 104 Of these, the EPR ex-
periments are most extensive, and we shall focus on them
here, EPR measurements on very dilute DMS materials
(with a Mn concentration of less than, say, 1% or 2%) es-
sentially give information about isolated Mn ions, and per-
haps pairs and triplets. The EPR line shape is then compli-
cated by features such as hyperfine and fine structure,
However, once the Mn concentration is greater than a few
atomic percent (as is typical in a DMS alloy), we have a
strongly exchange-coupled system of spins, and the EPR
then probes the dynamics of such a system as a whole. In this
situation, the EPR is characterized by very pronounced and
yet remarkably simple dependence on temperature and sam-
ple composition, The salient features of this behavior are
illustrated in Fig, 20. The first thing to note in the figure is
that the EPR linewidth broadens dramatically as the tem~
perature is lowered and as the Mn concentration is in-
creased, Furthermore, at a fixed temperature, the EPR
linewidth shows a clear dependence on the anion in the sys-
tem: namely, given a fixed cation (e,g" Cd++), the
Iinewidth increases with increasing anion size (i.e., in the
order Cdl_xMnxS, Cd1_.xMnxSe, Cdl_xMn~ Te),
Despite ample experimental data, and the universality
and apparent simplicity of the phenomena described above,
there have been few attempts at a theoretical interpretation
that go beyond phenomenological models, The Lorentzian
nature of the EPR line shape, along with the large isotropic
exchange in these materials (J is around 10K), suggests that
the resonance is exchange narrowed, the EPR width being
primarily determined by some anisotropic spin-spin interac-
tionY2,1l3 The linewidth of this Lorentzian resonance at a
temperature T and at Mn concentration x can then be for-
mulated as\!4
where X is the static magnetic susceptibility, (AH) is the
linewidth at infinite temperature, and the function r( T,x)
represents the contribution from dynamic spin-spin correla-
tions,
In order to make further headway in formulating the
theory of EPR linewidth-and of spin dynamics in gen-
eral-one must now address two fundamental questions:
What is the dominant anisotropic pair interaction that is
responsible for the line broadening? How do the spin-spin
correlations evolve with temperature?
In response to the former inquiry, a first guess might be
150 IDO 50 100 150 2.00 50 150 200
TlK)
FIG. 20. Temperature dependence ofthe electron paramagnetic resonance
linewidth for Cd, _ x MnxBV1 family of alloys, for various values ofx. Note
that at any value of x and T, the width ofthe line progresses with the size of
the anion (from Ref. lIO).
to attribute the line broadening to the dipolar interaction (as
in MnO and MnS, 116 as well as in EuXSrl_XSI(7), However,
it has been shown recently that the dominant anisotropy
cannot be dipolar, 108 The role of dipolar broadening is prin-
cipally ruled out by looking at the variation of the EPR
linewidth with the anion in Cd l _ xMn" Te. Cd 1 _ "MnxSe,
and Cd l _ x Mnx S, It is found that the assumption of dipolar
broadening cannot even qualitatively explain the observed
progression from narrow to wide EPR Hnewidths seen in
Fig. 20 as the anion is changed from S to Te. Furthermore,
the theoretically calculated magnitUdes of (IlH) are in- 00
consistent with those obtained by extrapolating finite tem-
perature data to the infinite temperature limit. This raises
the possibility that the broadening stems from anisotropic
exchange, The exact nature of this anisotropy is still an open
question, However, considering that the Mn-Mn exchange
in the AiI_xMn"Bvl alloys arises from a superexchange in-
teraction mediated by an intervening anion, it is likely that
the solution may lie in a Dzyaloshinski-Moriya interac-
tion 1l8 of the type j),(Si XS), where the strength of the
anisotropic spin-spin coupling is proportional to the spin-
orbit coupling on the anion. Preliminary calculations show
that the relative variation of the linewidth with the anion is
consistent with such an interaction, and the extrapolated
estimates of (AH) are also in the correct range. 110 How-
00
ever, a theoretical formulation of anisotropic exchange in
DMS is needed in order to substantiate the viability of this
hypothesis,
(15) The variation of the EPR linewidth and line shape with
00 temperature bears directly on the evolution of the spin-spin
correlations and the freezing of spins at low temperatures. It
is found that, in the paramagnetic region, the dramatic
broadening ofthe EPR with decreasing temperature is large-
ly due to the temperature variation of the static susceptibil-
ity. As the spin-glass region is approached, the variation of
the dynamic spin-spin correlations becomes more impor-
tant. Unfortunately, it is precisely in this region of interest
that EPR becomes more difficult to measure and interpret,
chiefly because of the extreme line broadening (with full
widths at half-maximum exceeding 20 kG) and because of

R43 J. AppL Phys., Vol. 64, No.4, 15 August 1988 J. K Furdyoa R43

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the deviation of the line shape from Lorentzian behavior. 106
A concerted effort to examine the spin dynamics using dif-
ferent probes, such as inelastic neutron scattering, pSR, and
EPR, will probably be needed in order to shed further light
on this yet unsolved problem of DMS physics.
v. EXCHANGE INTERACTION
We now discuss the exchange interaction between the s
andp band electrons oftheA~~xMnxBvI DMS and the 3d 5
electrons associated with the Mn -I- + ions. It is because of this
sp-d exchange that magneto-optical and high field magneto-
transport properties ofDMS are qualitatively different from
those observed in their nonmagnetic counterparts. In this
context it is important to recall that band structures of the
A~I_xMnxBvI alloys (we are referring to the sp bands) are
themselves very well characterized. This fact enables us to
distinguigh unambiguously the exchange contributions
from other aspects of semiconductor behavior that are non-
magnetic in origin, making it possible to isolate and study
the details of the exchange contribution with precision and
confidence.
A. Theoretical model and approximations
The sp-d exchange interaction influences physical phe-
nomena which involve electrons in the conduction and va-
lence bands (e.g., magnetotransport, interband and intra-
band magneto-optics), exciton levels (e.g., Faraday
rotation), and impurity levels (e.g., bound magnetic po-
laron, giant negative magnetoresistance, metal-semiconduc-
tor transition). We shall develop the model specifically for
band electrons, but the basic concepts and consequence of
exchange interaction (e.g., its effect on the g factors) are
equally applicable to impurity and exciton levels, since all of
these are determined essentially by the same band-edge pa-
rameters.
Consider first a nonmagnetic semiconductor (e.g.,
CdTe or Hgl_xCdx Te) in the presence of an external de
magnetic field. When the field is applied, the conduction and
valence bands are split into Landau levels, each Landau level
being further split into sublevels corresponding to the two
spin orientations of the electron. Various models have been
employed for calculating the magnetic-field dependence of
Kondo-like exchange term Hex to the original Hamiltonian
Ho, so that the total Hamiltonian HT is now 12, 13.22.23
HT=Ho+Hex
= Ho + 2.: Js[>'d(r - R; )8 i °0", (16)
Ri
where Si and 0" are the spin operators for the Mn + + ion and
for the band electron, respectively, Js[>,d is the electron-ion
sp-d exchange coupling constant, and rand Ri are the co-
ordinates of the band electron and of the Mn + + ion, respec-
tively. The summation is only over the lattice sites occupied
by the Mn + + ions.
Two convenient approximations can be made to sim-
plify Hex. First, since the electronic wave function is very
extended, so that the electron "sees" a large number of
Mn + + ions at any time, we can make use of the molecular
field approximation, replacing Si by the thermal average
(8) taken over an Mn + + ions. For paramagnetic systems, if
the applied field H is in thez direction, (8} = (Sz), a quanti-
ty intimately related to the magnetization of the system [see
Eq. (7)].
Second, and again because the electronic wave function
spans a large number of lattice sites, we can replace
pp-d(r - R i ) by xJsp-d(r - R), where R denotes thecoordi-
nate of every site of the fcc (or hcp) cation sublattice, with
the summation now carried out over all R.. We are thereby
expressing the exchange interaction in terms of the virtual
crystal approximation. With these assumptions, we have
Hex = Uz (Sz)x L Js[>,d(r - R), (17)
It
with the summation extending over all cation sites.
As pointed out earlier, a major advantage of Eq. (17) is
that in that form Hex has the periodicity ofthe lattice, This
allows us to use the same wave functions for solving the
exchange interaction problem as those used for diagonaliz-
ing Ho. Let us, as an example, consider a zinc-blende crys-
tal. 120-123 To deal with that problem, the set of basis func-
tions frequently employed is that used in the Pidgeon-
Brown model. Thus, in commonly used notation, for the r 6
band we use the basis vectors
ulO = IM)r = S t, 6

the Landau "ladders" in semiconductors-e.g., the well- U zo = 11, - ~}r6 = S~; (18)
known Pidgeon-Brown model used extensively in the case of
narrow-gap semiconductors. 1I9 We shall not review these for r" bands
models here, but shall simply assume that the Landau level = 1M> =
U 30 (l/.,f2)(X + iy) i.
structure of an electron in a nonmagnetic semiconductor is
described through some appropriate Hamiltonian, which we u40 = i~, ~~) = i( 1//2) (X - iY) t,
shaH denote by H o, and which contains all information re-
quired to describe the semiconductor with the exception of u50 = 1~'1) = (U.J6)[(X-iYH +2Zt].
the sp-d exchange contribution. Uw = I~, -!) = i( 11/6) [(X + iy) 1 - 2Z i]; (19)
and for r 7 bands (which enter into the Pidgeon-Brown for-
1. The exchange Hamiltonian and its basis functions mulation explicitly)
When the semiconductor in question contains localized u70 = 1M) = -i(1/~)[(X-iY)j -Z~],
magnetic moments (e.g., Hgl_xMn" Te), its band structure
will be modified by the exchange interaction of these mo- U so = 11, -1> = (lIv1JH (X + iYH + Z fl. (20)
ments (i.e., the 3d 5 electrons) with band (Le., sp) electrons. It will be instructive to consider the formal conse-
Such interaction is expressed formally by adding a new quences of the presence of Hex in the total Hamiltonian sepa-

R44 J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna R44

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rately for three cases: for a parabolic conduction band, in
order to clearly identify the physical role of Hex; for wide gap
semiconductors, where certain convenient approximations
are allowed, making the problem particularly tractable and
clear; and finally, for the case of narrow-gap DMS, where the
situation is more involved (not because of the presence of
Hex' but because of the details of the original Ho appropriate
for the narrow-gap case).
2. Parabolic conduction band: An idealized Illustration
of exchange effects
We note immediately that the macroscopic average
(Sz) vanishes when H = 0, and the entire exchange contri-
bution given by Eq. (17) thus also vanishes. It is likewise
clear from the form of Eq. (17) that the exchange contribu-
tion is fundamentally linked to the operator CT" and is there-
fore expected to play a significant role in those physical
properties which directly involve the spin state of the elec-
tron. We illustrate the consequences of Hex by considering,
as an example, an electron in the r 6 conduction band of an
open-gap semiconductor, assuming the band to be parabolic.
We can then write the energies of the two spin substates of
the I th Landau level as
E/ (t) = Eg + (l + !)wc + ~(g"'11BH -
E{ (~) = Eg + (l + !}1Uu c -1(g*P R H -
where Eg is the energy gap (the energy is measured relative
to the top of the valence band), We is the cyclotron frequen-
cy, g* is the "band" g factor of the electrons (i.e., that ob-
tained by solving H o), and a is the exchange integral for the
s-like r 6 electrons,
no being the volume of an elementary cell.
The Landau ladder (l + i}w c originates from theoper-
ator (e/ mc) p.A, and the term ± 19* f1- B H from the operator
g*J.tnO'cH, both of which are present in theHo when the mag-
netic field H is nonzero. The term ± !Noax(Sz) arises due
to Hex.
Noting that the exchange contribution xNoa{Sz) to the
Landau level energies always appears side-by-side with the
g*f1-nH, we can then rewrite Eq. (21) in the form
where the upper and lower signs correspond to the i and ~
spin states, respectively, and golf is an effective g factor, de-
fined by
geff =g* -Noax(Sz)/( fln H )
= g* + aM l(gMn fl~H).
Here we have used Eq. (7) to expressgetf explicitly in terms
of the magnetization M.
The situation in a AiI_xMnxBvI alloy is thus essentially
as in a nonmagnetic material, but with the spin splitting de-
scribed through a modified g factor which now, through M,
depends on temperature, composition, and magnetic field
(inasmuch as IV! is given by the Brillouin-like function, and
R45 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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therefore M I H is not constant as the field H varies). In the
low field, high-temperature limit, where Mis linear in H, M /
H in Eq. (24) may be replaced by the magnetic susceptibil-
ity.
The consequences of exchange for a parabolic conduc-
tion (r6) band are schematically illustrated in Fig. 21,
which shows separately the effect of gil< and ge!f' Since the
sign of a is positive, we note from Eq. (24) that in an open-
gap DMS the effect of the exchange term is to oppose g*. The
points to be noted in Fig. 21 are then as follows: When the
magnitude of aM /(gMn f1-~H) =~ge" is less thang* (as can
easily be the case in a narrow-gap DMS such as
Hg! __ xMnx Te, x> 0.07, where g* itself can be quite large;
or at higher temperatures, where M is small), the exchange
contribution simply reduces the magnitude of geff.
When l.lgelf! > ig* I, the sign of the spin splitting is
changed (i.e., gelf is positive, while g* itselfis negative). And
for even larger values of age>;' when the spin splitting ex-
ceeds the cyclotron splitting, the presence of exchange leads
to a mixing of the usual sequence of Landau levels. The fea-
tures illustrated by Fig. 21 remain qualitatively true also
when the bands are nonparabolic, but with the complication
that then the magnitUde of the spin splitting is different for
different Landau levels, and the details of the problem must
Noax(Sz>),
be dealt with numerically, as discussed in Sec. V A 4, below.
(21a)
Noax(Sz»'
(2Ib)
a)
(22)
b)
(23)
C)
res
"""",,,-.......y
(24) FIG. 21. A schematic representation of the spin splitting of the first two
Landau levels of the conduction oa.'1d in the parabolic approximation, with
and without sp-d exchange contributions. With no exchange effects (S, >
= 0), spin spliUing is given by g*l1sH, whereg'" is negative. The right-hand
side of the figure shows the effect of exchange for three successively increas-
ing values of (Sz). For small but finite {S,> (case a), the size of the total
spin splitting g.ifP aH is reduced relative to g*jtBJi. As (Sz) increases (case
b), the sign of the splitting is reversed, owing to the fact that a > O. Further
increase in (Sz) leads to mixing of the Landau level sequence (level 0 + lies
aboue level 1-· ).
J. K. Furdyoa R45
 The contribution of the exchange mechanism to the en- neglected term g*,upaoH, which acts on the spin of the elec-
ergy states of the r)l band is more complicated because of the tron, The magnetic splitting in a wide-gap A~I_xMn"BvI
degeneracy of that band at the r point, Its dominant effect alloy will then qualitatively have the features of "ordinary"
can, however, be expressed by replacing the Luttingter pa- spin splitting (i.e., the same mUltiplicity, symmetry, and se-
rameter K, which is the parameter predominantly determin- lection rules), but its magnitude will be determined entirely
ing the fourfold spin splitting of Landau levels in the r R by the exchange contributions Hex appropriate for the re-
band, with 8 ,124 spective (i.e., r6 or r 8) bands.
(25) As pointed out earlier, Hex can be diagonalized in the
bases (18)-(20). We are primarily interested in the behav-
Here f3 is the exchange integral for the p-like electrons of the ior of the bottom of the conduction (r6) band and the top of
r g band, defined by the valence (r 8) band at k = O. For these two cases, Hex
(3= (XjJsp-d!X)/fi o' (26) leads to the matrices
The values of a and /3 are determined experimentally in
magneto-optical or quantum transport experiments for each
<w r" IH i\ll r" ) _113A
ex - I0
o
-3AI
II (28)
material (see below), and are listed in Table V. With typical and
values of a and the low-temperature susceptibility corre-
sponding to, say, xzO.l, the exchange contribution togeff in 3B 0 0 0
a typical A~I _ "Mn"Bv1 aHoy can be over 100, and the effect 0 B 0 0
('i'r.\Hex !'lI r ) =
on Kelf is even larger. 0 a -B 0
0 0 0 -3B
(29)
30 Exchange effects In wide-gap DMS where
1 aM
Most of the electrical and optical phenomena of interest
in AHBV! materials and their alloys involve electrons and
A= "61 Noax(Sz} = ----- , (30)
6 gMn,ue
holes in the vicinity of the r point. Thus, in order to under- 1 (JM
stand the vast majority of the effects involving sp-d ex- B =6 N o /3x(Sz) = (31)
change, it is sufficient only to consider how the exchange 6 gMn Po
affects the top of the valence band and the bottom of the and
conduction band. a = (S IPp-d IS >1° 0, (32a)
In discussing wide-gap A~i__ xMn_~Bvl alloys, we recog-
{3 = (X IJ sp-d IX) 1°0 , (32b)
nize further that the magnetic splitting due to Hex is much
greater than the Landau andlor spin splitting predicted by
Thus, the quantities A and B are simply terms which deter-
ordinary sp band theory, because in wide-gap materials the
mine the Zeeman splitting of the respective bands. For ex-
effective masses m * are large and the "sp band" g factors [g*
ample, referring to the parabolic case described in the pre-
in Eq. (24) ] are of the order of unity. In the parabolic exam-
ceding section, the term A can be related to the effective g
ple used above we can then neglect the terms containing fwJ c
factor
andg* in Eq. (21). More generally, it is justified-and very
convenient-to neglect the operators (33)
(elm*c)p + g*,unO'"H (27) The corresponding energy levels at the center of the
in Ho, which are responsible for nonexchange cyclotron and Brillouin zone for a wide-gap DMS in the presence of a mag-
spin splittings. In this approximation the magnetic splitting netic field are shown in Fig. 22. This figure is extremely
of the energy levels is due entirely to the exchange term Hex. useful for understanding the majority of phenomena which
Mathematically, however, the operator Hex resembles the occur in wide-gap DMS as a result of exchange interaction.
Note again that the splitting is qualitatively identical to "or-
dinary" spin splitting which takes place in nonmagnetic
TABLE V. Experimental sp-d exchange constants Nul): and NJ3 for the
A;I_xMnxBvl alloys (in eV). semiconductors (two spin levels for r 6' four for r 8)' and in
this sense the exchange contribution can be naturally ab-
Alloy Noa NrfJ sorbed into the concept of an effective g factor whenever the
concept of ag factor is meaningful. The situation differs from
Zn' __ xMnx S the case of nonmagnetic semiconductors primarily by the
Zn, __ x MnxSe 0.26 - J.i1 fact that the magnitude of spin splitting is extremely large,
Zn, __ xMn, Te- 0_18 - 1.05
that its behavior is determined primarily by the properties of
Cd' __ xMllx S 0.22 - 1.80
Cd'_xMllx Se 0_26 - 1.11
the magnetization (Le., that it varies with temperature and is
Cd, _xMllxTe 0.22 -0.88 not necessarily linear in H), and that-in this approxima-
Hg, __ xMllx S tion-it is completely independent of the band structure (ex-
Hg\ __ xMnxSe 0.4 -0.7 cept for the extent to which the band structure affects the
Hg'_xMnx Te 0.4 -0.6 values of a and fJ). However, the selection rules governing
transitions between the levels shown in Fig. 22 remain the

R46 J. Appl. Phys., Vol. 64, No.4, 15 August iS88 J. K. Furdyna R46

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r-'--t---t-+-++- !-i >
_ _--L---+-!--"-+_ !-t >
~----~--~~!+t>
' - -_ _ .J...--_~ + ~ ) I
FIG. 22. A schematic picture of the spin splitting of the top of the valence
band (rs ) and the bottom of the conduction band (ro ) for a wideogap
A;!_ xMnxBvI alloy in a magnetic field. The diagram also shows the electric-
dipole-allowed transitions (arrows) for the two circular polarizations rotat-
ing transverse to the applied field (usually observed in the Faraday geomc
try. designated by u +- and a _0)' and for the linear polarization parallel to the
field (observed in the ordinary Voigt geometry, designated by 11"). The Fara-
day geometry transitions marked a and d are significantly stronger than
those marked band c.
same as between spin levels of a nonmagnetic semiconduc-
tor.
4. Exchange effects in narrow..gtlp DMS
In the case of narrow-gap DMS-owing to the small-
ness of the effective masses and to the large value of g* -the
cyclotron splitting and the band structure contribution to
spin splitting can now be comparable to the exchange-in-
duced splittings, and thus can no longer be neglected. One
then usually proceeds by extending the Pidgeon-Brown
model-which has heen extremely successful in dealing with
nonmagnetic narrow-gap semiconductors, such as lnSh or
HgTe-to include appropriate exchange terms.22.!22,125-!28
Briefly, the Pidgeon-Brown modeI 1l9 expresses the
Hamiltonian Ho as an 8 X 8 matrix, corresponding to the
eight basis functions given by Eqs. (18)-(20). Since Hex can
be diagonalized in the same basis functions, the exchange
interaction contributes only additive terms to those which
are already present in the Pidgeon-Brown formulation, Ll,120
The presence of such additive terms does not introduce any
additional mathematical complexity, and the process of so-
lution of the modified Pidgeon-Brown Hamiltonian is iden-
tical to solving the unmodified case. For mathematical de-
tails of the formulation and solution ofthe problem, we refer
the reader to earlier publications?2,122,125-128
Although the complications introduced into the Pid-
geon-Brown model by the inclusion of Hex are mathemat-
ically rather minor, the presence of the exchange terms
brings havoc into the otherwise orderly behavior of the Lan-
dau ladder. Physically, the primary effect of exchange is to
modify the spin splitting of Landau levels. However, unlike,
say, lnSb, the spin splitting is now determined jointly by
contributions of band structure and magnetization, so that
there is no direct relationship between the cyclotron splitting
(which depends on hand structure alone) and the spin split-
ting, 127 Furthermore, the spin splittings oftlle Landau levels
R47 J. Appl. Phys., Vol. 64, No.4, 15 August ,988
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are now temperature dependent, and are frequently larger
than cyclotron splittings. Finally, the size and sign of the
spin splitting-and thus also the sequence of Landau lev-
els-will now depend on the composition of the DMS alloy,
on temperature, and on magnetic field, This has already been
illustrated qualitatively by Fig. 21 in the connection with the
parabolic conduction band,
A particularly striking effect of exchange interaction on
the band structure is the magnetic-field-induced overlap of
valence and conduction bands in an originally zero-gap sem-
iconductor, such as the case of Hg 1 _ xMnxSe for x < 0,05,
This is in contrast to it nonmagnetic zero-gap semiconduc-
tor, such as HgTe or HgSe, where the application of a mag-
netic field "opens" the gap, The effect can be qualitatively
understood as foHows,
Without the sp-d exchange contlibution, the energies of
the lowest conduction Landau level and the highest vaience
o Landau level move apart as the field increases. The spin
splittings of these levels-being always smaller than the
Landau splittings in a nonmagnetic semiconductor-cannot
compensate for this divergence, and a sman gap (of the order
of! fuv c ) is thus induced by the magnetic field.
The situation in a zero-gap DMS is different in that
there is now a giant contribution to the spin splitting which is
independent of band structure. This effect is particularly im·
portant for the valence band, where the spin splitting due to
exchange can be as much as two orders of magnitude larger
than the Landau energy of the heavy-hole band. As a result,
the top Landau spin sublevel of the valence hand can in-
crease above the lowest Landau spin sublevel of the conduc-
tion band, leading to a truly semimetallic configuration, This
effect has been investigated theoretically and experimentally
by Byszewski et al. 12Y
Bo The physical origin of the sp-d exchange constants
As will be noted from Table III, the behavior of the
exchange constant a and 13 is remarkably systematic: they
are of opposite sign ([3 < 0 and a > 0), the magnitude of f3 is
consistently larger than a, and a and /3 appear to be insensi-
tive to the Mn concentration (e.g., the value of a determined
for Zn\ __ xMnx Te with a specific x will apply to
Zu1_.xMn x Te foral! x),
It is clear that such systematic behavior must involve a
common, and a relatively simple, physical mechanism.
Bhattacharjee, Fishman, and Coqblin 13() were the first to
identify the underlying physics behind the behavior of a and
13. Briefly, these authors point out that there are two pro-
cesses which contribute to the exchange interaction between
band electrons or holes and the 3d 5 electrons of the Mn + +
ions:
(1) There always exists a 1/r potential exchange inter-
action between the band (s or p) and the d electrons. This
process tends to align the spin of the electron parallel to that
associated with the Mn -+- -+- ion, and because of this may be
referred to as aferromagnetic interaction, In our convention,
this process makes a positive contribution to the exchange
constant.
(2) In addition, there is a contribution due to hybridiza-
tion of the 3d slevels with the sand p band electrons, At the r
J. K. Furdyna R47
point, the sod hybridization is forbidden by symmetry, On
the other hand, the pod hybridization is always allowed, and
leads to a very strong negative (Le., antijerromagnetic) con-
tribution to the exchange constants. This negative contribu-
tion due to the pod hybridization turns out to be much
greater in magnitude than the potential contribution de-
scribed under (1) above. 20 •13 !
Since the exchange-induced optical and electrical effects
in the A~I_ xMnxBvI alloys involve primarily band-edge
properties, we conclude that the exchange constant a, which
applies to the r 6 bands (s-like at the r point), arises almost
exclusively from the potential interactions, and is therefore
positive. The exchange integral fJ, on the other hand, de-
scribing the r 8 bands (p-Uke at the r point), contains poten-
tial (positive) as well as hybridization (negative) contribu-
tions, the latter of the two being larger. The value of.B is thus
dominated by hybridization, so that fJ itself is negative and
considerably larger than a. Recently, this problem has been
put on a sound quantitative footing by Ehrenreich and co-
workers,z°,46,131 the predicted behavior being in remarkably
good agreement with the experimental band-edge values of a
andfJ·
To illustrate the relationship of the dominant, hybridi-
zation part of the exchange constants to the band structure
of the material, we write fJ in two parts
f3 = (J pot + /3 hyb ,
where f3 pot is the potential (ferromagnetic) contribution to
f3 and /3 hyb is the pod hybridization contribution. The value
of (Jpot may be assumed to be approximately130 equal to a.
The hybridization part f3 hyh may be written in the form l3(), 131
No {3hY'n = 32V;d( (+0-
e + d
U,:!;
ef!
where Vpd is the hybridization parameter, and the other
quantities have been defined schematically in Fig. 5.· The
value of V]Xl can be found from known values of a and(J, and
is typically close to 1 eV. We note parenthetically that the
Mn + + -Mn + + exchange constants J d -d can be expressed in
terms of the same parameters, since the d-d exchange is
dominated by the superexchange process, involving media-
tion of an anion, which is a twofold step (d-p-d) of otherwise
the same hybridization process. For additional details, we
refer the reader to Refs. 20, 46, and 131.
It should finally be recalled that, as formulated, .B ap-
plies to the r 8 bands and a to the r 6 band, which in wide-gap
DMS happen to correspond to the valence and conduction
bands, respectively. However, in Hg-based DMS with low
values of x (Le., in the zero-gap situation), the conduction
band corresponds to one of the branches of the r 8 band (see
Fig. 6), and conduction electrons are therefore described by
{3, not a, until the gap "opens." This of course accounts for
the difference in sign of the g factors observed, e.g., in zero-
gap and open-gap Hg 1 _ xMnx Te, 132
C. Examples of the effects of sp d exchange interaction
6
The exceptionally large spin splitting of the band edges,
or of Landau, impurity or excitonic levels, which arises in
R48 J, Appl. Phys., Vol. 64, No.4, 15 August 1988
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the A~I_xMnxBvI alloys as a consequence of the sp-d ex-
change interaction, has led to a multitude of new, often spec-
tacular electrical and optical effects. We illustrate this with
several representative examples,
I. Infrared msgnetoaoptlcs In narrowagap OMS
The Landau level structure of the conduction and va-
lence bands of narrow-gap semiconductors can be very effec-
tively probed by infrared interband I27 •132,133 and intra-
band l26 magnetospectroscopy. In DMS, however, the
"traditional" properties of the magneto-optical spectra are
modified in a qualitative manner because of the dependence
of the Landau level energies on the magnetization of the Mn
subsystem M [see Eqs. (6)-(9)]. We describe several such
important modifications.
(a) Because M depends on temperature, the entire Lan-
dau level structure in DMS becomes temperature depen-
dent, leading in turn to a strong temperature dependence of
maglletotransmission spectra, especially where spin-flip
transitions are involved. In sharp contrast, analogous spec-
tra of nonmagnetic semiconductors (e.g., in HgTe or
Hg 1 _ x Cd x Te) are virtually temperature indepen-
dent. 134.135
(b) As a result of the exchange interaction, the spin
splitting of Landau levels [E/ (t) - El (0 in Eq. (21) Jcan
exceed cyclotron splitting (E{ + I (i) - E/ ( i ) 1, again in
contrast with nonmagnetic semiconductors. This can alter
the usual Landau level sequence, and consequently the or-
dering of magneto-optic transitions associated with these
levels. 127
(c) As already discussed, in zero-gap DMS the anoma-
v
HE _
v Cd
+<7\)'
)
lously large spin splitting can also raise the energy of the top
Landau level of the valence band above the bottom of the
(34) conduction band. Thus, instead of opening the energy gap of
a zero-gap semiconductor, here the magnetic field can in-
duce an overlap between the conduction and valence bands.
Furthermore, because this overlap arises essentially through
the contribution of Ivl to the g factor, it can be removed at
very high magnetic fields, where 1'vf saturates, but the cyclo-
tron splitting continues to increase with field. We then have
a magnetically induced semimetal-to-semiconductor transi-
tion, which has a particularly important effect on the se-
quence of interband magnetotransmission peaks. 132
(d) For DMS with a narrow but open energy gap (e.g.,
Hg 1 __ xMnx Te with x> 0.07), interband magneto-absorp-
tion experiments have shown that the electronic g factors
can be large and positive_ 132,133 This feature, associated ex-
clusively with the exchange interaction, is unique to DMS,
since in nonmagnetic narrow-gap semiconductors (such as
HgTe or InSb) the g factor is always negative.
2. Quantum transport
The magnetic field dependence of Shubnikov-de Haas
oscillations also depends on the details of the Landau level
spectrum, and in narrow-gap DMS (e.g., Hg1_xMnx Te)
can be analyzed to yield both the band and the exchange
parameters. The results are quite consistent with the param-
eters obtained from interband magneto-optics on the same
material. 125
J. K. Furdyna R48
 The most striking result of the experiment is the ob-
served anomalous dependence of the amplitude of Shubni-
n-Cd,_xMnxSe
x .. 0.1
kov-de Haas oscillations on temperature, 125.136 As the tem-
T .. 4.2 K m "+1
perature is decreased, the amplitude of the oscillations in o m"O
n-type Hg , ~ xMn" Te or Hg, ~ x Mn", Se at first increases m ,,-!

with decreasing temperature in the normal fashion, but, as ><I>

the temperature continues to decrease, the oscillations at E
some point rapidly disappear, and re-emerge at still lower m"'+!
m"O
temperature with a different (actually opposite) phase. m=-i
The reason for this a priori unexpected behavior is that
the amplitude of Shubnikov-de Haas oscillations contains a
factor 136
(35)
where m* and mo are the effective and free-electron masses,
respectively. Since in DMS the effective g factor [see Eq.
(24) ] is very large and is rapidly changing with temperature
due to the contribution of M, at a certain temperature the
value of the argument of the cosine can go through an odd 0.5 1.0 1.5 2.0
multiple of rr/2, resulting in the disappearance of the Shub- Magnetic Field (Tes!o)
nikov-de Haas oscillations, and their subsequent reemer-
FIG. 23. Magnetic-field dependence ofthe Is and 2p donor levels for an n-
gence with an opposite sign. This same mechanism can in type wide-gap DMS (e.g., Cd 1 _ x Mn"Se). The bottom of the conduction
fact be used to produce the novel magnetothermal oscilla- band corresponds to 0 on the vertical scale. Note that spin splitting is larger
tions, i.eo, quantum oscillations which are observed at a con- thaIl the orbital splitting. The fact that Is ( !) and Is (t ) do not converge at
stant magnetic field by sweeping the temperature. 137 H = 0 is mel1.nt to symbolize the existence of the magnetic polaron associat-
ed with the bound electron (dot) in the Is ( i) state.

ls( ~) -> Is( i) spin-flip transition easily observed. In Fig. 24

3. Electric~dlpole spin resonance of d()nor~bound
electrons
Electric-dipole spin resonance (EDSR) of donor-
bound electrons, first observed in Cd l ~xMnxSe, provides a
beautiful demonstration of the exchange enhancement of
spin splitting and its consequences in a wide-gap DMS. U8
Consider a hydrogenic donor in Cd l _ x Mnx Se, whose ener-
gy levels are shown in Fig. 23. Transitions between the ls( i)
and ls( i) states are normally electric-dipole forbidden.
However, in the absence of inversion symmetry, this transi-
tion is made possible by the admixture of 2p( }) terms to the
ls( t) wave function, and of 2p ( t) terms to the 1$( ~) wave
functions. The operator making this possible in wurtzite
crystals, such as Cd] ~ x Mn ... Se, is the perturbation Hamilto-
nian
we show far-infrared (FIR) magnetotransmission spectra
observed in n-type Cd, _ "Mnx Se, showing the EDSR line at
several temperatures. Note that, for a constant FIR wave-
length, the EDSR line moves to higher fields with increasing
temperature. This manifests the fact that, as the temperature
increases, the magnetization-and thus the effective g factor
for the Is level-decreases, requiring higher and higher
),,, 118.8 lAm
q1l8!!C
...'" 4.2 K
12 K
I::

where cis the unit vector along the c axis, sand k are spin and
(36)
..
o
III
20 K

momentum operators, and A is a constant determined by

inversion asymmetry. As can be seen from Eq. (36), the
interaction is highly anisotropic in nature, and consequently
the selection rules which arise from this mechanism are
highly polarization dependent. 138
Clearly the amount of admixture of2p ( t) terms into the
ls( t} wave function, which determines the strength of the
transition, intimately depends on the energy separation be-
tween the ls( t) and 2p( t) levels. Now at H = 0, this separa-
tion is about 13 meV in Cd, ~ "MnxSe. However, owing to
the enhancement of the g factor by the exchange interaction,
the ls( t) and the 2p(!) levels can be brought sufficiently
close even at a fairly low field (say, 2 T; see Fig. 23) so that
the matrix element is large enough to make the
(I 4 6
Magnetic Field (Tnla)
FIG. 24. Far-infrared magnetotransmission data obtained in the Faraday
geometry on an n-typeCd,_,Mn,Se (x = 0.10) sample at several tempera-
tures. The sharp dip on the slowly varying background is EDSR, allowed by
the mixing of Is and 2p wave functions, as discussed in the text. Note that
EDSR moves to higher fields as the temperature increases, indicating that
the effective g factor for the donor has the same temperature dependence as
the magnetization. The second line which appears as the temperature rises
is ascribed to EDSR of thermally excited conduction electrons (after Ref.
138),

R49 J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna R49

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fields to satisfy the condition
(37)
1Uu=E1s (f) -Else!).
(The structure in the resonance seen in the figure at higher
temperatures is probably due to conduction electron-spin
resonance which emerges as the conduction band becomes
thermally populated, and which corresponds to a slightly
different g factor.)
Since a spin splitting of 20 meV or so can be readily
attained as a result of the sp-d exchange, this situation offers
the interesting possibility of doing spectroscopy on the hy-
drogenic donor levels under conditions when the ls( t) level
crosses the 2p( i) level, or even penetrates into the conduc-
tion band. In nonmagnetic semiconductors such experi-
ments would require megagauss magnetic fields. Such tran-
sitions are, however, possible in DMS under ordinary
laboratory conditions, and should bring new insights not
only into the physics of donors, but possibly even into the
hydrogen atom itself.
4. Exchange splitting of the exciton transitions
Zeeman splitting of the free-exciton ground-state pro-
vides one of the most direct and convenient situations for
measuring exchange effects in wide-gap DMS. 120,121,!39-147
For simplicity, we shall first consider excitons in zinc-blende
A1I~-"MnxBvI alloys, The problem can be conveniently dis-
cussed in terms of Fig. 22, showing schematically the Zee-
man splittings of the band edge, which apply equally well to
the splittings of the exciton level. Also shown in the figure
are selection rules and corresponding polarizations for exci-
ton transitions. Here u- and u+ denote transitions elicited
by light which is circularly polarized in the plane perpendic-
ular to the applied magnetic field (usually realized in the 50-
called Faraday geometry), and 17' corresponds to linear po-
larization, with the electric field of the photon parallel to the
field H (the ordinary Voigt geometry),
The experimentally observed magnetic-field depend-
ence of the exciton transition energies are shown in Fig. 25
for Zn 1 _~ xMnx Te. 147 Qualitatively, there is nothing unusual
about the nature of the spectrum, in the sense that the same
selection rules are involved as in a nonmagnetic semiconduc-
tor. What is unique is the very size of the effect-splittings of
the order of 100 meV or more, to observe which in a nonmag-
netic semiconductor one would require fields of the order of
a megagauss. Second, in practical terms the entire Zeeman
splitting is caused by the exchange term Hex' and is therefore
determined quantitatively by the parameters A and B de-
fined in Eqs. (30) and (31 ). Owing to the size of the splitting
and the ease of measuring sharp exciton lines, this feature
provides an exceptionally convenient experimental tech-
nique for determining a, /3, and the details of magnetization
M, This optical access to 1\1 has been exploited, for exampie,
for observing the high field magnetization steps using exci-
ton splitting as the measuring technique, as illustrated i.n
Fig. 26,
Zeeman splitting in wurtzite A~I_ xMnxBvi alloys be-
haves similarly, with the added minor complication due to
the fact that the top of the valence band is no longer degener-
ate at the r point. This introduces a small splitting of the
exciton spectrum at H = O. Except for this, everything that
has been said about zinc-hlende A~J_~ x Mnx BV1 materials ap-
plies equally well to the wurtzite members of the DMS fam-
ily.
For further details concerning excitons in DMS, the
reader is referred to the excellent and comprehensive treat-
ment of this subject by Gaj,l21
5. Giant Faraday rotation in wide-gap OMS
The exceedingly large Zeeman splitting of the absorp-
tion edge and of the exciton level in wide-gap DMS also

--,-----·-r--·--·--I--~

Zno.95 MnO.05 Te
T =1.4 K
>100
'"
.§
-~--------l
'"...... I
u7 80
<I
(!)
z
}-- 60
}--

--'
CL-
UJ
Z
o}--
u
i:.S 20

__ ~ __ ~ ____ L - -
o 5 iO 15 20
MAGNETIC FIELD (Ti
FIG. 26. Magnetic-field dependence of the energy difference between the d
FIG. 25. Magnetic-field dependence of the energies of transitions a, b, c, and a tral1sitions of the Is exciton inZu, _xMn" Te (x = 0.05) correspond·
and d (see Fig. 22) of the l.l'exdton in Zu'_xMnx Te (x = 0.05), observed ing to the data in Fig. 25. Experimental data are shown by the points. The
at 1.4 K in magnetoreflectance in the Faraday configuration. Solid and open solid curve is the best theoretical fit to the data, including the contribution
circles correspond to transitions observed with the IY+ and (T _ circular po- of Mn + + -Mn + + pairs. The dashed curve shows the Brillouin function fit
larizations, respectively (after Ref. 147). without the pairs (after Ref. 147).

R50 J. Appl. Phys., Vol. 64, No.4, 15 August 1988 J. K. Furdyna R50

Downloaded 30 Jun 2012 to 129.215.149.92. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
results in a proportionately large difference in dispersion
(i.e., large difference in the index of refraction) of the two
opposite circular polarizations oflight in the Faraday geom-
etry, particularly in the immediate vicinity of the band edge.
This in turn provides the mechanism for Faraday rotation,
which attains extremely large values Cofthe order of 1000°/
em kG) at liquid-helium temperatures. 121 The immense size
of the effect is illustrated by Fig. 27.
Because of its size and ease of measurement, Faraday
rotation in DMS-like the spin splitting of the exciton, to
which it is closely linked-has frequently been used as a
diagnostic tool to map the details of magnetization, both
static and dynamic. 105.121,148-151 Its very large size also holds
promise of practical magneto-optical applications in the visi-
ble and near-infrared range, such as isolators, circulators,
and other nonreciprocal devices. 152
Faraday rotation (JF can be expressed analytically in the
form l5 )
()F = ~; {3 - a M IfCtl I,
21k gMnJiB (E; _fi2u/)3/2
where the quantity [~ is a constant defined in Ref. 153, I is
the sample thickness, and fit.u is the photon energy. The form
of Eq. (38) identifies rather transparently three major inde-
pendent factors which determine the value of OF' There is a
contribution from the magnetization M, from the values of
the exchange constants (f3 - a), and from the photon ener-
gy and its proximity to the energy gap, given by the term
involving rw and E g • Parenthetically, since OF involves
/3 - a, and we have already remarked that a is approximate-
ly equal to the part of /3 arising from the potential exchange
interaction (see Seco V B, above), we note that eF is primar-
ily a measure of /3 hy" defined in Eq. (34).
Because of the particular importance (from a device
point of view) of the behavior of Faraday rotation in the
room-temperature region, we note that OF can be recast in a
convenient form for the temperature range where Curie-
10
Cdl_xMnxTe
X =0.23
T=5K
8 H =5 kG
L' 0.351 em
:e
';:
::I
6 FIG. 27. Transmission as a function of wave num-
;::-
~ ber of initially linearly polarized light through a
:ec
...>- 4 day rotation. At ! 5 000 em -- I the rotation exceeds
iii
z T. (For details, see Ref. 1530)
...
w
~
°16,000 14.000
WAVE NUMBER (em-I
R5i J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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Weiss law holds (which includes room temperature). Using
Eq. (10), and reassembling terms, we then obtain fOf a given
A~I_ xMuxBvl alloy the explicit dependence of OF on the
temperature, composition, and photon energy:
OF = P [x/( T + (JoX) ]No(f3 - a)
fh»2
X HI (39)
{[Eg(O) +xAEg]2 _-Ji2w 2p12 '
where 00 is the Curie-Weiss temperature defined in Eq.
(12), ~Eg equals Eg (1) - Eg (0), Eg (1) and Eg (0) are the
energy gaps for x = 0 and x = 1, respectively (see Eq. (5)
and Table III], and P is a constant. In Eq. (39) OF is in
degrees, Tand 00 in K, the energies No (/3 - a). fuu, and Eg
in eV, H in G, and I in cm. The energy gap is written in the
spirit ofEq. (5), to show the explicit dependence of OF on x.
The constant P has the value
p= (35 ± 2) K deg/G em
obtained empirically from the data in Ref. 153, and is in
(38) principle independent of the materiaL Note, however, that
an additional dependence of (Jp on temperature will follow
from the temperature dependence of Eg (see Table HI).
6. Acceptors and negative magnetoresistance in
H9t_xMn x Te
The behavior of acceptors in a positive-gap
Hg l _ x Mn~ Te as a function of magnetic field is extremely
interesting and leads to very pronounced negative magneto-
resistance. 154,155 This is linked intimately with the effect of
the sp-d exchange on the r 8 valence band. It can be shown
(for greater detail, see Refs. 10, 23. 24, or 123) that in the
presence of a magnetic field the exchange interaction pro-
duces a peculiar mixing of light- and heavy-hole band contri-
butions to the acceptor wave function, which in turn causes
the Bohr orbit of the acceptor to grow in size as the field
increases. 10,23, 156
Cd, _ xMnx Te (x = 0.23) slab, sandwiched be-
tween two linear polarizers. displaying giant Fara-
- 8000'. The experiment is carried out at 5 K and 5
13.000 12,000 1/,000
l
J. K. Furdyna R51
 This unusual behavior can be seen as follows. 10,23 In the
presence of a magnetic field the exchange interaction results
in a magnetic-field-induced anisotropy of the constant ener-
gy surfaces associated with the four spin split components of
the valence band near the r point. The form of the anisotro-
py can be obtained via k'p perturbation for small k, with the
fonowing result:
E±3/2(k) = _~1i2r(_3_+_1_)(k; +k~)
2 l 4mlh 4mhh
+_l_k;] ±B,
m 1h
where m 1h and lnhh are the effective masses of light and
heavy holes, respectively, and B was defined in Eq. (31).
Thus, the constant energy surfaces are ellipsoids of revolu-
tion about magnetic field (I.e., about the z direction), prolate
(cigar shaped) for the E ± 3/2 (k), and oblate (disk shaped)
for theE ± 1/2 (k) levels. With B negative, the E_ 312 (k) level
corresponds to the highest lying point of the valence band,
i.e" it is closest to the acceptor level, which is particularly
important when the acceptor binding energy is less than the
magnitude of B. Note that this spin sublevel is characterized
by a large longitudinal mass (m hh ) and a small transverse
mass [m L ;:::; (4/3) m lh ] • As the magnetic field increases, the
other sub-bands move further and further away from the
acceptor level, which is then increasingly dominated by the
properties of E_ 3/2 (k), Thus, with increasing magnetic
field, as the value of B exceeds the acceptor binding energy,
the acceptor Bohr orbit acquires an increasing admixture of
the light-hole mass. The acceptor wave function then swells
in the direction transverse to the magnetic field H, because,
effectively, the mass involved in determining the orbit size
decreases,
This very unusual feature has three immediate conse-
quences: first, the ionization energy of the acceptor de-
creases with field, leading to a "boil-off" offree carriers (op-
posite offreeze-out) with increasing magnetic fields; second,
the increased spatial extent of the acceptor wave function
leads to increasing impurity conduction (and ultimately to a
magnetically induced Mott transition); and third, owing to
the disklike shapes of the acceptor wave functions, the effects
arising from the swelling of the Bohr orbit are expected to be
anisotropic. m These consequences are manifested in the
form of a dramatic negative magnetoresisiance,154.155.158 of
nearly an order of magnitude per T at low temperatures,
(41)
which is anisotropic with respect to the direction ofH. This
extremely strong effect, shown in Fig. 28, is one of the most
striking manifestations of the sp-d exchange interaction, dis-
tinguishing DMS alloys from nonmagnetic semiconductors.
l" Magnetic4ield-induced meta/~insulator transition in
OMS
n-type Cd! __ xMuxSe also exhibits a striking negative
magnetoresistance associated with sp-d exchange ef-
fects. !59,//)O The microscopic model for the effects observed
in Cd j _ x Mnx Se is not as funy understood as in the case ofp-
type Hg I _ xMnx Te, but is obvious1y very different, since it
involves donors, described by the properties of the r 6 band
of a wide-gap semiconductor. One possible explanation that
may account for this behavior is the destruction of the mag-
netic polaron, which also (like inp-typcHg! _ xMnx Te) re-
sults in a swelling of the impurity wave function as the mag-
netic field is increased, 161

IOSr----r---,---~-_r_-_,_-___,_-__,

!
10' " Hg,_ xMoxTe -1'
I
X '" 0011
1.4 K

iOOO~i---:-----!;ci_-!;ci- _ I
2 3 4 5 6 7
MAGNETIC FIELD ( Tesla )

FIG, 28. The behavior of resistivity in a magnetic field observed inp-typt: Hgi _xMn, Te (x;:::O. J l, acceptor conccntrationp;::: 10 10 cm- 3 ), The plots on the
left show transverse resistivity as a function of inverse temperature at several constant fields. The data manifest two thermal excitation energies (two slopes)
corresponding to different mechanisms: the holc "boil-off" at high temperatures characterized hy the sharper slope, and impurity conduction at low
temperatures. The figure on the right shows the giant negative magnetorcsistlillce as a function of applied Held, observed in the impurity conduction range, at
1.4 K. The dramatic drop in resistance is ascribed to the Jpatial growth of the acceptor wave functions with increasing field (after Ref. 158).

R52 J, Appl. Phys., VoL 64, No.4, 15 August 1968 J. K. Furdyna R52

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 The negative magnetoresistance in p-Hg 1 _ xMnx Te
and n-Cd 1 _ "Mn" Se is so strong that, in certain ranges of
impurity concentration, both systems exhibit a magnetic-
field-induced metal-to-insulator transition. This has been
demonstrated by Wojtowicz et al.162.163 who showed that,
above a certain critical field He. the conductivity of both
systems displays the functional magnetic field and tempera-
ture dependence in the form
a(T,H) = a(O,H) +A(H)T I/2 ,
i.e., that the conductivity extrapolated to T = K remains
finite. This is the criterion by which the system is defined to
be metallic.
The values of O'(O,H) for both P-Hgl_xMnx Te and
n-Cd 1 __ xMn"Se are shown in Fig. 29. The similarity of be-
havior of the two materials is indeed striking. Guided by this
remarkable similarity, the authors of Refs. 162 and 163 pro-
posed that, despite differences between the microscopic
mechanisms which are responsible for the dramatic magnet-
ic-field-induced drop in resIstance, the two systems consti-
tute a new universality class, in which the metal-to-insulator
transition takes place entirely in a single spin-polarized
band. 161.162 The spin polarization of the system is, of course,
a direct consequence of the giant spin splitting occurring in
both materials as a result of the sp-d exchange at low tem-
peratures, thus making DMS the only known family of ma-
terials which can host such a universality class.
8. Bound magnetic po/arons
All the above effects occur in the presence of external
magnetic fields. We finally mention one which is observed
when the magnetic field is zero: the bound magnetic polaron
(BMP). The BMP phenomenon can be understood as fol-
lows: Consider, as an example, an electron bound to a donor.
The hydrogenlike orbit of the electron encloses a large num-
ber ofMn + + ions ( - 300 for x;:::; 0.05), with which the elec-
tron interacts through the sp-d exchange. This interaction
polarizes the Mn + + spins, leading to a finite magnetization
on the scale of the donor orbit. In addition, the spontaneous
fluctuations of magnetization can also lead to a finite mag-
netic moment on the same local scale. As a result of both
contributions the bound electron perceives a finite magneti-
zation, and energy is therefore required to flip the spin of the
donor electron even when there is no external magnetic
40 )(~o.085
""13
. ue-
'EO.4
S u
~20 2>8 S type Hg,_xMn x Te and n-type Cd, .. xMnxSe. The
'0
10
R53 J. Appl. Phys., Vol. 64. No.4, 15 August 1988
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field. 164 Since the first observation of bound magnetic polar-
ons in n-type Cd, _ xMnxSe (donors) 165 and in
01 1 _ xMnx Te (acceptors),166 a great deal of attention has
been given to this subject in the DMS context,167.168 includ-
ing the possible role of the BMP in the negative magnetore-
sistance ofCdl_xMnxSe already mentioned.
For additional details and a full theoretical treatment,
the interested reader is directed to the review of the bound
(42) magnetic polaron problem in DMS by WOIff. 169
° VI. DMS INTERFACES, QUANTUM WEllS. AND
SUPERlATTICES
One of the most exciting recent developments in the area
of DMS, presenting an entirely new set of challenges and
opportunities, is the successful preparation of A~I_ xMnxBvI
superlattices and heterostructures by molecular-beam epi-
taxy.12.13.170.171 It should be clear by now that the strong
variations of the energy gap with composition encountered
in these systems (see Fig. 7) make the A~I_ xMnxBvI multi-
layers highly suitable for "band-gap engineering," and the
wide limits oflattice parameter tuning shown in Figs. 1 and 2
offer important lattice-matching opportunities in this
context. To date, high quality superlattices consisting
of Cdl __ xMnxTe/Cdl_yMnyTe,I70.171 Znl_xMnxSel
Zn l _ yMnySe,l72 Hgl_xMnxTe/HgI_yMnyTe,173 and
Cdl_xMnxTe/Hgl_yMnyTe (y¥=x, including x=O)
(Ref. 174), have been prepared.
Since the dominant property of layered structures is
their two dimensionality, we begin by describing the behav-
ior of a simple two-dimensional electron gas, such as would
exist in a metal-insulator semiconductor (MIS) structure
involving a A~I_xMn"BvI material. We then turn to the
A~I_ "MnxBVI quantum wells and supedattices, and de-
scribe those physical properties which have already been es-
tablished experimentally for such heterostructures. Next, we
discuss novel magnetic phenomena which can be observed in
the layered A~I__ x MnxB V1 structures. Finally, we give con-
siderable attention to those features that, although not yet
observed, are likely to emerge from the marriage of the rich
spectrum of physical properties. specific to DMS with the
new degrees offreedom offered by the quantum well and the
superlattice configuration. In preparing this section, we have
relied to a large extent on the review article by Furdyna,
Cdo.gsMno.osSe
0.6
n=4-1017em3
FIG. 29. Magnetic-field dependence of the extrapo-
lated zero-temperature conductivity a (0, H) for p-
Hg J _ xMnx Te data show that the transverse and
longitudinal magnetoconductivity, although differ-
0.2 ent, yield the same value of critical field (after Ref.
163; for details, see that reference).
O--f!P---"~--'"--"'''''
10 15 20 25 30
H (kOel
J. K. Furdyna RS3
Kossut, and Ramdas, 17 updating the material as required by
newer developments.
A. Two-dimensional electron gas in narrowugap DMS
systems
The earliest investigation of a two-dimensional (2D)
electron gas involving an A {I_ x Mn x B VI alloy was carried out
on MIS structures prepared on the surface of p-type
Hg 1 _ "Mnx Te with x in the range ofO. 10-0.13. (This com-
position was chosen so as to make the resulting energy gap,
0.08--0.12 eV, sufficiently large to limit electron tunneling
from the inversion layer to the valence-band states in the
bulk.) In the presence of a magnetic field, pronounced oscil-
lations of the electrical conductivity were observed in the
electron inversion layer as a function of the gate voltage
across the MIS structure, 175 much as in traditional nonmag-
netic MIS structures. In the case involving DMS, however,
the positions of the oscillations also showed a pronounced
dependence on the temperature, providing direct evidence
that sp-d exchange, which causes the temperature depend-
ence of the Landau level energies in bulk DMS, is also pres-
ent in 2D DMS systems.
Subsequently, magneto-optical studies were performed
on electron-inversion and hole-accumulation layers involv-
ing DMS,176 again showing the presence of sp-d exchange
effects. For example, the very strong magnetic-field depend-
ence of the high-frequency conductivity in accumulation
layers of p-type Hg 1 _ xMnx Te (Ref. 176) was interpret-
ed-at least qualitatively-as a modification of the hole ef-
fective masses due to the sp-d exchange. 120 Such magnetic-
field-dependence of the hole masses appears to be a unique
feature of 2D DMS systems.
A particularly interesting example of a 2D DMS struc-
ture is the 2D electron gas confined to the vicinity of the
boundary between two monocrystalline grains, such as occa-
sionally occur in Hg 1 _ x Mux Te crystals grown by the Bri.dg-
man method. 177 The electron mobilities in such layers were
found to be higher than those observed in the i.nversion lay-
ers of the MIS structures described above. In fact, the quality
of the inversion layers at the grain boundaries of such
Hg 1 _xMnx Te bicrystals was sufficiently high to allow the
observation of well-defined quantum HaH-effect plateaus. 178
Although the Shubnikov-de Haas oscillations occur-
ring in the 2D electron gas at the grain boundaries of p-type
Hg 1 _ x Mn x Te(x=O.1) bicrystals are rather spectacular,
the data did not reveal resolved spin splittings of the Landau
levels. This is probably due to the fact that at this value of x
contribution of the sp-d the exchange to the g factor is rela-
tively small because of the antiferromagnetic interactions
between the Mn + +- ions. For this reason, the 2D electron gas
was also studied m. 179 at grain boundaries in the quaternary
HgO.75 Cdo.23 MnO.02 Te alloy, where the energy gap is primar-
ily determined by the Cd content, and the smaller concentra-
tion of Mn -+ + ions results in the values of magnetization
(and therefore g factors) greater than in the previous
(x = 0.1) case. The quantum Hall-effect data in these qua-
ternary samples did indeed show resolved spin splittings of
the Landau levels of the 2D electrons. The magnitude and
the temperature dependence of the splitting was in agree-
R54 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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ment with calculations based on the assumption that the
values of the sp-d exchange constants in the inversion layer
are the same as in the bulk. 178.180 The important feature to
stress in this case is that, because of the temperature depend-
ence of the effective g factor, the positions of the quantum
Hall-effect singUlarities in the OMS case are also tempera-
ture dependent, another effect which is unique to the 20
DMS structures.
It should be added that the quantum Hall-effect experi-
ments on OMS also show a dramatic dependence on hydro-
static pressure. 179 In particular, the presence of pressure ap-
pears to lead to a further spectacular improvement in the
resolution of the oscillatory features, Quantum Hall data
observed on the above quaternary aHoy in the presence of
hydrostatic pressure are shown in Fig. 30. The role of pres-
sure in this context is presently not understood, and offers
interesting opportunities for speculation.
80 DMS quantum wells and superlattices In the absence
of a magnetic field
The first reports of successful preparation of quantum
wells and supedaUices of Cd1_xMn" Te/Cd 1_ yMny Te by
MBE date back to 1984.11°·171 More recently, superlat-
tices of Zn 1 __ xMnxSe/Znl_ yMnySe,172 Cdl_xMnx Tel
Hg i _yMny Te, 174 and Hg 1 _ x Mnx Te/Hg1_yMnyTe
(x# y, including x = 0 or y = 0) (Ref. 173) have also been
grown by this powerful technique. Of these, the
Cd l _ xMnx Te and Zn,_ xMnxSe systems are the most thor-
oughly studied.
Even the very first measurements on these layered sys-
tems l70 indicated that their electronic properties are strik-
ingly different from those observed on bulk materials; for
example, the intensity ofthe luminescence peak observed in
Cd! _xMnx Tesuperlatticewas found to be about 1500 times
stronger than in the bulk! The above superlattices are usually
of remarkably good quality, showing sharp layer boundaries
as seen by transmission electron microscopy (TEM), excel-
lent x-ray rocking curves, and clear evidence of zone folding
2d - Hg O•75 Cd().2. Mn O• 02 Te
400 T=4.2K p{300K)=5kbar 8
~~ 300
E
.£:.
o
~>< 200
><
Q..
100
o
B (resla)
FIG. 30. Hall resistivity Pxy and diagonal resistivity Px> observed under
hydrostatic pressure in the 2D electron gas at a bicrystal interface in
Hg,l.75CdO.2,Muo.02 Te. Note the well-resolved spin splitting (2+,2 -) in
p xx and the well-defined plateaus ill Pxyo
J. K. Furdyna R54
of the acoustic phonon dispersion curves, as observed by
Raman scattering. IMI
A;I_ x Mnx BVl -based supedattices and heterostructures
can be readily prepared by molecular-beam epitaxy (MBE).
Details of the growth technique, presented extensively in
several technical and review papers, do not differ significant-
ly from the preparation of AHBvl-based structures in gen-
eraL We shaH therefore not discuss them here, except to
mention that the A;I_xMnxBvI epitaxial structures can be
grown, among others, on GaAs substrates, a fact which may
be ofimportance in future attempts at a monolithic integra-
tion oflayered DMS components with GaAs-based devices.
Furthermore, the MBE method, which is a nonequHibrium
growth technique, can be used to prepare in layer form struc-
tures which cannot be grown in the bulk. This has been suc-
cessfully applied to the preparation of zinc-blende
Zn j _ xMnxSe well beyond the limits indicated in Table 1, IR2
to thin layers of MnSe,183 and to Zn l _ xFexSe of high Fe
content. 184 Finally, it should be mentioned in the context of
thin DMS film preparation that atomic layer epitaxy (ALE)
has also recently been emerging as a promising new growth
technique for the preparation of A~I_xMnxBvl layers and
superlattices of exceptionally high quality. J85-187
An inherent structural property ofDMS superlattices is
that they involve layers which are substantially strained.
This is evident from the example of Cd l _ xMn" Tel
Cd! __ yMny Te (x# y), considering the relatively rapid vari-
ation of the lattice constant with x (see Fig. 2 and Table II).
The presence of strain then modifies the band offsets. thus
complicating the subsequent analysis of the data. Strain-re-
lated shifts of the heavy- and light-hole levels are an ever
present part of the DMS superlattice picture, leading to two
distinct excitonic optical transitions !RS-l9G related to the two
resulting hole species. Needless to say, strain effects are also
responsible for large differences in the optical properties be-
tween superlattices grown along the (100) and the (I 11 )
crystallographic directions. 19 !
A measure of the high quality of the Cd l xMnx Te and
Zn\ _ x Mn" Se superlattices is that both systems have mani-
fested stimulated emission. 192-194 This is of considerable in-
terest from the point of view of future applications of these
FIG. 3 L Dark-field images of the MnSe "spin sheet" sllperlattice reported
in Ref. 183. In the images, bright bands correspond to ZnSe layers, the wide
dark bands are zinc-blende ZUo.s> Mno.4 ; Se, and the thin dark bands are
zinc-blende MnSe layers. 6-8 A thick.
R55 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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systems because oftne possibility of tuning the emitted radi-
ation by an external magnetic field 194 and also---owing to the
large energies of the transitions occurring in the
Zn! _ xMnxSe/ZnSe superlattice-because of the eventual
possibility of stimulated emission in the blue region of the
spectrum.
In contrast to the superIattices and quantum wells in-
volving wide-gap DMS discussed above, at this time consid-
erably less experimental information is available on similar
structures consisting fully or in part of narrow-gap
A~I_xMnxBvI materials, such as Hg1_xMn xTe
IHg l _yMny Te or Cd1_xMn x Te/Hg] _ yMny Te. However,
even preliminary results 195 of far-infrared magneto-absorp-
tion measurements obtained on these layered systems exhib-
it unusual and interesting features. Their properties should
be particularly interesting in the presence of a magnetic field,
as may be inferred from the spectacularly rich (although not
yet fully understood) magneto-optical spectra observed on
these systems. 195
c. The magnetism of 20 OMS layers
Although the investigation of magnetic properties of
layered DMS structures has been only recently undertaken,
the observations already made indicate that the type of mag~
net ism occurring in these quasi-two-dimensional systems
differs in many ways from that observed in corresponding
bulk materials. The study of this problem is of importance
not only because of its fundamental nature, but also be-
cause-as was already demonstrated for bulk AiI _ x MnxB vr
alloys-the optical and electrical properties of2D DMS sys-
tems are expected to depend in a very sensitive way on the
magnetization exhibited by these materials.
The first indication of differences between the magnetic
behavior in 2D and in bulk DMS samples comes from Ra-
man scattering. ]81 It was noticed in these measurements that
the Raman Hne associated with low-temperature magnon
excitations was conspicuously missmg in
CdO. 5 Mno.s Te/Cd o.89 MnO. ll Te superlattices, in contrast to
bulk Cdo.s Mno.5 Te, where magnon lines are prominently
present in Raman spectra obtained under identical condi-
tions. Instead, in the case of the superlattices, the spectrum
observed at low temperatures shows only wen-resolved Ra-
man paramagnetic resonance lines, such as those occurring
in bulk Cdo.s Mflo.s Te at high temperatures, i.e., in the ab-
sence of any short range magnetic order. Thus, it was con-
duded 181 that, unlike bulk material, the layered samples
studied exhibit a paramagnetic rather than magnetically or-
dered behavior.
Systematic studies of the changing character of magnet-
ic behavior with decreasing dimensionality of the structure
were made possible more recently by the successful growth
of ultrathin zinc-blende MnSe epilayers (down to -8 A.)
sandwiched between thicker (45 A) layers of nonmagnetic
ZnSe. 183 It is natural to expect that bulk zinc-bIende MnSe
will show an antiferromagnetic ordering of type III, similar
to that observed in j1-MnS (see Fi.g. 16) .196 This i.s indeed
corroborated by low-temperature studies of the thicker
MnSe layers ( - 30 A. or higher) in the presence of magnetic
field, in which the posi.tion of the luminescence peak shows
J. K. Furdyna RSS
no magnetic field dependence (no observable Zeeman shift),
consistent with the existence of antiferromagnetism in the
samples.
Surprisingly, however, the luminescence line observed
at low temperatures in the very thin ( - 8 .A) layers of zinc-
blende MnSe sandwiched between ZnSe, such as those
shown in Fig. 31, exhibited a vigorous shift toward longer
wavelengths in the presence of an external magnetic field. 183
The large magnitude of the observed shift, signaling a large
value of magnetization, is inconsistent with antiferromag-
netic ordering, and can be taken as a signature of paramag-
netic behavior in such ultrathin "spin sheets."
A very interesting result, leading to similar general con-
clusions, has been recently obtained by A wschalom et al. 197
and Hong et al., 19 who measured the low-temperature mag-
netic susceptibility in Cd l _ xMnx Te layers for various layer
thicknesses and various values of x, using a SQUID magne-
tometer. Briefly, thick samples (d:::::86 A.) exhibited a wen-
defined cusp in the susceptibility at a temperature closely
corresponding to the spin-glass transition in the bulk. How-
ever, as the measurements were made on progressively thin-
ner layers, the cusp in the susceptibility became increasingly
distorted, and eventually disappeared completely in favor of
a relatively monotonic paramagneticlike behavior even at
the lowest temperatures, as shown in Fig. 32.
In this connection we wish to recall that in the empirical
picture of magnetic freezing put forth in Sec. IV, we had
argued that the spin-glass-like transition (i.e., the occur-
Cd o.8S Mn O. 15 Te
L: 18 A duced the concept of a "spin superlattice." Such a system
"
CdO.93Mno.07Te ""
L = 86 A · · ..
1.5 4.5 1.5
TEMPERATURE (K)
FIG. 32. Magnetic susceptibility as a function of temperature observed in
epitaxial layers of ed, _xMux Te for various Mn concentrations and thick-
nesses. Note that the spin-glass-like transition cusp, well defined in the
x = 0.15, L = 75 A data, disappears for the x = 0.15 alloy when the layer
thickness is reduced (after Ref. 197; for details, see that reference).
RSS J. Appl. Phys., Vol. 64, No.4, 15 August 1986
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rence ofthe CUSp in the magnetic susceptibility) is intimately
linked with the formation of antiferromagnetically ordered
clusters. The disappearance of the cusp in the thin
Cd l _xMnx Te layers may thus indicate the suppression of
antiferromagnetic order, even on the short range cluster
scale.
While the above results still await a rigorous microscop-
ic analysis, it remains clear that the low-temperature behav-
ior of the A;I_xMnxBvl alloys depends intimately on the
short range Mn + + - Mn + + interactions, i.e., on the detailed
topology of the Mn subsublattice. By changing the magnetic
environment of the Mn ions, one can therefore alter the na-
ture of the short range magnetic ordering. The "spin sheet"
configuration mentioned above I 83 can serve as an example of
such modification, since the presence of intercalating ZnSe
layers certainly leads to a reduction of the coupling of
Mn + + ions belonging to different sheets, thereby altering
the number of possible magnetic nearest neighbors of a given
Mn++ ion,
Finally, returning specifically to the disappearance of
the antiferromagnetic properties in ultrathin epitaxial layers
of Cd! _ xMnx Te and MnSe-and arguing in a more general,
thermodynamic sense--it is tempting to ascribe this absence
(or at least the reduction) of ordering to the Mermin-Wag-
ner theorem, 198 which states that in the limit of two dimen-
sionality-and in the absence of spatially anisotropic mag-
netic interactions within the plane containing the spins-
magnetic order is not possible. One realizes that neither of
the conditions required by the theorem is ideally satisfied,
but it is nevertheless true that we are approaching this limit
as the magnetic layers are made thinner and thinner. The
observed tendencies observed in the ultrathin layers of MnSe
and Cd 1 _ xMnx Te are at least consistent with the predic-
tions of the theorem.
Do Exchange effects in OMS superlattices and quantum
wells
The effect of sp-d exchange on the behavior of superlat-
tices was first considered by von Ortenberg,199 who intro-
would consist oflayers ofHgl_xMnxSe and Hg1_yCdySe,
with x and y so chosen that the energy gaps (and, therefore,
the effective masses) are the same in both materials. The g
factors in the layers, however, are quite different in such a
system. An electron traveling perpendicular to the layers
would thus experience an approximately homogeneous po-
tential in the absence of an external magnetic field, but when
the field was applied, the potential "seen" by the electron
would have the periodicity of the superlattice, owing to the
large differences in spin splittings which take place in alter-
nate layers. This magnetically induced periodicity of the po-
tential would lead to the formation of "minibands" separat-
4.5 ed by "minigaps" which, owing to the special properties of
the g factor in Hg 1 __ x Mnx Se, would also be highly tempera-
ture dependent.
Exchange-induced effects in supedattices involving
wide-gap A ~I_ x Mnx BVI alloys can be equally dramatic. Con-
sider, for example, a single quantum weB of a modulation-
doped superlattice depicted in Fig. 33, with the wens consist-
J. K. Furdyna RS6
ing of wide-gap non-DMS material sandwiched between
wide-gap n-type DMS barriers, for example,
Cd! _ xMnx Te/CdTe/Cd i _ xMnx Te. In discussing the con-
sequences of sp-d exchange in a system of this kind, we shall
make use of three conditions, aU of which are readily realized
in DMS materials, namely:
0) The spin splitting of energy levels in DMS layers is
considerably greater than in adjacent non-DMS layers (easi-
ly by two orders of magnitude in the case of wide-gap DMS
at low temperatures);
(ii) The spin splitting in DMS layers can be comparable
to the ionization energies of shallow impurities;
(iii) The spin splitting in wide-gap DMS far exceeds the
energy difference between consecutive Landau levels of the
same spin (i.e., the cyclotron splitting).
By an appropriate choice of the Mn mole fraction x, the
energy gap of the barrier material depicted in Fig. 33 may be
so adjusted that the donor level is slightly above the ground-
state El of the electron confined in the well, El being deter-
mined primarily by the well width. At low temperatures the
donor electrons will then "spill" from the DMS layer onto
the E, states, rendering the system conducting in the layer
plane.
When a magnetic field is applied to this system, one of
the spin components of the donor state will shift strongly
down in energy, while the E J level in the nonmagnetic wen
will remain practically unaffected by the field. The electrons
will then transfer back to the donor states in the DMS layers,
with a corresponding decrease of the conductivity (a kind of
"freeze-out" effect). Model calculations for the population
oftheE 1 state ina nonmagnetic well as a function of the field
carried out using actual materials parameters (specifically
foraCd! _xZnx Te/Cdl_yMn yTesystem) showthatthe be-
havior just described should be quite feasible under practical
laboratory conditions. 17
A reverse effect (which one could call "electron boil-
off") would be expected to take place in a complementary
system, consisting of DMS wells and n-type nonmagnetic
barriers, with parameters so chosen that in zero magnetic
field the donor levels are now slightly below the El state in
the welt In this configuration, application of the field forces
the donor electrons to transfer to the wen states (owing to
the downshift of the lower spin level within the wen), where
2D conductivity can then take place. Needless to say, the
phenomena described in this section depend critically on our
ability to appropriately dope the superlattices. It is therefore
important to point out that major progress in modulation
non-
OMS non-
OMS DMS
y ....
OMS
...., OMS
Ed
J___ '1Ed
E,
.II • •
-~-----~ .... ~
8"0 B¢O
FIG. 33. A non-DMS quantum well between DMS barriers, illustrating the
sp-d exchange-induced freeze-out. Only the ground state (spin-down) is
shown for nonzero magnetic field (after Ref. 12).
R57 J. Appl. Phys., Vol. 64, No.4, 15 August 1988
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doping of the Cd1 .. "Mux Te system has recently been
achieved,2OO making considerations such as those above
quite realistic.
The fact that the relative position of the donor levels in
the barriers and the EI states in the wells can be adjusted
suggests the possibility of resonant tunneling across the bar-
riers tuned by the magnetic field or by the temperature. A
sequential tunneling (originally demonstrated in nonmag-
netic superlattices for the case involving resonance of the
ground state El and the first excited-state E2 in successive
wells) 201 is in the present case conceivable when the two spin
components of the El state coincide with the donor levels in
the adjacent barriers, as shown in Fig. 34. Such a configura-
tion may ultimately lead to the construction of tunable far-
infrared emitters. Furthermore, since the transitions be-
tween the spin-up and spin-down levels in question involve
circular polarizations, the outgoing light of such emitters
would likewise be circularly polarized. 17
As pointed out elsewhere,12 the quantum-well struc-
tures involving DMS aHoys may show novel features in
quantum oscillation phenomena, of which the most unusual
would occur in a system illustrated in Fig. 35. It should be
noted that the sequence of oscillations in the system shown
would take place in the order which is reverse to that usually
observed in a nonmagnetic 2D electron gas. That is, in the
case of nonmagnetic semiconductors, the sequence of quan-
tum oscillations is determined by the fact that the index of
Landau levels sequentially crossing the Fermi level decreases
as the magnetic field is increased. In the case shown in Fig.
35, however, one may expect the series of oscillations to be-
gin with that associated with the lowest Landau level (la-
beled 0- ), foHowed by those corresponding to levels 1-, 2 - ,
etc., as the field increases. This phenomenon is a conse-
quence of the fact that in wide-gap DMS, spin spliUings far
exceed the spacings between consecutive Landau levels, as
mentioned at the outset of this discussion. This sequence will
continue until the Mn++ spins saturate. The sequence of
oscillations should then reverse, since the Landau splittings
would continue to increase with the field, eventually restor-
ing the standard behavior of the Landau ladder relative to
the Fermi level.
Another interesting case is that of a shallow non-DMS
quantum well sandwiched between DMS barriers. Here we
DMS
non-OMS
E"
j
OMS
E[
.II •••
FIG. 34. DMS quantum weHs between non-DMS barriers in the presence of
an external electric and magnetic fields, showing sequential resonant tun-
neling between spin-split states in the wells facilitated by the donor levels in
the barrien; (after Ref. 17).
J. K. Furdyna RS?
 OMS
~on­
OMS
FIG. 35. A DMS quantum well between nonmagnetic barriers, illustrating
the mechanism for the unusual sequence of quantum oscillations in such a
DMS heterostructure. B, and B2 denote two different values of the applied
magnetic field. Note that the energies of the spin-down states in the DMS
layers do not continue to decrease indefinitely with increasing field due to
saturation of the magnetization, as illustrated by the right-hand side of the
figure (after Ref. 12).
may expect the electron states in the nonmagnetic well to
acquire some of the characteristics of the DMS material,
such as sensitivity to the magnetic field and temperature.
This is because the effective depth of the well, given by the
difference between the positions of the band edges in the
adjacent layers, is itself strongly dependent on the field, and
in a shallow wen the energy EI is strongly dependent on the
wen depth. Such an effect may be viewed as being due to the
"leakage" into the DMS barriers of the wave function of the
electron confined in the wen, so that the electron in the non-
magnetic layer interacts (at least in part) with the Mn + +
ions via the sp-d exchange.
Finally, the photoluminescence measurements on
CdTe/Cd, __ xMnx Te (Refs. 202 and 203) supedattices in
the presence of a magnetic field show that the spin splittings
of the energy levels in the CdTe well are surprisingly large,
although the wells consist of a nonmagnetic material whose g
factors are small in the bulk. Although such an enhancement
is, in principle, possible due to "leakage" of the wave func-
tions of quantum-well confined electrons into the DMS bar-
rier layers in the manner described immediately above, the
magnitude of the observed effect is unexpectedly large and
cannot be quantitatively explained by this simple mecha-
nism. This disagreement led the investigators to the conclu-
sion that the excitons in the quantum wells and superlattices
are trapped at the heterointerfaces.202-204 This conclusion is
further supported by time-resolved exciton recombination
studies 205 and by the strong polarization of light emitted
from these quantum wells in the presence of an external mag-
netic field. 206 The trapping of excitons at the interfaces is
now viewed207-209 as being due to sp-d exchange of the holes
in the wells with Mn + + ions in the barriers, a phenomenon
somewhat analogous to the formation of magnetic polarons
in bulk DMS alloys.
The situations cited above are by no means an exhaus-
tive list of the phenomena made possible by the sp-d ex-
change interaction in the context of quantum wens and su-
perlattices involving DMS, but are rather meant as specific
illustrative examples of the exciting opportunities which this
ASS J. Appl. Phys., Vol. 64, No.4, i5 August 1988
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interaction holds in store for the experimenter as well as the
theoretician.
VII. CONCLUDING COMMENTS
In this paper we have described the structural, elec-
tronic, and magnetic properties of A~!_xMnxBvI DMS al-
loys, as well as the properties arising from the sp-d exchange
interaction in these semiconductors. The approach has been
to deal with the A~I_xMnxBV[ materials as a unified group,
that is, to emphasize those physical properties which are
common to all A1I_xMnxBvI alloys. In following this phi-
losphy, we have omitted, or presented in lesser detail, certain
topics, such as methods of materials preparation, specific
experimental techniques, physical phenomena that occur in
only a limited subgroup of A;l x MnxBVI, and the entire sub-
ject ofDMS other than the A~I_ xMnxBvI systems. To make
up in part for these omissions, we shall briefly list these top-
ics here, with appropriate references for the interested read-
er.
Materials preparation and crystal growth of
A fI xMnxB VI alloys: This subject has been presented with
admirable completeness in the comprehensive review by Pa-
jaczkowskaY More recently, Giriat and Furdyna30 have
also reviewed this subject in considerable detail. References
quoted in both these reviews represent a rather complete
bibliography on materials purification, synthesis, and crys-
tal growth relevant to the A~I_xMnxBvI alloy family.
Raman scattering studies ofDMS: Inelastic light scatter-
ing is an extremely effective technique for the study of ele-
mentary excitations (phonons and local modes,210 mag-
nons,211.212 Raman EPR,213 stimulated spin-flip
Raman,214.215 the bound magnetic polaron, 165.167.216 etc.) in
bulkI65.167,210--216 as well as layered 217 DMS. We have of
course referred to specific Raman scattering results where
appropriate in the present review, but these references are
insufficient to do justice to the role which Raman scattering
has played in extending our understanding of DMS. To
make up for this, we wish to refer the reader to the excellent
review of the subject by Ramdas and Rodriguez,218 and to
sources cited therein.
Elastic properties ofDM'S: In the present article we have
dealt with crystallographic, electronic, optical, and magnet-
ic properties ofDMS, which have been the subject of numer-
ous investigations and are therefore "ripe" for review. By
comparison, little has been done in the area of elastic proper-
ties of the A~I xMnxBvI alloys. Nevertheless, the studies
that have been performed219.220 reveal some intriguing prop-
erties that may be unique to DMS, in that they may reflect
the inftuence of the magnetic properties of these materials on
mode softening observed in ultrasonic attenuation experi-
ments. Important physical insights into the effect of magnet-
ic ordering on elastic properties are likely to emerge from
future studies in this area.
Quaternary DMS alloys: The composition of a given
All_ x Mnx BVI alloy determines the lattice parameter, the en-
ergy gap, and the magnetic properties of the material. Thus,
in the process of changing the energy gap by varying the
value of x, one automatically also changes the magnetic sus-
J. K. Furdyna R5S
··············································'r···
ceptibHity and the lattice constant of the material. In certain
situations it may be desirable to change these variables inde~
pendently. For example, one may wish to increase the energy
gap of Hg 1 _ x Mnx Te, but not to increase the manganese
content beyond a certain limit (as was done in the case of the
samples used in the quantum HaH effect, discussed in Sec.
VI A). This is possible by preparing a quaternary system
Hl __ x_yCdxMny Te, in which both x andy jointly determine
the energy gap, while x alone determines the magnetic prop~
erties. Similar strategies of tailoring suitable four-compo~
nent systems can be followed in order to independently con~
trol the energy gap and the lattice parameter, or the lattice
parameter and magnetic properties. A great deal of system-
atic research on the preparation and on the physical (pri~
marily magnetic and optical) properties of quaternary alloys
of the type A~I_X __ yC~IMnyBVI and A~I_ xMnxBY~yC;I has
been done by Woolley and co~workers, and we refer the read-
er to their publications for further details concerning this
subject. 61,221-224
New DMS alloys: Although the major activity in the
field of diluted magnetic semiconductors has been concen-
trated on the A~I_ xMnxBvI alloys, it is important to realize
that other types ofDMS are also beginning to emerge. These
are: Pbl_xMnxBvI and Pb, _ x (RE)x Bvl alloys, 225-227
(where RE indicates "rare earth"), (A~!_xMnx}zAs3 al-
loys, and A;I_xFexBvl and AiI __ xCoxBvI ternary systems.
Of these, perhaps the most intense activity at this time is
centered around theA~I_ xFexBvI ailoyfamily, for three rea-
sons:
First, owing to the fact that the Fe+- -I- ion in the ground
state lacks a permanent magnetic moment, the magnetic
properties of these alloys differ from their Mn~based coun-
terparts. In particular, these systems exhibit Van Vleck par~
amagnetism at low temperatures,228,229 and for that reason
should be of considerable interest to the magnetician. 230,231
Second, the alloy Zn I _ x Fe x Se turns out to be surpris-
ingly amenable to growth by molecular~beam epitaxy
(MBE), 184 with x ranging from 0 aU the way to 1. It is quite
possible that related alloys-Zn1_xFe"S, Cd] __ xFexSe-
will show similar behavior. This is particularly significant,
since such ready predisposition of this family of aHoys to be
grown by MBE shouid lead to new insights into the MBE
growth dynamics. And, of course, the end product of the
process provides the researcher with samples of exceptional~
ly high iron content (up to pure FeSe) for the purpose of
studying the electronic and magnetic properties, and for
eventual incorporation of the high Fe concentration layers
into supedattices.
Finally, an extremely important feature of the
Ai!-x FexB vl aHoy group is the influence which the presence
of Fe atoms have on the electrical properties specifically of
Hg,_ x Fe x Se and its quaternary derivatives (e.g.,
Hg j x_yCdxFeySe). This has recently been explained as
follows. The Fe+-+- level lies at about 230 meV above the
bottom of the conduction band of HgSe, as shown in Fig. 36,
with Fe'- +- acting as a resonant donor. The position of the
Fe -I- + thus establishes the Fermi level, since all conduction-
band states below that level can be filled by ionizing the
Fe-+- -{- ions to Fe+ -:- +. In this situation, the electron concen-
R59 J. AppL Phys., Vol. 64, No.4, 15 August 1988
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\ \
\
x '0.0
FIG. 36. A schematic picture of the band structureofHg, _xFe,Se near the
r point for several values of x. The Fe + +- level is shown as a resonant donor.
There are approximately 5X 10'" em -3 conduction-band states available
below the Fe+ ~ level. For x > 3 X 10- 4, an these states are filled by ioniza-
tion of Fe· + ions to Fe++ r ions. This provides a natural limit for the
Fermi level (after Ref. 29).
tration is determined by the band structure and its corre-
sponding density of states (like in a true semimetal, e.g., Bi)
rather than doping or nonstoichiometric defects, as long as x
(the Fe concentration) exceeds the number of available elec-
tronic states below the Fe++ level. (For Hg1_xFe"Se this
number equals 5 X 10 18 em -3, which corresponds to
x ~O,OOO3.) The role of Fe in this system is illustrated sche-
matically in Fig. 36.
Furthermore, it has been suggested by Mycielski232 that
the ionization of resonant Fe +- + donors to Fe + + + occurs in
such a way as to maximize the separation in space between
the ionized sites, which may in turn result ill a spatial order-
ing of the ionized centers (at least partially). Such an or~
dered, periodic array of ionized impurities can then be
shown to lead to reduced scattering rates as compared to a
random distribution of ionized impurities. 233
ExcelIent reviews of the physics ofHgl_xFexSe and re-
lated alloys, together with a rather complete list of refer~
ences, have recentiy been published by Reifenberger and
Kossut2 34 and by Mycielski. 235 ,236
Helicon-induced electron paramagnetic resonance in
narrow-gap DMS: The electron gas which exists in narrow-
gap DMS, such as n~type Hg1_xMnx Te and Hg1 __ xMnxSe,
is characterized by a high carrier concentration, a small ef-
fective mass, and a high electron mobility. Such an electron
gas is of course opaque to Jow~frequency electromagnetic
waves. The medium can, however, be made transparent by
the application of a strong magnetic field (such that @c r > 1,
CUe >@, where We and@arethecyclotron and signal frequen-
cies, respectively, and r is the relaxation time). Under these
conditions, waves which are circularly polarized in the same
sense as the cyclotron motion of the highly mobile electrons
can travel with little damping along the direction of the ap~
plied field. Such waves are known as helicons237 ,238 and are
analogous to whistler waves in plasma physics.
The interesting aspect of helicons in the context of nar-
row~gap DMS is that this magnetic~fie!d-induced transpar-
ency can be used for the purpose of studying electron para~
magnetic resonance (EPR) of Mn'" +- ions in highly
conducting specimens, where EPR experiments are normal-
J. K. Furdyna RS9
ly limited by the very shallow skin depth. Helicons, however,
penetrate the medium with little damping and "see" the
Mn + + ions, with which they can couple resonantly at the
EPR condition.
Helicon-induced EPR has been studied extensively in n-
type Hgl_xMn x Te (Ref. 239) and Hgl_xMnxSe.107,240,241
Paradoxically, it has been shown that the strength of the
resonance is in fact enhanced by the free-carrier concentra-
tion of the semiconductor. This is another fascinating fea-
ture of the DMS alloys, based not on the sp-d exchange but
on the unique macroscopic interplay of the dielectric re-
sponse function of the free-electron gas and the dynamic
magnetic susceptibility of the manganese subsystem.
DMS-based device applications: The high crystallo-
graphic and electronic quality of the A~I__ xMnxBvI alloys,
along with the wide spectrum of new physical effects which
occur in these materials, holds promise of novel practical
applications. We have not dealt with device applications in
the body of the review, since this aspect of the DMS alloys
has not yet reached maturity. However, some of the applica-
tions should at least be mentioned at the conclusion of this
review as concrete possibilities.
The application ofthe yellow electroluminescence of the
Mn + + centers in Zn-based DMS, discussed in Sec. HI C, is
at the most advanced stage/5 •76 and is beginning to play an
important role in fiat panel display technology. The use of
Hg) _ x Mnx Te in the area of infrared detection of 5- and 10-
pm radiation, in configurations similar to those employing
Hg I _ xCd x Te, has also been periodically proposed. 8 Similar-
ly, we have already mentioned in Sec. VI B the quantum-
well laser, the feasibility of which has now been demonstrat-
ed.192-194 The construction of a Zn j _ x Mnx Se/ZnSe-based
blue laser remains a particularly attractive possibility in this
area.
By comparison, litHe has been done so far to expioit the
spectacular effects arising from the sp-d exchange interac-
tion, which culminate in the giant spin splittings and giant
Faraday rotations observed in the A~I_xMnxBvl alloys. It
should therefore be stated with particular emphasis that the
high physical quality ofthe available crystals-as well as the
extent of our theoretical understanding of the sp-d ex-
change-makes the implementation of exchange-based
DMS devices realistic at the present stage of development.
The large size of Faraday rotation and associated dis-
persion of circularly polarized modes in the A~I_xMnxBvI
alloys offers three types of applications to be considered.
Since a rotation ofthe order of 45° is readily obtained at room
temperature in moderate magnetic fields with a high figure
of merit, 152 one may contemplate nonreciprocal optical de-
vices (isolators and circulators) as a practical possibility.
Faraday rotation may also be readily made use ofin optical
modulation and switching. Finally, the large size of the effect
can be exploited in highly sensitive optical-fiber fed dielec-
tric magnetometers, for measuring minute static as well as
dynamic (up to GHz frequencies)!05 magnetic fields.
The large Faraday rotation involves, of course, large
phase shifts of two counterrotating circular polarizations, If,
instead of working with linear polarization, one employs a
single circular polarization traveling along the applied mag-
R60 J. AppL Phys .• Vol. 64, No.4, 15 August 1988
Downloaded 30 Jun 2012 to 129.215.149.92. Redistribution subject to AIP license or copyright; see http://jap.aip.org/about/rights_and_permissions
netic field, one can then construct a magnetic-field tunable
phase shifter. This is of interest in interferometry as well as in
optical cavity tuning (e.g., to optimize laser output).
Finally, since the large spin splitting of energy levels
brought about by the sp-d exchange interaction in
A~I_xMnxBvl alloys corresponds to the far-infrared (FIR)
region of the spectrum, application of DMS as tunable
(FIR) detectors and sources appears highly promising. We
have already discussed one possibility of a tunable coherent
circularly polarized FIR emitter in Sec. VI D, in connection
with resonant tunneling in superlattices involving doped
wide-gap DMS. Furthermore, the observation of stimulated
spin-flip Raman scattering in n-type Hg1_xMn" Te (Ref.
214) suggests the possibility of using narrow-gap DMS for
the construction of a stimulated spin-flip Raman laser which
is tunable over a wide range. Although the spin splitting
effects underlying these applications are the largest at liquid-
helium temperatures, careful attention to the trade-oft's
which take place between the Mn concentration and tem-
perature in their respective effects on magnetization should
make it possible to design DMS materials in which the sp-d
exchange-induced splitting is large enough at 77 K to make
the far-infrared devices described above operable at that
temperature.
ACKNOWLEDGMENTS
The author is indebted to R. L. Aggarwal, M.
Dobrowolska, W. Giriat, K. C, Hass, J. Kossut, Y. R. Lee,
A. K. Ramdas, and N. Samarth for numerous discussions
and for sharing their insights during the preparation of this
review. He also wishes to acknowledge the support of NSF
Grants No. DMR-8520866 and DMR-8713767, and
DARPA/ONR Grant No. N14-86-K-0760,
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