T. D.

SOKOLOVSKII: Phonon Spectrum of Boron Nitride with Wurtzite Structure 493

phys. stat. sol. (b) 118, 493 (1983)
Subject classification: 6; 8; 22
Institute of Physics of Solids and Semiconductors,
A d e my of Sciences of the Belorussian SSR, Minsk1)
Phonon Spectrum of Boron Nitride with Wurtzite Structure
BY
T. D. SOKOLOVSKII
Using the quantum mechanics methods the interatomic force constants for the rigid-ion model of
boron nitride with wurtzite structure are calculated. An analysis of the symmetry of the fundamen-
tal vibrations of the lattice is performed by construction of the projection operators. The calcula-
tions of the phonon dispersion relations along seven directions of high symmetry of this lattice
are carried out in the harmonic approximation. In terms of this model the phonon state density
and the specific heat temperature dependence are determined for boron nitride with wurtzite
structure, the results being in good agreement with the experimental data on the specific heat.
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1. Introduction
It is known [l, 21 that the information about the energy of phonons is necessary for the
investigation of many important properties of crystals.
The dynamical theory of the crystal lattice of Born [l] allows to investigate the
energy characteristics of phonons in perfect crystals. Merten [3] used this theory for
studying wurtzite-type crystals. To define such crystal properties the knowledge of the
interatomic force parameters is needed. I n some cases these parameters can be deter-
mined from the experimental data. But it is not always possible, due to the lack of
knowledge of the initial macroparameters. This, in particular, is the case for boron
nitride with wurtzite structure.
I n this paper the interatomic force parameters of boron nitride are calculated allow-
ing to determine the dispersion relations of the phonons at the points and lines of high
symmetry for wurtzite as well as phonon state density and specific heat of boron nitride
with wurtzite structure. The results are obtained in the harmonic approximation tak-
ing into account both central and angular interactions [4] of rigid ions of boron and
nitrogen, which are at the nearest distances. The contribution of the long-range Cou-
lomb forces [ 5] is also considered within this model, The above-mentioned ion inter-
actions are described by eight interatomic force parameters, obtained in this paper
by quantum-mechanical methods.
2. Interatomic Force Parameters
Here the interatomic force parameters of pair interaction are dealt with. Each ion of
the wurtzite lattice, as well as that of sphalerite, has four nearest ionsof opposite polari-
l) Prospekt Brovki 17, Minsk, USSR.
494 T. D. SOKOLOVSKII
ty forming a regular tetrahedron. However, due to the lower wurtzite symmetry as
compared to that of sphalerite, not all four peaks of the tetrahedron are equivalent to
each other. As a consequence, a larger number of interatomic force parameters should
be introduced for wurtzite than for sphalerite, in particular, for diamond [6]. Accord-
ingly, we have two nonequivalent force matrices for nearest neighbour ions of boron
and nitrogen,
2 ) = 0 n; 0 *
10 0 4J
Thus, seven interatomic force parame ers are defined from the symmetry con1 itions
of the wurtzite lattice. They are determined by calculating the electron and nuclear
contributions to the corresponding projections F,( I RI) of the interatomic force, depend-
ing on the distance I RI between the nuclei of these ions, as well as on the direction in
the unit cell. Let the nucleus of boron ion 1 in equilibrium state be at the origin of
the coordinate system, while the nucleus of nitrogen ion 2 on the threefold symmetry
axis. Then the projection P,([ RI) of the force F(I RI) on the axis Ox: is calculated by the
formula
P,(IRI) = 2,ef J IyI2 X
dP - ZlZ2e2x IRI-3,
(3)
where Zle+, Z2e- are the effective charges of ions 1 and 2; v is the volume in which
the electrons of ions 1 and 2 are distributed and over which the integrals have been
taken; r is the radius-vector of any point of the volume V ; X is the projection of the
vector r on the coordinate axis Ox; xi s the projection of the vector R on the coordinate
axis Ox; y is the wave function defined using the sp3-hybridized orbitals v1 and p2
of valence electrons of ions 1 and 2,
Y = -4% + BY, 7 (4)
where A, B are the coefficients determining the electron population of the orbitals p1
and pz normalized to unity. The conception of hybridized wave functions was develop-
ed by Pauling [7], Slater [S], and others. For instance, for crystals with tetrahedral ion
coordination, in particular, in the case of sphalerite and wurtzite lattices the solution
of a number of problems [7 to 101 showed that the chemical bond between the nearest
ions can be described quantum mechanically by the sp3-hybridized wave functions,
built from the wave functions of the valence electrons. In the proposed method the
radial functions of the valence electrons of boron and nitrogen atoms are calculated
by the Hartree-Fock method according to the procedure suggested by Brattsev [ll].
With these functions being sufficiently accurate, the Feynman [12] theorem can be
considered to be valid. This makes it possible to apply electrostatics for calculating
the interaction forces between the ions [S]. The angular parts of the wave functions
of the valence electrons of boron and nitrogen atoms are taken as spherical harmonics
used in the theory of hydrogen atom.
The wave functions pl and pz, generally speaking, are not orthogonal, hence their
electron populations are not additive. Nevertheless, they can be orthogonslized. It is
Phonon Spectrum of Boron Nitride with Wurtzite Structure 495
convenient to use the method of the symmetric orthonormalization [13]. The elements
of the overlap matrix S for the nearest boron and nitrogen ions were calculated. Then
the new wave functions yi , pi were defined by the formula
This transformation causes the minimum deformation of the initial functions yl, p2.
Now it is assumed that the functionsq,, p2 are orthonormalized in relations (3) and (4).
Then the electronic populations of the wave functions y1 and y 2 according to (4) are
A2 and B2. The nucleus and two 1s-electrons of each of boron and nitrogen atom can
be considered as cores with charges 3e+ and 5e+, respectively. Therefore, the effective
charges of the boron and nitrogen ions are equal to eT = Z,e+= (3 - A2) e+, e z =
= 2,e- = ( B2 - 5) e-, where e+, e- are the proton and electron charges. It follows that
eT + eg = 0, i.e. the electroneutrality principle is fulfilled in the BN crystal.
The effective charge value of a nitrogen ion equal to 0.379e- was chosen so that the
maximum energy of the transverse optical phonon in the infinitely long wave limit,
was in agreement with the I R spectra data [14] of 3.36 x l OI3 s-l. I n this way the radial
function Fa( ] RI) has been calculated, allowing to determine the central P, and angular
Q, components [ 4] of the interatomic force parameters: ax, /?,, yl, a, , F,, a;, F; according
to the formulae
For boron nitride with wurtzite-type structure these parameters appeared to be
0 1 ~ = 0,7787; 16, = 1.817; y1 = 6, = 0.3671; E, = 0.9085; a; ==a,; E; = 1.947. These
parameter values are given in units of lo2 N/m .The calculation showed that, not all
seven interatomic force parameters are different,.
3. Phonon Spectrum
The normal mode frequencies of the vibrations of crystal lattice ions are described by
with the elenients WEF(q) of the Fourier-transformed dynaniical matrix in the given
model,
where q is the phonon wave vector, k, lc' are the indices, denoting the ion numbers in
the primitive cell of the crystal, i.e. for the wurtzite structure k, k' = 1, 2, 3, 4;
x, y are the indices of the Cartesian coordinates, i.e. x, y = 1, 2, 3; Df i ' ( q) is the matrix
element of the short-range forces; CB[(q) the matrix element of the Coulomb long-range
forces. Thus, for wurtzite W( q ) is a (12 x 12) matrix.
It is important to take into account the symmetry of this dynainical matrix. I n the
present paper group-theoretical methods were used for simplifying the structure of the
dynamical matrix D( 0) . With this aim in view the projection operators were deter-
mined by
1 Wt r ( q) - 4n2v26,,6kv( = 0 ,
W::(q) = D:;(q) + c::(Y) >
(7)
(8)
ONq) = CI zk?(q, A) T(q, 4 >
(9)
A
where&Y(q, A) is the complex conjugate matrix element of the j-th irreducible multi-
plier or weighted representation [15, 161 of the point group Go(q) of the wave vector q;
T( q, A) the reducible representation of the group Go( q) ; A the orthogonal matrix
(3 x 3) corresponding to the element of the group Go(q).
496 T. D. SOKOLOVSKII
The application of projection operator techniques allowed us to determine the uni-
tary transformations of the dynamical matrix at the point and lines of high symmetry
of the first Brillouin zone of the wurtzite lattice of boron nitride. With the point
group of the wave vector q = 0 being isomorphic to the lattice point group, the largest
effect of accounting the symmetry can be expected at this point. I n this case the
unitary transformation is as follows:
Ur =
0 0 0 0
0 0 0 0
a, a2 a3 a4
0 0 0 0
0 0 0 0
0 0 0 0
0 0 0 0
a, a2 -a3 -a4
0 0 0 0
0 0 0 0
b, b, -b, -b4
bl 62 b3 b4
a5
-ia,
0
-ib,
0
a5
- ia,
0
-ib,
0
b5
b5
a5 a7 a7
ia5 -ia, iai
0 0 0
ib, -ib, ib,
0 0 0
a5 a7 a7
i a, -ia, i a,
0 0 0
ib, -ib, ib,
0 0 0
b5 b, b,
b5 b, b,
as 9
-ins in,
0 0
-ib, ib,
0 0
-a9 -a,
i u, -ias
0 0
-bs -bs
ib, -ib,
0 0
bs bs
an
-iall
0
-ibll
0
- a11
i a,
0
61,
-b11
ibll
0
all
0
ib,
0
-a11
-%a,
0
-bll
-ib,
0
ia1 1
bll
Here Kovalevs notations [l6] are used for the irreducible multiplier representation
z, , t 5, z, , tll, which appear twice in the reducible representation T( q, A) and are related
to the corresponding columns of the unitary transformation Ur. The Ur matrix ele-
ments are the complex numbers az , bl ( I = 1, 2, 3,4, 5, 7, 9 , l l ) as well as the numbers
i = and 0. The symmetry conditions of the wurtzite lattice allow to choose arbi-
trarily the numbers al , bz, which, however, must not be equal to zero and the modulus
of each vector-column of the matrix Ur must be equal to unity. If we apply the trans-
formation of Ur to the dynamical matrix D(O), then it is possible to factorize it into
six matrices of second order located along the principal diagonal of the matrix D(0).
I: M L R A
+-----G(v) (arb.units/
Fig. 1. Phonon spectrum of boron nitride with the wurtzite-type structure. a) Phonon state den-
sity, b) phonon dispersion branches along seven directions: IK, KH, HA, Ar, rM, ML, LA
Phonon Spectrum of Boron Nitride with Wurtzite Structure
497
Fig. 2. Temperature dependence of specific heat of
boron nitride with the wurtzite-type structure (dots:
experiment [18], solid line: calculation)
s
70-
?
9 5-
2
Ul A I I 1 1 I I
-L
1
0 200 400 600 800
J / N -
For the sake of brevity the relation is given as
where the matrices Dl, D, describe the longitudinal branches, while the matrices
D3, D4 describe the transverse branches of the normal mode vibrations of the wurtzite
lattice at point r, with both D,, D, giving one acoustic and one optical branches of the
dispersion relations of phonons.
A similar situation is observed for the wave vector q = (0, 0, nj2 Ic]), where c is the
basis vector directed along the hexagonal axis of the wurtzite lattice.
However, at other symmetry points of the first Brillouin zone, where the order of the
point group of the wave vector is smaller than that at the point, the symmetry
effect is less significant. Besides, when the Coulomb long-range forces are taken into
account, the symmetry of the dynamical matrix C( q) decreases, resulting in the split-
ting of the energy of optical phonons. Thus, instead of six different values of the phonon
energies at I? point, predicted on the basis of the wurtzite lattice symmetry there are,
actually, seven of them. This is seen from Fig. 1 b where the dispersion curves along the
principal directions and at the high symmetry points of the first Brillouin zone of boron
nitride with wurtzite structure are shown. The curves are calculated in terms of the
above-mentioned model. Along the ordinate axis the values of the normal mode fre-
quencies of vibrations of the lattice in units of 1013 s-l are given. The abscissa axis
exhibits the conventionally designated points through which the wave vector end runs.
I n this case the relative values of the lengths of FK, KH, HA, Ar, FM, ML, LA
are 213, i@3, 213, i@3, f 33, fq8, i 3 3 , respectively. Because of the lattice symmetry
along the FA direction the transverse branches of the phonon dispersion curves are
pairwise degenerated, though it is not the case for the r K direction. The calculations
confirm thesepredictions. I n r M as well as in IK directions there is no degeneracy
of the energy levels, though in Fig. 1 b for the accoustic branches due to the narrowness
of these lines it is not shown.
I n terms of theabove-described mode1,using the Blackman method [17], the calcula-
tions of the state density function G(v) of the phonons in boron nitride with wurtzite
structure were performed (Fig. 1 a), taking into account 24084 points of the first Bril-
louin zone. This function is characterized by a series of extreme points related, in
general, to the optical branches of the normal modes of the crystal vibrations and the
acoustic vibrations make the main contribution to one of them.
The knowledge of the G(v) function made it possible to calculate the temperature
dependence of the specific heat of boron nitride with wurtzite structure in accordance
498 T. D. SOKOLOVSKII: Phonon Spectrum of Boron Nitride with Wurtzite Structure
with
These results are given in Fig. 2 by a solid curve, while dots show the experimental
data [ZS]. It follows from (10) that with the change of temperature the same energy
value of the phonon affects differently the heat capacity value. Therefore, the agree-
ment between the data obtained here and the calorimetric data [18] over a considerable
temperature range shows that all the frequencies are given sufficiently exact in G(v).
On the other hand, although there is a lack of experimental data on dispersion rela-
tions of the wurtzite modification of boron nitride in literature, the optical phonon
energy values in the centre of the Brillouin zone (Fig. 1 b) agree with the data on the IR
spectra [14]. Thus, the method suggested, where minimum information is used, allows
to obtain important results.
Acknozoledgement
The author would like to thank the Computation centre of the Academy of Sciences
of the BSSR for help with the calculations.
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