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P I-I YSICA L R E V I E %' VOLUiA E 172, NUM 8 RR 3 15 AU GUST 1968

Application of a Modified Random-Element-Isodisplacement Model


to Long-Wavelength Optic Phonons of Mixed Crystals*
I. F. CHaNott ANn S. S. MrTaA
Department of Electrical L~'ngineering, Unimrsity of Rhode Island, Kingston, Rhode Island
(Received 22 January 1968)

The random-element-isodisplacement (REI) model has been modified to include the polarization field,
thereby enabling it to predict the long-wavelength longitudinal optic frequencies of a mixed crystal. A cri-
terion has been obtained to determine whether a given mixed crystal will exhibit "one-mode" or "two-mode"
behavior. Under certain conditions the modified REI (MREI) model may also be made to work for mixed
crystals with one-mode behavior. The so-called "virtual-crystal model" applicable to this type of crystals
becomes a special case of the MREI model. Given the properties of the "pure" end-members AB and AC, the
MREI model then can determine whether AB&,C, is going to display one-mode or two-mode behavior,
and can predict the concentration dependence of the TO and LO modes, A large number of examples of both
types of mixed crystals is given.

I. INTRODUCTION Many attempts have been made to account for the


behavior of a mixed crystal system. Matossi'7 has
far as the behavior of the long-wavelength optical
A S

phonons is concerned, there seem to exist two


considered a linear diatomic chain model which con-
siders only nearest-neighbor force constants to discuss
types of mixed crystals. In one class of mixed systems, the one-mode behavior of Nal, K Cl. This model is
the "one-mode" behavior type, each of the k 0 optic
idealized with a periodic regular distribution of A ions
mode frequencies (infrared or Raman-active) varies
continuously and approximately linearly with concen-
and 8 ions in A& +,C, whereas the true distribution is
believed to be random. His treatment dealt with the
tration from the frequency characteristic of one end
50-50 mixed case only. The calculations for Nal K Cl
member to that of the other end member. Furthermore,
yield two infrared-active modes: One lies in between the
the strength of the mode remains approximately con-
stant. Examples' '
of this behavior are Na1, K,Cl,
interval of frequencies of the two pure components
NaCl and KCl; the other one lies outside. The former
Nit, Co, O, KClr, Br„Kr,
Rb, Cl (Ca, Ba) Sr, Fs, r, has an intensity about one order of magnitude higher
GaAsl, Sb, Znl, Cd S, and ZnSel Te, . In the other than the latter. Mitsuishi' has used this model and
class of mixed crystal systems, the "two-mode"
calculated the two frequencies for KClp. 5Brp. 5 and
behavior type, the two phonon frequencies for each of
Kp. ;,Rbp. 5Cl. The values of the in-between modes agree
the allowed optic modes of the pure crystal are observed
with the experimental results. However, the weaker
to occur at frequencies close to those of the end mem-
mode outside of the interval predicted by this model is
bers. In addition, the strength of each phonon mode of
yet to be experimentally observed for any crystal.
the mixed crystal is approximately proportional to the
Langer, Park, and Euwema" extended Matossi's
mole fraction of the component it represents. Ex-
amples' "
of the two-mode type behavior are InP& +s„ model to describe the two-mode behavior of the LO
frequencies in CdS1,Se,. These authors chose a 12-
Sir, Ge„GaPr +s„cdSr,Se„and ZnSr, Se,. molecule cell and assigned a perfect ordering for each
*Work supported in part by the U. S. Air Force In-House composition. The total chain is assumed to be composed
Laboratory Independent Research Fund under Contract No.
AF19(628)-6042. ' D. W. Feldman, M. Ashkin, and J. H. Parker, Phys. Rev.
t Forms a part of a thesis submitted in partial fulfillment of theLetters 17, 1209 (1966).
requirements for the Ph. D. degree at the University of Rhode ' Y. S. Chen, W. Shockley, and G. L. Pearson, Phys. Rev.
Island, Kingston, Rhode Island.
151, 648 (1966).
f. Present address: Components Division, IBM, East Fishkill, "H. W. Verleur and A. S. Barker, Phys. Rev. 149, 715 (1966).
N. Y. "M. Balkanski, R. Beserman, and J. M. Besson, Solid State
'F. Kruger, O. Reinkober, and E. Koch-Holm, Ann. Physik Commun. 4, 201 (1966).
85, 110 (1928).
' P. J. Gielisse, J. N. Plendl, L. C. Mansur, R. Marshall, S. S. ~4
J. Parrish, C. H. Perry, O. Brafman, I. F. Chang, and S. S.
in Proceedings of the International Conference on the Physics
Mitra, R. Mykolajewycz, and A. Smakula, J. Appl. Phys. 36, Mitra,
2446 (1965). of II-VI Semiconductors {W. A. Benjamin, Inc. , New York, 1967).
A. Mitsuishi, in U. S.-Japan Cooperative Seminar on Far "H. W. Verleur and A. S. Baker, Phys. Rev. 155, 750 (1967).
Infrared Spectroscopy, Columbus, Ohio, 1965 (unpublished). "O. Brafman, I. F. Chang, G. Lengyel, S. S. Mitra, and E.
R. K. Chang, B. Lacina, and P. S. Pershan, Phys. Rev. Letters Carnall, Phys. Rev. Letters 19, 1120 {1967);in Proceedings of the
17, 755 (1966). International Conference on Localized Bxcitations in Solids (Plenum
' A. S. Barker and H. %. Verleur, So]id State Commun. 5, 695 Press, Inc. , New York, 1968). The individual references for the
(1967). various mixed crystals studied so far are in the following order:
'R. F. Potter and D. L. Stierwalt, in Proceedings of the Inter- Naq, K Cl (Ref. 1); Ni& Co 0 (Ref. 2); KClq Br, K,Rb~ CI
national Conference on the Physics of Semiconductors, Paris, 1964 (Ref. 3); (Ca, Ba)&,Sr, Fs (Refs. 4 and 5); GaAsi &Sb (Ref. 6);
(Academic Press Inc. , New York, 1965), p. 1111. Znq, Cd, S (Ref. 7); ZnSeq ~Te~ (Ref. 8); InP& ~As~ (Ref. 9);
7 G. Lucovsky, E. Lind, and E. A. Davis, in Proceedings
of the Sii Ge~ (Ref. 10); GaP&, As, (Refs. 11 and 12); CdS~ Se,
International Conference on the Physics of II VI Semiconductors- (Refs. 13—15); ZnS~ ~Se~ (Ref. 16).
(W. A. Benjamin, Inc. , New York, 1967). "F.
Matossi, J. Chem. Phys. 19, 161 (1951).
' O. Brafman, I. F. Chang, and S. S. Mitra (unpublished). "D. W. Langer, Y. S. Park, and R. N. Euwema, Phys. Rev.
' F. Oswald, Z. Naturforsch. 14a, 374 (1959). 152, 778 (1966).
172 924
LONG —KA VE LENGTH OP TI C P HONONS OF iM l XE D CRYSTALS
of repetitions of the cell. The second assumption is Recently, t.ucovsky, Brodsky, and Burstein" have
made on the nearest-neighbor force constant. In one reviewed the experimental results on mixed crystals.
case, two independent force constants fe and fo', which They have discussed the models which have been used
are derived from the observed phonon energies of the to describe the variation of the observed vibrational
pure CdS and CdSe crystals, are used. In the other case, frequencies with concentration. They also suggest a
one common force constant F =fs' (fs— ' fe)—
sc, with fs criterion, based on whether or not localized modes and
linearly increasing and fs linearly decreasing with x, is gap-modes form, for predicting the behavior of the optic
used. Although the predictions show a singularity at phonons of mixed crystals.
the @=0.5 composition, this model does predict two Two empirical criteria, which have been proposed to
optical modes and shows a fair over-all agreement with predict the behavior of the mixed crystals, are worth
the observations. discussing in some detail. The first observation is con-
The above models are essentially one-dimensional. cerned with the reststrahlen spectrum. The reststrahlen
However, Dean" has shown that the spectra of one-, bands of the pure components are mostly broad (ionic
two-, and three-dimensional disordered lattices are nature) and overlap in the case ot the one-mode type
qualitatively similar. He has also reviewed the theo- systems, while in the two-mode type systems, the
retical work on the dynamics of disordered lattices. bands are well separated. (The separation between the
Verleur and Barker" '5 have considered a model k 0 LO and the TO frequencies of a diatomic crystal
based on short-range clustering to describe the two- may be considered as the spread of a reststrahlen band. )
mode behavior of mixed crystals, GaPt &s, and "
Balkanski et ul. have suggested that the long-range
CdS&, Se,. They assume that like-negative ions have a average crystal potential variation may have been
tendency to cluster around positive ions within a range large enough for the one-mode systems to shift the
of no more than a micron or two. They consider 6ve eigenfrequencies of each of the constituents towards
basic units of nearest-neighbor ions around a positive a unique value but which may not be enough for the
site and introduce a clustering parameter to obtain the two-mode cases. This seems to lead one to make a dis-
weighted fractional distribution of these 6ve basic tinction between ionic and covalent crystals and to
units in the crystal. Considering only nearest-neighbor suggest a criterion for the one-mode and two-mode
and second-neighbor interactions between two units, behaviors. However, the fact that CdS~ Se, ZnSI, Se„
the authors obtain 13 eigenfrequencies. Although the and GaPt &s, belong to the two-mode class whereas
reststrahlen spectra of the crystals considered show only GaAs~, Sb„Zn~, Cd, S, and ZnSe~, Te, belong to the
two gross features, this treatment uses a large number one-mode class does not lend support to such a criterion.
(7 or 8) of TO modes in the multiresonance damped The second observation concerns the mass of the
oscillator representation of the experimental data. A substituted atom made in a mixed crystal. I
closer inspection of their values, however, reveals that " ucovsky
et a/. pointed out that the substitution is being made
for each mixed crystal studied, two out of the many on the heavier element for the one-mode system with
modes considered stand out in strength over the rest. the exception of Na~ K Cl, where the masses of the
Barker and Verleur' have considered a simple model three atoms are comparable. For the two-mode sys-
to account for the one-mode behavior of Ba~ Sr,F2. tems, on the other hand, the substitution is made for
Using six 6tting parameters, they have shown that the the lighter element. However, an exception to their
model can yield one-mode or two-mode behavior de- observation is the two-mode behavior displayed by
pending on the values of certain parameters. They also ZnS~ Se„ in which the masses are Zn=65, S=32, and
point out that the one-mode behavior results from the Se=79; thus the substitution cannot be de6ned as
approximate equality of the mode frequencies of pure performed on either the heavier or the lighter element.
BaF2 and SrF2. However, this criterion does not seem It is also confusing when the term "substitution" is
to hold good for GaAs&, Sb„where the optic frequencies applied to the mixed system Si~ Ge in the sense
of the end members are well separated yet the mixed described above. Nevertheless, if the mass substitu-
system exhibits one-mode behavior. Barker" has also tion is, indeed, made according to the manner described
given a treatment for the long-wavelength optic pho- by Lucovsky et aL, the conditions necessary for the
nons of mixed crystals in which long-range dipolar existence of localized and gap modes in mixed system
forces and a short-range order parameter have been are fu16lled for two-mode systems and are not ful6lled
included. According to this model, for crystals which for one-mode systems. Therefore, they propose the
exhibit one-mode behavior the ion vibrations are not existence or nonexistence of local and gap modes as the
localized to any signi6cant extent at any concentra- conditions for diGering mixed crystal behavior. How-
tion. ever, this condition can be shown to be incorrect for
some cases and a stronger condition based on the
"P. Dean, Lattice Dynamics, edited by R. F. Wanis (Permagon
¹w
Press, Inc. ,
' A. S. Barker,York, T965), p. 56T.
in Proceedings of the International Conference "0.Lucovsky, E. Burstein, and M. Brodsky, in Proceedings of
on Localized Excitations in Solids (Plenum Press, Inc. , New York, the InternationalConference on Local&ed Excitations in Solids
1968). (Plenum Press, Inc. , New York, 1M8).
926 I. F. CHANG AND S. S. MITRA 172

random-element-isodisplacement (REI) model is de- bors and no effects of order are actually present. The
rived in this paper. statistical average of the neighbors depends on the
In Sec. II, we discuss the REI model" and its modi- fraction parameter x. For example, in the case of
6cations. A different approach to the problem is also GaPi &s„x is the fraction of anion sites occupied by
indicated. Modilcations, which take the polarization As. Accordingly, each Ga is regarded as surrounded
6eld into consideration, have been made such that the by exactly 4x ions of As and 4(1 — x) ions of P. Further-
model can predict not only the long-wavelength TO more, both As and P ions are assumed to have exactly
frequencies of a mixed crystal but also the k 0 LO 12m next-nearest neighbors of As and 12(1— x) next-
modes. In Sec. 111, based on the modified REI (MREI) nearest neighbors of P, respectively. By the definition
model, we derive a strong necessary condition which of isodisplacement, relative motions occur only between
governs the mixed-crystal behavior. The numerical atoms of different species. Thus the equations of motion,
calculations of several two-mode systems are presented which are on per-atom basis, can be written for the
in Sec. IV. Furthermore, if certain conditions are ful- mixed crystal AB& C as
6lled it is shown that the model can also describe the ——(1—x)Fg~(ug —Ng) —xFgc(u~ —uc), (1)
mgug
behavior of one-mode mixed crystals, although ori-
ginally it was proposed only for two-mode crystals. This mBuB FAB(NB NA) &FBC(NB Nc) (2)
u~) —(1 —
—x)Fac(+c —Ia),
is discussed in Sec. V. Finally, an empirical rule for mcuc= F~c—
(uc (3)
calculating the k 0 LO modes of a mixed crystal from
the corresponding TO modes is described in Sec. VI. where u~, NB, and Ng are the isodisplacements for the A,
B, and C atoms, respectively; and vs~, esB, and mg are
II. REI MODEL AND ITS MODIFICATIONS the atomic masses (mg(mc). F~~ is the force constant
between an A ion and four surrounding B ions which
The appearance of the reQection spectrum of a two- form an equivelent B ion on the per-atom basis.
mode mixed crystal with its separated characteristic Similary, xF&c(N& Nc) re— presents the force applied
bands of the two constituents suggests that there is a on A ions due to the C ions. The remaining term FBq
high degree of independence between the interactions is the force constant which describes the interaction
of the cations with the one type of anions and that of force between the I;wo anion sublattices. All these three
the cations with the other type of anions (the role of the force constants are actually functions of the lattice
and anion will be reversed if the substitution is made on constant. This functional dependence is assumed to be
the cation). As a zeroth order approximation for the linear v ith concentration x, i.e. ,
mixed crystal AB~,C„one would then imagine a model
which has a rigid cation A sublattice vibrating inde- ~A. B ~A C ~B0
pendently against both rigid anion B and C sublattices.
= 1 —Hx. (4)
~ABO ~ACO ~BOO
If one does not consider any interaction between B and
C atoms or between A atoms and a combination of B Chen et al. have related these variations to the vari-
and C atoms, this model could yield two reststrahlen ation of the lattice constant with a constant of propor-
bands. The strength of each band would indeed depend tionality 3p, where y is the Gruneisen constant. This
on the amount of B and C present, but the observed relation may not be proper in view of the fact that the
dependence of the reststrahlen frequencies on mole Gruneisen constant used by Chen et a/. , is a general one
fraction x would not be explained by this simple model. and not particularly for long-wavelength optic phonons.
The REI model, advanced by Chen, Shockley, and The force constants I'gB at x=0 and F~g at x=1 can
"
Pearson, however, is a more realistic model, although be directly related to the frequencies observed for the
based on the above concept. It assumes that the cations pure compounds AB and AC. The third force constant
as well as the anions of like species vibrate as rigid units, is used as an adjustable parameter by Chen et al. , to
i.e., each unit vibrates with one phase and amplitude. fit the data of GaPi &s . They are able to predict the
One notices that this assumption of isodisplacement is reststrahlen frequency of GaPi +s, as a function of x
true for the reststrahlen frequency in an ordered di- which shows very good agreement with the experimental
atomic crystal, since there is no phase shift from unit result.
cell to unit cell for k 0 modes. The model thus considers However, in this paper, we are adopting a different
a "quasi-unit cell" containing one unit of AB& C . approach to the problem. Since this model is proposed
x-ray diffraction measurements on most of these mixed for the entire composition range x=0 to x=1, it is
crystals, whether one-mode or two-mode type, do indeed natural and necessary that the model vill predict the
indicate unique unit cell dimensions throughout the k 0 vibrational modes for the two pure components.
composition range. The model thus essentially attempts We would thus like to determine all the parameters of
to predict the main features of infrared and Raman this model from the observed quantities of the end-point
spectra. The second assumption of the REI model is compounds, such as mass, dielectric constants, optic
randomness, which suggests that each atom is subjected mode frequencies, etc. Instead of using the force con-
to forces produced by a statistical average of its neigh- stant between the two anion sublattices as an adjust-
172 LONG —WAVELENGTH OPTIC PHONONS OF MIXED CRYSTALS 927

able parameter, we subject all the force constants to = PAco(1 8)/ttAc co TO, Ac g

satisfy a boundary condition: The model must at +AB 0+ +BCO


least be valid at x= 0 and x = 1, where the optic phonons or'= (1 8) =OO 1 ssl ~

of the pure compounds and the local or gap mode, as the


case may be (induced by the impurity atom in the limit
of in6nite dilution), occur. One can obtain this boundary The above model can also be extended to predict
condition by solving the equations of motion. First we the long-wavelength LO modes if one takes the polari-
define zation ield into consideration. The equations of motion
and polarization can be written as'2
W1 NA NB ~2 'NA NC
R1 — 1—
E1R— E12(tsAB/ts AC) '"R2+Z1E ) (12)
and substitute them into the di6erences of equations of
(1) and (2), and (1) and (3). We obtain E21(ts AC/tsAB) R1+ZOE ~ (13)
P = Z1R1+ZOR2+n„E, (14)
—(1—x) FAB —FAB —xFBC W1 where
mA mB mB—
mAmc
FAC FBC JAB = PAC=
x —s W2, (6) mA+ mB rrtA+ 5$ c
mB—
JAB PABl/2
FAC FAC FBC R1 —— 8'g= (NA
—NB),
~ ~

W2= S- —(1—x) Ws vl/2 v1/2


mA mc
FAB FBC R, =
@AC
W2 —
—gAC (NA stC)— (16)
(1 — —(1—x)

1.
x) —
W1. (7) vl/2 v'/2
mc
(n„ is the high-frequency polarizability and e is the
The eigenfrequencies are determined by the following volume occupied by one ion pair). Solving Eq. (14)
equation: for E with the aid of Gauss's law,
—to'+E
=0 (8) 7 D=V (E+47rP)=0,
co'+Es—
or and substituting it into Eqs. (12) and (13), we obtain
(E1+Es)co + (E1E2 E12E21)= 0 ) (8') 4xZy'
where R1+ E1+ R1
FAB FAB FBC
E1=(1—x) + +x / 4' Z1Z2
mA mB JAB
+ E12 —
+ R2=0, (17)
FAC FAC FBC PAC
Es=x + +(1—x) 4mZ2'-
mA mc mc
R2+ E2+ R,
E12 x+A c/mA xFB c/rrtB

E21 = (1—x)
FAB
—(1—x)FBC + E»~
(tt A c
+ —R, =o,
47rZ1Z2$

mA mc
where, for the high-frequency dielectric constant, we
Identifying the solutions of Eq. (8') at the limiting
have used
values @=0, and @=1 as the TO phonon frequencies
and local and gap modes of the two end members of the e =1+42m„. (19)
mixed crystal, we obtain the boundary conditions The solutions of the transverse parts of (12) and (13)
which are to be used to determine the model parameters: are identical with those of (8). The longitudinal solu-
tions are determined by the determinant which is a
~ABO/tSAB te TO, AB y (10)
quadratic equation in co', of the two differential equa-
(~Aco++Bco)/rrtc co gsP p
(10') tions (17) and (18):

oo +Er+42rZ1 /e~— E12 (tt A B/tsA C) +4arZ1Z2/&ao =0


(20)
E21(ttAC/tsAB) +42rZIZ2/eoo co +Es+42rZ2 /ecs
"M. Born and K. Huang, Dyrtarrticat Theory of Crystal Lattices (Oxtord University 'Press, London, 1954).
928 I. F. CHANG AN D S. S. M ITRA
or indicate the appearance of a gap mode at @=0. Ac-
—(E1+4m Z1'/O„+E2+42rZ2'/e„)(o' cording to the treatment in Mazur et ul. , one thus
O1'
expects a local mode for Na impurity in KCI. However,
++1EO It12+21+It142rZ2 /om+It242rZ1 /oaa no such local mode has been observed and the mixed-
%21(IAAC/i2AB) ++12(i2AB/IAAC) ) crystal system exhibits one-mode behavior. ' Thus one
X42rZ1Z2/O„= 0. (20') must seek a stronger condition which can predict the
right mixed-crystal behavior. This indeed can be found
Thus the TO and LO frequencies of AB& C for any
by using the MRKI model.
value of x may be obtained by solving Eqs. (8) and Examining Eqs. (10), (10'), (11), and (11'), we must
(20). This is done in Secs. IV and V for several crystals have the following inequalities in order to have a local
of two-mode and one-mode behavior. mode at @=1 and a gap mode at @=0. According to
Mazur's definition of the local and gap modes, we have
III. CONDITIONS FOR DETERMINATION OF
MIXED-CRYSTAL BEHAVIOR &ABO+FBCO &A co(1 —&)
(1—8))oo1»2)o12To, Ac= ) (22)
As discussed in Sec. I, a number of attempts have
been made in the past to obtain a criterion to account FAco+FBco FAB0
for the differing behaviors of mixed crystals. It is pos- ++ boy+ TO, AB (23)
sible, based on the present model, to obtain a necessary
condition (which may also be a suKcient one) which
dictates the one-mode or two-mode behavior of a mixed where cot, ~ is the top frequency of the optic branch of
crystal system. AC and cob, is the bottom frequency of the optic branch
&

Since two-mode mixed crystals always exhibit local of AB.


and gap modes when one component or the other is We assume that the force constants in (22) and (23)
infinitely diluted in the mixed system, one naturally are of the same order of magnitude (this is true for
tries to search for the local-gap mode condition and most cases as may be seen in Sec. IV). Furthermore, the
then to apply it to the mixed-crystal behavior. For the top frequency of the optic branch (o1„~) is certainly
present discussion it is sufhcient to define a local mode higher than coTo. Thus the adjusted effective force
as an impurity mode lying above the optic band of the constant for o12» is about the same as FABo+&Bco.
host lattice, whereas a gap mode is that lying below the Equations (22) and (23) then reduce to
optic band. For these impurity modes a necessary con- m~ 4 p, gc Cmg, mc (22')
dition has been derived by Mazur et a/. 23 Their result
may be summarized as follows: When substitution is mc+ pea (23')
made on the light mass, a lighter impurity gives a
localized mode which rises out of the top of the optical Equation (23') is trivial since it is contained in Eq. (22')
band, and a heavier mass causes an optic-branch gap (222c) pAc) 222B) pAB). An examination of condition
mode to fall in the gap between optic and acoustic bands (22') reveals that this is a stronger condition since the
of the host crystal. On the other hand, when substitu- local-gap mode conditions are contained in it. In other
ting for the heavier mass by a lighter impurity, one words m~&pgc guarantees the local-gap mode con-
gets two modes, a local mode situated above the optic dition 222B & 222A, 222c (local mode of 8 in AC, and gap mode
band and a gap mode situated above the acoustic band of C in AB). Applying this condition on Na1, K Cl we
but below the optic band of the host lattice. %hen 6nd that although it satisies the local-gap mode
substituting with a heavier impurity for the heavier condition (222N, &222K, 222o1), it does not satisfy the
atom no new modes, gap or local, are generated. How- stronger condition (2NN, &pKo1); therefore, it should
ever, the above condition does not necessarily predict exhibit one-mode behavior, which is indeed the case.
the right mixed-crystal behavior. For example, the Table I shows the result of this condition tested on some
mixed system Na& K Cl does satisfy the local-gap mixed crystals. Those which obey the inequality
mode condition m~&p~c exhibit two-mode behavior, whereas the op-
mK=39&mci=35 5 posite is true for the one-mode behavior. In summary,
and then, a two-mode (one-mode) mixed crystal must (not)
mN, = 23(mK —39, (21) have one substituting element whose mass is smaller
than the reduced mass of the compound formed by the
indicating the appearance of local and gap modes at other two elements.
@=1;whereas
mwg —23 Qmc$ —35.5 IV. MODEL CALCULATIONS FOR SYSTEMS
WITH TWO-MODE BEHAVIOR
mK= 39& mN„= 23 (21')
2' P. Mazur, E. %V. Montroll, and R. B. Potts, J. Wash. Acad. From Eqs. (10), (10') (11), and (11') we know that
Sci. 46, 2 (1956). all the parametersin Eqs. (17) and (18) may be ex-
LONC, -WAVELENCTH OPTI|- PHONONS Or MIXEn CRYSTALS
TABS,E I. Conditions governing mixed crystal behavior.

One-mode system
NaI K Cl KC11 Br, NiI, Co 0 Ca1 Sr F2 Ba SrI,F2 GaAs1 Sb, Cd Zn1 S
Mixed mNa=23 moj=35. 5 mNj 58 7 moft, =40 mga, = 137 mA, = 74.9 = 112.4
meed
crystal &pal=20&pKgr= 26.3 &psrF2 = 26.6 &pt."oo = 19
&peasb &ps, F~ = 26.6 &pzns = 21.5
ABI,C mK — —39 = 79.9 m@0=58 8 ms, =87.7
mp, ms, =87.7 msb=121 8 mzn= 65.4
&pNacj —14 &pKgj= 18.6 &piVio 19 &pCaF2 19 &peaF2 30 4 &peaAs &pads —24.9
Local-gap mode Gap mode at X=0, local and only gap mode at X = 0 or X= 1 are allowed
condition of gap modes at X=1 are allowed
Mazur et al.
Condition no no no no no no no
mB &pA e~
Two-mode system
GaP1 As, InP1 As CdSI, Se~ ZnS1 Se Si1 Ge
Mixed mp —31 mp=31 ms=32 ms=32 Msj= 28
crystal &poaAs = 36.4 &PjnAs=46 &PCdse =46 4 &PZnSe=35 8 &Me, = 72.6
ABI,C, mAs= 74 9 mAs=74. 9 ms, =79 mse=79
&pe, p = 21.4 &pInp —23 &pt"ds 24.9 &pzns = 21.5
Local-gap mode Gap mode at X=1, local and gap modes at X=O are allowed
condition of
Mazur et al.
Condition yes yes yes yes yes
mB&pA c

pressed in terms of known quantities of the pure It is clear from Eq. (28) that we can identify
compounds. The only two parameters need to be 4&Z1 /to TO, AB as the oscillator strength 41rpAB of the
identified are Z~ and Z~. This is easily done below. resonance coTo, AB»mila»y, 47rZO'/ro'To, Ac is the oscil-
Setting @=0 for Eqs. (17) and (18), and since ZO=O lator strength 4xp~t.- of the resonance coTo, ~g. For a
at x=0, we obtain one equation for the pure compuond mixed crystal of the two mode type, the observed
AB and one coupled equation: reststrahlen bands not only shift in frequency with con-
centration x but also vary in strength with the molar
Ri+ — + —Zg'—Ri
Fgggo 4m
— 0-
-——
, (24) fraction parameter. Thus we would expect the strength
—Pga 4rrZ s/co'To„, where t'=1 and 2 signifies AJ3 and AC,
respectively, is a function of x. %e assume it to be
~ACO++BCO
Rs+- Rs a linear function, since curve fitting of reststrahlen

t'~ABO
"
bands by damped oscillator models of some mixed
crystals, e.g. , CdS& Se, and ZnS&, Se, indeed show "
+ I
—J"BCO~ ~f AC~

II R, =o. (25) a linear variation of oscillator strength with concen-
mc l «pABP
I
l
mA tration x. Accordingly, we assume for any value of x,
These equations should give the longitudinal solu- 4rrZ1'(x)/to'To, t(x) = (1—x)4orpAB, (30)
tions, one of them is the Lo of AB and the other is the
4rrZO'(x)/to'To, s(x) = x41rpAc, (31)
gap mode of AC in AB, i.e.,
Pago 4mZg'
GD
2 l
= 2
xo, aa (26) 520-

and
(~ACO+~BCO)/mC OO sap ~ (27)
It is already known from Eq. (10) that FABo/pAB 1s
to'» AB. Thus Eq. (26) reduces to
4m. Z~' 240
LO, A. B
2
TO, AB ~ ~
220—
&oo -0)2 TO, AB
C
Comparing Eq. (28) with the I yddane-Sachs-Teller & 200
(I ST) relation" we obtain
4' Zy 6g 4X'pgg I l l I I
oo'To, AB= to To, AB (29) 0 .2 .4 .6 S


IO
&eo
CcIS X CdS@
'4 R. H. Lyddane, R. B. Sachs, and E. Teller, Phys. Rev. 59, Pro. 1. Long-wavelength optic phonons in CdS& ~Se, . ( )
673 (1941). theory, (0) LO (Raman), and (C) TO (infrared).
930 I. F. CHANG AND S. S. MITRA
TAEz E II. Parameters of two-mode type AB&,C„ro in cm ', E in cm '/g.

ABI C CdSI Se~ ZnS1 Se QaP1 As

MassA, B, C 112.4, 32.064, 78.96 65.37, 32.064, 78.96 69.72, 30.974, 74.922
eIc(Gap)'
&yAB(TO), 236, 188 270, 220 366, 271
ruAc(TO), &oAc(loc)~ 169, 268 206, 300 268, 339
~~so ~~eo ~aeo" ~ 138.93, 152,65, 126.43; 0.13224 156.82, 185.76, 197.40, 0.18303 287.28, 352.58, 197.66, 0.26598
G)AB(LO), ~AC(LO)p PABg SAC 305, 211, 24.9, 46.4 350, 252, 21.5, 35.8 406, 295.5, 21.4, 36.1
~„~a, ~„~e, ~p~a, ~p~e 5.75, 6.183, 3.854, 3.455 5.2, 5.75, 3.538, 2.855 8.457, 10.9, 1.95, 2.253
+ Local and gap-mode frequencies can be calculated if phonon densities of the host lattices are known accurately. Approximate estimates using theories
of P. G. Dawber and R. J. Elliott, Proc. Roy. Soc. (London) A273, 222 (1963); Proc. Phys. Soc. (London) 81, 459 (1963); and S. S. Jaswal, Phys. Rev.
137, 302 (1965) give values surprisingly close to the experimental measurements quoted here (see Refs. 14-16).
b Multiplied by 10 4.

where c0To, .(x) are solutions of Eq. (8). Table 11 shows istics of the k 0 phonons and related quantities of the
all the model parameters which are either known end members one can not only predict the behavior type
constants or derived from known quantities of the two of the mixed crystal but also the phonon frequencies
pure compounds AB and Ac. The coTo, s for any at any given mixing ratio.
value of x may now be obtained by solving Eq. (8) In order to test the reasonability of the assumption of
with the parameters listed in Table II. ceLQ;(x) are linear variation of the oscillator strengths with concen-
determined by solving Eq. (20) with the aid of Eqs. tration, Eq. (20) has been solved for 4sZts/ce'To, t and
(30) and (31), again using the parameters of Table II. 4BZs'/a&'To s using the experimental TO and LO fre-
6„, appearing in Eq. (20), is assumed to vary linearly quencies for all x. 4trZ, '/~'To; thus calculated are next
with x: identiied with . 4';.
e„(x)= xe„(AI C)+ (1 x) e„(A— B) . (32)
4s Z s(x)/tesTo „—
—4s p, (x) . (29')
The calculated values of ~To, 1,' ~TO, ~, +Lo, 1 L0, 2
Experimental values of 4sp;(x) are available from the
functions of x are compared with the experimental
analysis of reststrahlen spectra. The calculated and
values for CdS1,Se, ZnS1 Se and GaP1 As in
experimental values ' of 4s.p, (x) for ZnSt, Se„are com-
Figs. 1— 3. The experimental LO frequencies were
" pared in Fig. 4. Equation (20) has two roots each for
obtained by Raman measurements" and are accurate
to &2 cm '. The TO frequencies were determined" "" 4s-Zr'/re'To, t and 4B.Zs'/~'To, s. As shown in Fig. 4,
one set of the solutions agree very well with the experi-
from reststrahlen spectra by Kramers-Kronig analysis
mental 4xp, values and indicate a linear variation with
and damped oscillator 6ts. They are accurate to
+3 cm '. For GaPt &s, only TO frequencies are x, justifying the assumption made in Eq. (30) and (31).
The calculated values of 4mZP/~'To, s for CdSt, Se, are
available
data. ""It from the analysis
will be of interest to measure the O fre-
of infrared reQection
I. also shown in Fig. 4. One set of the roots indeed show a
near linear behavior.
quencies of GaP& +s,
by the Raman eRect and compare
with the predicted values presented here.
Note that the paremeters used in Eqs. (8) and (20) V. MODEL CALCULATIONS FOR SYSTEMS
were not chosen for the best 6t of the experimental WITH ONE-MODE BEHAVIOR
points for all x. Instead they were obtained from the The MRKI model described above can be applied
physical constants of the end members. Obviously, if the to one-mode systems as well. However, the boundary
former procedure was employed, the agreement between conditions of the force constants have to be redeined.
observed and calculated values can be brought even This is because in one-mode mixed crystals local and
closer. The reason for not doing so is that our objective
was to demonstrate that starting from the character- 42oj-
GaP, „As
s60I- 400
340 =, 380
320 -360—
E
O
K FIG. 3. optic
Long-wavelength
300 fn 340— phonons in GaPq ~As~.
( )
FIG. 2. Long-wavelength op tic theory, (0) LO (Raman), and (4)
280 phonons in ZnS1 ~Se~. ( ) 320— TO (infrared).
4j
260—
theory, (0) LO (Remen), and (4)
300—
TO (infrared). ~~

~ 240 280—
I I
220 .6 .8
I I l I
X eoAs
0 .2 4 8 3 lO
ZnS X Zn Se '-~
I. F. Chang and S. S. Mitra (unpublished).
LONG —9,'A VELENGTH OPTIC P HONONS OF M IXE D CRYSTALS 93k

TABLE III. Parameters of one-mode type AB~ C„ar in cm ', F in cm '/g.

ABI C Ni1 Co 0 KC11 Br K1 Rb C1 Cd Zn1, S


mA) mB) mC 16, 58.71, 58.933 39.102, 35.453, 79.909 35.453, 39.102, 85.47 32.064, 65.37, 112.4
~AB(TO), ~Ac(TO), B 402, 348, 0.25283 141.8, 116.5, 0.57696 141.8, 122.7) 0.53811 270, 236, 0.48172
~ABo ) ~ACo ) ~BCp 203.185, 203.97, 748.4 37.395, 84.286, 75.42 37.395, 81.74. 90.15 156.824, 269.65, 549.746
~AB(LO), (oAc(LO) 578, 549.5 210, 167 210, 185 350, 305
err2AB) &OGAC 5.7, 5.3 2.13, 2.33 2.13, 2. 19 5.2, 5.75
~PAB) 47rPAC 6.1653, 7.7467 2.55, 2.45 2.55, 2.81 3.538, 3.854
Fp') 8 203.185, 0.24996 37.395, 0.04648 37.395, — 0.0096 156.824, 0.11415

Multiplied by 1Q 4.

gap modes do not occur when the concentration of either FABO+FBCO FACO
of the members approaches zero. The above boundary E1E2—— (1—8)'=0, (x=1) . (37)
conditions may be achieved in two ways. The first is
based on the assumption that the triply degenerate The above two equations yield the following result:
local and gap modes split into two modes the trans- — FAB=FAC= FBC=F—
=FO(1 ex). — (38)
verse and the LO modes. This scheme is shown in Fig. 5.
The lines TO and LO with subscripts j. and 2 refer to Thus it results in one force constant only which varies
the general situation. Sy this assumption the boundary »nearly froinFABO Ic TO, AB/IIAB toFAco oo TO, Ac/@Ac.
conditions for the force constants are obtained by setting In view of Gruneisen equation of state, this may be
Eq. (10) equal to (10') and Eq. (11) equal to (11'), i.e., regarded as an analog of Vegard's law for the force
FABo FACo+FBCO constant. The above equation also indicates that Eq.
=+ TO, AB &
(33) (35) holds good for all values of x. Substituting (35)
JAB mg into (8) we thus obtain the nonzero root
FAco(1 &) FAao+F—
aco F— Fac
(1 —0) =to
(1 x)FAa Aa

mB
TG, Ac. (34) & To +I++2 + +x
mA mB mB
These two equations force a degeneracy on the system, ~AC ~AC ~BC
essentially making TO1 and TO2 lines as well as LO1 +* + +(1—*) (39)
and LO2 lines degenerate. Thus a one-mode behavior mA mg mg
occurs (see solid curves of Fig. 5). Using these two
equations the parameters of several one-mode type
Substituting Eq. (38) into (39) we obtain
mixed systems are calculated and the results are shown
in Table III. ~2To=E =I' 4o
The second method is to reduce the second-order
equation (8) into a first-order equation in IO2 for x= 0 and This result indicates that we have essentially arrived
@=1.In other words we have, for one root, cu2=0. The at the virtual-crystal" solution from the MREI model.
condition for this is that at @=0 and @=1
+1+2 +12+21 (35)
which can be reduced to
f ABO FACO+FBCO
E1K2= =0, (x= 0), (36)
Locot

ZAS x Se.

GOP
O

~N
0"'
l-X SX

2
l FIG. S. Double root scheme (method 1) for obtaining boundary
0 conditions. Subscripts 1 and 2 refer to the general situation.
.2 .4 .6 .8 LO Conditions (33) and (34) force 1 and 2 to merge into the solid
X
curves.
FIG. 4. Dependence of 42Z2/aPTo, on x. (X, ) solutions of
'

Eq. (20) (4OZ 2/a&2ro, ;), (V,n) experimental values, and ( ) "L.Nordheim, Ann. Physik 9, 607, 641 (1931). T. Muto, Sci.
linear assumption. Papers Inst. Phys. Chem. Res. (Tokyo) 34, 377 (1938).
932 I. F. CHANG AND S. S, MITRA 172
620- 22
Ni „CoO
580"
- 200
I
E
.
g 540- I80-
'3 FIG. 8. Long-wavelength optic
~500- FrG. 6. Long-wavelength
phonons in Ni& Co.O. (
optic
) ~ l60-
Lsj phonons in K~,Rb Cl. ( ) —.—
X X theory (method 1), ( ) theory
m460- theory (method 1 and method 2),
(O, I) LO (infrared), and (O, I) l40" (method 2), (0)
LO (infrared),
TO (infrared). and (C) TO (infrared).
&420-
g l20
380 1 I I
0 .2 4 .6 8 l0
340 KCl X RbCl
0 .8 IQ
Ni0 X coo
RbCl, whereas Jones ef al. "
give 116 cm '. Since the
comparison is made with the mixed-crystal data of
The force constant Fo and 0 computed for mixed crystals
Mitsuishi, a value of 123 cm ' was used in the present
Ni~, Co,O, Zn~ Cd, S, K Cl~, Br, and K~ Rb Cl
calculation.
are shown in the last row of Table III. Substituting the %hen the calculated values of TO and LO phonon
constants in Table III into Eqs. (8) and (20), the k 0
frequencies of the mixed crystals are compared with the
TO and LO frequencies are calculated, for two methods, experimental values, one finds that the model parame-
throughout the range @=0 to @=1 for the four mixed
ters obtained by the second method give excellent agree-
systems of Table III. The results compared with ex- ment. Although the first method displays one-mode
perimentally obtained values are shown in Figs. 6-9.
behavior, it gives relatively poor agreement except for
Except for the case of Cd, Zn~, S, none of the LO the case of Ni~ Co, O for which excellent agreement is
modes of either the end members or the mixed crystals
obtained by either method. Note that Ni and Co have
have been determined by direct experiment. For our almost the same mass. The results from the first
comparison LO's were obtained from TO's by either the method are included here to show that the virtual-
LST relation (using the es and e„obtained from rest-
strahlen spectra) or from Drude's rule. LO's ob- " crystal model derivable from our second method is not
the only way to obtain one-mode behavior, although the
tained by either method agreed within &2 cm '. In
latter seems to be well suited to describe the dependence
the case of Zn~ Cd, S, the TO and LO values shown in of the optic phonons of one-mode type mixed crystals
Fig. 9 were from the infrared measurements of Lucovsky with concentration.
et al. ~ Their result shows a small anisotropy splitting
( 6 cm ') for all values of x. However, for the purpose VI. AN EMPIRICAL RELATION
of comparison with the present calculations, average
FOR THE LO MODES
values of TO were used. Brafman, Chang, and Mitra"
have recently measured the LO frequencies of Cd, Zn&, S Equation (20') is a quadratic equation in ~'. The sum
by the Raman effect for a few values of x. These values of the roots obey the following relation:
agree within experimental error with the infrared
values of Lucovsky et al.
M Lo, 1+4& Lo, 2 El+47rZ1 /eoo+Z2+4sZ2 /eoo ) (41)
In determining the model parameters we have, in whereas the sum of the roots of Eq. (8') yields
general, used the end-member TO frequencies given in
the papers on the mixed crystals rather than those
te To, 1+re To, 2 Ill+Its ~ (42)
quoted in literature. Only in a few cases there were a From (41), (42), and (29') one obtains
difference of several cm '. For example, Mitsuishi'
gives a value of 123 cm ' for the TO frequency of
4vrpg
oo, + oo. = ooo(1+
220
+~'To, sl 1+
( 47rps)
~
(43)
200 e„
H l80 for any concentration x.
FIG. 7. Long-wavelength
IX l60- phonons in KCh ~Br . ( ——optic
) An inspection of Eq. (43) suggests, for trial solutions,
theory (method 1), ( ) theory
I40' (method 2), (o) LO (infrared), & Lo, t=& To, t(1+47rpr/e~),
and (C) TO (infrared). ~ Los= &
& !20
e„) (44)
To(, 1s+ p4ss/,

I I t I Equations (44) are strictly true for @=0 and @=1


0 .2 .4 .6 .8 lO
because they are identical with the LST relation.
KCI X K Br

However, for any other value of x, although they are


2~I. F. Chang, S. S. Mitra, J. N. Plendl, and L. C. Mansur,
"O. Hrafman, I F. Chang, and. S. S. Mitra (unpublished).
Phys. Status Solidi (to be published). "G. 0. Jones, D. H. Martin, P. A. Mawer, and C. H. Perry,
Proc. Roy. Soc. (London) A261, 10 (1961).
LONG —WAVELENGTH OPT IC P HONONS OF M I XE 0 CRYSTALS 933
TAnLE IV. LO modes (in cm ') calculated from Eqs. (44) and (20).

CdS1 Se ZnSI, Se GaPy-zAs~


X Empirical Exact solution Empirical Exact solution Empirical Exact solution
relation (44) of Eq. (20) relation (44) of Eq. (20) relation (44) of Eq. (20)
LO, LO, LO, LO, LO, LO, LO, LO2 LO1 LOg LOg LOg
0.0 305 188 305 188 350 220.3 350 220.3 406 271 406 271
0.1 304.5 190.6 304.6 190.3 347.9 224. 7 349.4 222.3 398.7 275.8 401.3 272. 1
0.2 302.9 193.2 303.7 192 345 228.8 347.5 224.9 391.6 279.9 395.1 275.0
0.3 300.5 195.9 301.7 194.1 341.4 232.6 344.4 228. 1 384.7 283.6 388.6 278.2
0.4 297.5 198.3 298.8 196.4 337.2 236.1 340.2 231.6 378 286.6 381.9 281.3
0.5 293.9 200.8 294.9 199.2 332.3 239.4 335 235.6 371.2 289.1 374.9 284.4
0.6 289.7 203.0 290.1 202.4 327.0 242.4 328.7 240. 1 364.6 291.1 367.7 287.3
0.7 384.9 205.3 284.4 206 321.0 245. 1 321.1 245. 1 358.2 292.6 360.3 290
0.8 279.8 207.2 277.8 209 314.7 247. 7 312.3 249.6 351.8 293.5 352.8 292.3
09 274. 1 209.1 270.5 210.3 307.7 250.0 302.5 250.3 354.4 294.0 345.2 294.2
1.0 269 2ii 268 211 300.4 252 300.4 252 339 294.4 339 294.1

consistent with Eqs. (41) and (42) they are not so when For infrared dispersion involving many optical modes,
one considers the products of the roots of Eqs. (20') although a generalized LST relation
and (8'). Moreover, they are also not consistent with
the generalized I.ST relation': ~. LO, s &TO, i = ~O ~~ (45')
"
L0, 1N L0, 2
K2 TO, 1%2 TP, 2
=—=1+
eo 4~pl

&c)
+, 4~p2
(45)
holds good, it does not, however, yield the LO mode
frequencies individually. In view of the agreement ob-
tained in Table IV, it is proposed that equations of the
although it has not been established that (45) should type (44) may be used as another approximate method
hold for mixed crystals. for obtaining individual LO's when the damped oscil-
Because of their simple forms, Eqs. (44), nevertheless, lator parameters are known. For mixed crystals of
may be regarded as approximate solutions for the LO's one-mode type, Eqs. (44) simply reduce to the LST
of mixed crystals. Indeed Eqs. (44) may be identified relation.
with the leading term in an expansion of the LO roots
of a multiresonance system given by Satten. LO's " VII. SUMMARY AND CONCLUSIONS
calculated from (44) with the aid of Eqs. (30) and (31)
are compared vrith those obtained from the exact
In this paper a phenomenological theory for the long-
wavelength optic phonons of mixed crystals has been
solutions of Eq. (20') in Table IV. Agreement is sur-
presented. Given the properties of the end members,
prisingly good. This may be understood from a com-
parison of Eqs. (44) and (45). Computing reLo i'ott, o s / the theory is able to predict whether a crystal ABl, C,
will show one-mode or two-mode behavior and also the
ot'To, iot'To, s from Eq. (44) one gets
dependence of the optic phonon frequencies on the mole
& r, o, iso Lo, s 4irpt 4s'ps $4irpt) 4irps) fraction x. The knowledge of the local or gap mode
=1+ + +k (46) frequencies for an infinitesimal amount of in AC or 8
)
I

I
I I

& To, lot To, 2 e~ coo e«& e(~


C in AB has been implicitly assumed for some of the
Comparing Eq. (46) with (45) one finds that the error cases considered. However, the theory can predict the
lies in the product (4irpi/e„)4irp2/e„, which has a maxi- existence or nonexistence or local or gap modes, and
mum around x=0.5 because of their near linear de- their frequencies are known, at least in principle, from
pendence of x. the properties of the host lattice with the aid of exist-
ing theories on crystals with imperfections. For crystals
360- that exhibit one-mode behavior, no such restriction is
340 necessary. Isolated models that have been used in the
past for depicting the behavior of mixed crystals, e.g. ,
F 520
CP
Fro. 9. Long-wavelengthoptic the virtual-crystal model or the REI model are shown to
~300- phonons in Zn& Cd~S. ( ) —— be special cases of the present theory.
m280- theory (method 1), ( ) theory
K (method 2), (O) LO (infrared),
and (C) TO (infrared). ACKNOWLEDGMENTS
g 260
240 We are very grateful to Dr. J. N. Plendl and L. C.
220
Mansur for many helpful discussions and for their
4 6 8 l0 keen interest in this work. Our thanks are also due to
ZAS X Cds
'0 1V. Cochran, Z. Krist. 112, 46& (1959). 7. Conte, Mrs. J. Howard, and Mrs. M. Barney for
» R. A. Sstten, J. Chem. Phys. 41, 281 (1964). t;heit. assistance ip comput@tiop ap. d typography,

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