de Haas–van Alphen effect in the diborides , , and

V. B. PluzhnikovI. V. SvechkarevA. V. Dukhnenko, A. V. Levchenko, and V. B. FilippovA. Chopnik

Citation: Low Temperature Physics 33, 350 (2007); doi: 10.1063/1.2720083

View online: http://dx.doi.org/10.1063/1.2720083
View Table of Contents: http://aip.scitation.org/toc/ltp/33/4
Published by the American Institute of Physics
LOW TEMPERATURE PHYSICS VOLUME 33, NUMBER 4 APRIL 2007

de Haas–van Alphen effect in the diborides ScB2, ZrB2, and HfB2

V. B. Pluzhnikova兲
International Laboratory for Strong Magnetic Fields and Low Temperatures, ul. Gaovitska 95,
Wroclaw 53-421, Poland and B. I. Verkin Institute for Low-Temperature Physics and Technology
of the National Academy of Sciences of Ukraine, pr. Lenina 47, Kharkov 61103, Ukraine
I. V. Svechkarev
B. I. Verkin Institute for Low-Temperature Physics and Technology
of the National Academy of Sciences of Ukraine, pr. Lenina 47, Kharkov 61103, Ukraine
A. V. Dukhnenko, A. V. Levchenko, and V. B. Filippov
I. N. Frantsevich Institute of Materials Science of the National Academy of Sciences of Ukraine,
ul. Krzhizhanovskogo 3, Kiev 03680, Ukraine
A. Chopnik
V. Chebyatovski Institute for Low-Temperature and Structural Studies of the National Academy
of Sciences of Ukraine, p/ya 1410, Wroclaw 50-950, Poland
共Submitted July 20, 2006兲
Fiz. Nizk. Temp. 33, 473–478 共April 2007兲

ScB2, ZrB2, and HfB2 single crystals with hexagonal structure were grown and the properties of
the Fermi surface of these compounds were studied using the de Haas–van Alphen effect
共dHvA兲. The angular dependences of the frequencies of the dHvA oscillations in the planes
共101̄0兲, 共112̄0兲, and 共0001兲 and the values of their effective cyclotron masses were measured.
The frequencies of the oscillations found lie in the interval 共0.96– 28.2兲 ⫻ 102 T and the mea-
sured cyclotron masses lie in the range 共0.09– 0.87兲m0. The values of the electron–phonon inter-
action constant ␭ on different sections of Fermi surface of ZrB2 were determined. The value of
the constant ␭ ranges from 0.05–0.16. © 2007 American Institute of Physics.
关DOI: 10.1063/1.2720083兴

INTRODUCTION ated the present investigations. We chose compounds which

are representatives of the 3d, 4d, and 5d transition metals
Transitional-metal diborides are of interest because of with boron–ScB2, ZrB2, and HfB2, respectively, and we mea-
their technical characteristics–high melting temperature sured by means of the de Haas–van Alphen effect 共dHvA兲
共⬃3000 K兲, hardness, thermal conductivity, and chemical the angular dependences of the sections of the Fermi surface
stability, which are all much greater than the properties of the 共FS兲 in the 共101̄0兲, 共112̄0兲, and 共0001兲 planes and the cyclo-
initial elements–for applied and scientific purposes. Many tron masses for the magnetic field oriented in the directions
experiments investigating their physical properties have been
关101̄0兴, 关112̄0兴, and 关0001兴. The dHvA effect in ZrB2 and
performed on polycrystalline samples but only advances in
HfB2 has been measured in Refs. 3 and 4 for the purpose of
the technology for growing single crystals and further devel-
establishing the general form of their FS. However, up to
opment of methods for calculating the electronic spectra
now their effective cyclotron masses have not been mea-
have made it possible to move to a more fundamental level
of investigation of the nature of these compounds.
The crystal structure of transition-metal diborides is of
the AlB2 type, hexagonal space group P6 / mmm. The unit
cell contains the molecule MeB2, where Me is a transition
metal in the position 共0, 0, 0兲 and two B atoms in the posi-
tions ±共1 / 3 , 2 / 3 , 1 / 2兲, as shown in Fig. 1. Each type of atom
forms a hexagonal network in alternating planes which are
perpendicular to the c axis. However, these diborides cannot
be regarded as strictly layered compounds, since another
quite strong interaction exists between the B layers via the
metallic layers. This affects the anisotropy of the physical
properties of these compounds and introduces additional un-
certainties into the computational methods employed.1
Excellent works on the calculation of the electronic
structure and the fundamental properties of transition-metal
diborides have been published recently.1,2 These works initi- FIG. 1. Crystal structure of the compounds MeB2 共Me–Sc, Zr, Hf兲.

1063-777X/2007/33共4兲/5/$28.00 350 © 2007 American Institute of Physics

Low Temp. Phys. 33 共4兲, April 2007 Pluzhnikov et al. 351

sured. For the compoundScB2 the observation and study of

the dHvA effect in the present work is the first investigation
of the properties of its FS.

EXPERIMENT

The diboride single crystals were obtained by high-

frequency crucibleless zone melting in the Kristall-111 setup.
The initial diboride powders were obtained by reduction
of the oxides of the corresponding metals 共purity 99.95
mass %兲 with amorphous boron 共purity 99.9 mass %兲. The
zirconium and hafnium diboride single crystals were grown
using a sintered powder seed and the scandium diboride
single crystals were grown using a fused seed. Detailed in-
formation on the technology for obtaining and checking the
quality of the single crystals is presented in Ref. 5.
The initial single-crystal ingots consisted of rods with
the cross section varying along a rod. These ingots were
worked with a diamond disk to remove “skins”—an approxi-
mately 0.3 mm thick stressed surface layer, after which they
were oriented by the x-ray method into a prescribed plane
and cut by the electric erosion method. In their final form the
samples for performing measurements of the effect were
1.5⫻ 1.5⫻ 4 mm rectangular parallelepipeds and their faces
were oriented perpendicular to the high-symmetry crystallo-
graphic directions.
The measurements of the dHvA effect were performed
by the standard modulation method at temperatures from
1.5 K and in magnetic fields up to 9 T. Signal detection was
performed at the second harmonic with the fundamental fre-
quency of modulation of the magnetic field 233 Hz. The de-
tected signal Vosc for a magnetic field H can be represented
as

Vosc ⬇ A p sin 冉 2␲F

H
冊
+␸ , 共1兲

where F is the frequency of the dHvA effect, proportional to

the extremal 共maximum or minimum兲 transverse cross-
sectional area SF of the FS,

ប
F= SF , 共2兲 FIG. 2. Typical dHvA oscillations and their FFT spectra for H 储 关0001兴 in
2␲e
ZrB2 at 1.5 K in magnetic fields 2 – 4 T 共a兲 and 6 – 8 T 共b兲.

and the amplitude of the dHvA oscillations is

冑H ␣ pm*c T/H
A p ⬇ J2共x兲 3 , 共3兲
p 2 sh共␣ pmc T/H兲
*
where J2共x兲 is a Bessel function with the argument x
= 2␲ pFh / H2, p is the index of the harmonic of the oscilla-
tions, h is the modulating field, ␣ = 2␲2kBc / eប, m*c is the
effective cyclotron mass expressed in units of the mass m0 of
a free electron.
Figure 2 shows the typical dHvA oscillations and the
corresponding fragments of the fast Fourier transform 共FFT兲
spectrum for the compound ZrB2 at 1.5 K, H 储 关0001兴, in the
magnetic field ranges 2 – 4 T 共Fig. 2a兲 and 6 – 8 T 共Fig. 2b兲.
RESULTS AND DISCUSSION
ScB2
The results of the measurements of the angular depen-
dences of the frequencies of the dHvA oscillations for high-
symmetry planes are presented in Fig. 3. Sections of the FS
with frequencies in the range 共2.09– 23.6兲 · 102 T were ob-
served. The dependences ␺, ␶, and ␸ show that these frag-
ments of the FS are strongly anisotropic, and the depen-
dences of ␴ and ␲ are close to an ellipsoidal form. The
cyclotron effective masses were determined from the tem-
perature dependences of the amplitudes of the dHvA oscilla-
tions, using the relation 共3兲, specifically, from the slope of
the plots of ln兵A关1 − exp共−2␣m*c T / H兲兴 / T其 versus T, to which
352 Low Temp. Phys. 33 共4兲, April 2007
FIG. 3. Angular dependences of the dHvA oscillation frequencies in the
compound ScB2.
a least-squares straight line was fit, with a constant magnetic
field H, as shown in Fig. 4 and presented in Table I. It should
be noted that the observed dHvA oscillations ␺, ␶, ␴, and ␲
in the共101̄0兲 and 共112̄0兲 planes at angles up to 60° from
关0001兴 approximately retain their amplitude and therefore the
light masses m*c ⬇ 0.3m0. This agrees qualitatively with the
measurements of the electron specific heat C p = ␥T,6 where
␥ = 2.2 mJ· mole−1 · K−2. But dHvA oscillations ␳, ␴, and ␸
with m*c ⬇ 0.5m0 − 0.9m0 are observed near H 储 关101̄0兴. Such
FIG. 4. Temperature dependences of the dHvA oscillation amplitudes and
the cyclotron masses obtained in the ScB2 : H 储 关0001兴 for ␲, ␴, ␶, and ␺
oscillations 共a兲; H 储 关101̄0兴 for ␸, ␳, and ␴ oscillations 共b兲.
Pluzhnikov et al.
TABLE I. dHvA oscillation frequencies, their symbols 共Greek letters兲, and
the corresponding cyclotron masses in the compound ScB2.
an increase of the cyclotron mass could be due to an increase
in the band mass as a result of a manifestation of the d
electrons of scandium in this region of the spectrum, but it is
not due to an intensification of the electron–phonon interac-
tion, since the spectrum-averaged electron–phonon interac-
tion constant is ␭ = 0.058.2
ZrB2
The magnetoresistance and the Hall effect were mea-
sured in the first investigations of the FS in ZrB2 in 1966.7
They showed that this is a compensated semimetal with an
effective concentration of 0.04 electrons/cell with no open
trajectories. In 1978 the dHvA effect was observed and
investigated3 and an attempt was made to interpret the dHvA
oscillations on the basis of calculations of the band structure
FIG. 5. Angular dependences of the dHvA oscillations in ZrB2.
Low Temp. Phys. 33 共4兲, April 2007 Pluzhnikov et al. 353

TABLE II. dHvA oscillation frequencies, their symbols 共Greek letters兲, and
the corresponding cyclotron masses in the compound ZrB2. Column
3—their band masses from Ref. 1, column 4—electron–phonon interaction
constant, column 5—dHvA oscillation frequencies presented in Ref. 3.

FIG. 7. Angular dependence of the dHvA oscillations in HfB2.

The angular dependences of the dHvA oscillation fre-

quencies measured in the present work are presented in Fig.
5. 共The notations proposed in Ref. 3 for the branches of the
spectrum of the oscillations are retained here.兲 As one can
see from Table II, good agreement with Ref. 3 obtains for all
branches of the spectrum with the exception of the ␨ branch
in the 共112̄0兲 plane, where we did not observe oscillations,
possibly because their amplitude was too low. The effective
cyclotron masses have been determined for the first time.
Their values are presented in Table II and Fig. 6. The masses
for the low-frequency oscillations ␣, ␤, ␦, and ␥ are less than
0.2m0, while the masses for the high-frequency oscillations
␯, ␮, and ␧ are large. Column three in Table II shows the
values of the band masses mb from Ref. 1 and column 4
shows the values of ␭calculated from the relation m*c = mb共1
+ ␭兲.

TABLE III. dHvA oscillation frequencies, their symbols 共Greek letters兲,

of CrB2,8 using the “rigid band” approximation. The model and the corresponding cyclotron masses in the compound HfB2. Column
obtained at that time for the FS of ZrB2 was confirmed by 3—dHvA oscillation frequencies presented in Ref. 4.
improved calculations performed by the FLAPW method
共full potential linearized augmented plane wave兲.1

FIG. 6. Temperature dependences of the dHvA oscillation amplitudes and

the cyclotron masses obtained in ZrB2 for H 储 关0001兴 for ␧, ␮, and ␯
oscillations.
354 Low Temp. Phys. 33 共4兲, April 2007 Pluzhnikov et al.

HfB2 electron–phonon interaction in the quasilayered compounds

The compound HfB2 is isostructural and isovalent with
respect to ZrB2 and has a low carrier density 共0.04 electrons/
cell兲 and a low value ␥ = 1.0 mJ· mole−1 · K−2.9 We measured
the angular dependences of the dHvA oscillation frequencies
and determined their effective cyclotron masses, which are
presented in Fig. 7 and Table III. Since the FSs of both
compounds are similar to one another, the previous notation
for the branches of the spectrum of the dHvA oscillations is
retained.
The agreement with the results obtained in Ref. 4 for the
low-frequency oscillations ␣, ␤, ␦, and ␥ with F = 共1.0
− 5.75兲 · 102 T, which originate from small fragments of the
MeB2, which possess remarkable physical and chemical
properties.
We thank Yu. B. Paderno for active support of these
investigations, Professors Ya. Klamut and V. NizhankovskiŽ
for helpful remarks during a discussion of the results of this
work, and N. Yu. Shitsevalov for assistance in making the
ScB2 single crystal.
The work was performed with the support of INTAS
under Project 03-51-3036.
a兲
E-mail: pluzhnikov@ilt.kharkov.ua

FS, is good. But we were able to detect a new high-

frequency branch of the oscillations ␧ with F = 18.1· 102 T,
characteristic for the main part of the FS.3 According to 1
H. Rosner, J. M. An, W. E. Pickett, and S.-L. Drechsler, cond-mat/
Table III, all oscillations have small effective masses in 0203030 共2002兲.
agreement with the low value of ␥ and the low density of
2
P. Vajeeston, P. Ravindram, C. Ravi, and R. Asokamani, Phys. Rev. B 63,
045115 共2001兲.
states at the Fermi level, equal to 3.69 关states 3
T. Tanaka, Y. Ishizawa, E. Bannai, and S. Kawai, Solid State Commun.
Rydb.−1 cell−1兴.2 26, 879 共1978兲.
4
T. Tanaka and Y. Ishizawa, AIP Conf. Proc. 231, 46 共1991兲.
5
G. Levchenko, A. Liashchenko, A. Evdokimova, V. Baumer, V. Filippov,
CONCLUSIONS Yu. Paderno, and N. Shitsevalova, J. Solid State Chem. 179, 2949 共2006兲;
The first study of the dHvA effect in the compound ScB2 R. Singh, M. Trenary, and Yu. Paderno, Surf. Sci. Spectra 7, 310 共2000兲.
6
J. Castaing, R. Caudron, G. Toupance, and P. Costa, Solid State Commun.
was performed and the first measurements of the cyclotron 7, 1453 共1969兲.
7
masses in the compounds ZrB2 and HfB2 were performed. J. Piper, J. Phys. Chem. Solids 27, 1907 共1966兲.
8
Using the values obtained from the calculations in Ref. 1 for S. H. Liu, L. Kopp, W. B. England, and H. W. Myron, Phys. Rev. B 11,
3463 共1975兲.
the band masses mb for ZrB2, the values of the constant ␭ 9
Y. S. Tyan, L. E. Toth, and Y. A. Chang, J. Phys. Chem. Solids 30, 785
were determined experimentally for the first time for differ- 共1969兲.
ent sections of its FS. The results obtained in the present
work can be used to clarify the specific nature of the Translated by M. E. Alferieff