Solid State Phenomena Vols 233-234 (2015) pp 97-100 Submitted: 2014-06-18

© (2015) Trans Tech Publications, Switzerland Revised: 2014-10-27

doi:10.4028/www.scientific.net/SSP.233-234.97 Accepted: 2014-11-05

Galvanomagnetic and Magnetic Properties of Pb1-yScyTe

E.P. Skipetrov1, a *, M.M. Markina1, K.V. Zakharov1, L.A. Skipetrova1,
A.A. Solovev1, A.V. Knotko2,b, E.I. Slynko3, V.E. Slynko3,c
1
Faculty of Physics, M.V. Lomonosov Moscow State University, 119991 Moscow, Russia
2
Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119991 Moscow, Russia
3
Institute of Materials Science Problems NAS of Ukraine, 58001 Chernovtsy, Ukraine
a
skip@mig.phys.msu.ru, bknotko@inorg.chem.msu.ru, cslynko.vasily@gmail.com

Keywords: Lead telluride-based alloys, transition metal impurities, electronic structure, scandium
resonant level, Fermi level pinning, galvanomagnetic and magnetic properties.

Abstract. The galvanomagnetic properties in weak magnetic fields (4.2≤T≤300 K, B≤0.07 T) as

well as magnetic properties (2≤T≤300 K, B≤9 T) of the single-crystal Pb1-yScyTe (y≤0.02) alloys
have been investigated. We find that an increase of Sc impurity content leads to a monotonous
growth of the free electron concentration (from 1016 cm-3 to 1020 cm-3). In heavily doped alloys
(y>0.01), it tends to saturation, indicating the pinning of the Fermi energy by the scandium resonant
level located inside the conduction band. The energy of the level is estimated (ESc≈Ec+280 meV)
and the model of electronic structure rearrangement of Pb1-yScyTe alloys with doping is proposed.
In the frame of this model, using experimental temperature and magnetic field dependences of
magnetization, the concentrations of magnetically active scandium ions are determined and
connection of the electronic structure with the magnetic properties of the alloys are discussed.

Introduction
Lead telluride-based alloys doped with 3d-transition metal (TM) impurities (Ti, Cr, V, Fe, …)
are diluted magnetic semiconductors whose magnetic properties are dependent on their electronic
structure [1]. It is known that deep levels of impurities from the first half of the TM row are mainly
resonant levels located in the conduction band of the alloys. Substituting Pb2+ ions in the metal
sublattice these impurities initially exist in electrically neutral Im2+ states. But since the impurity-
induced deep levels are usually situated above the Fermi level, transitions to the electrically active
Im3+ states due to the self-ionization processes (Im2+→Im3++eband) take place. An increase of the
impurity content leads to the filling of allowed bands lying under the level with electrons up to the
pinning of the Fermi level by the impurity level. Thus, in heavily doped alloys densities of occupied
and empty states in the impurity band should correspond to concentrations of impurity ions in 2+
and 3+ states with different electrical and magnetic activities.
Scandium is a new TM impurity which influence on the electronic structure, on the electrical and
magnetic properties of the lead telluride-based alloys are poorly studied yet. From general
considerations one can suppose that by analogy with Ti [2] and Cr [3] impurity levels, Sc donor
level in PbTe should be located substantially higher the conduction band bottom. Besides, since the
scandium is a first element in the TM row, electrically active Sc3+(3d0) ions should be nonmagnetic,
where as electrically neutral Sc2+(3d1) ions should possess localized magnetic moment (S=1/2).
Thus, an essential rising of the magnetization of the heavily doped alloys should takes place after
the Fermi level pinning during the doping.
In order to reveal the scandium impurity level in PbTe and to establish correlation between its
electronic structure and magnetic properties we have studied galvanomagnetic and magnetic
properties (2≤T≤300 K, B≤9 T) of Pb1-yScyTe (y≤0.02) alloys.

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98 Achievements in Magnetism

Experimental Details
A Pb1-yScyTe single-crystal ingot with nominal Sc content y=0.01 was grown along <111> axis
from a mixture of pre-synthesized PbTe and Sc5Te8 by reacting the pure elemental constituents
using vertical Bridgman technique. It was cut perpendicular to the growth axis into 28 wafers (we
will refer to these wafers by their sequential numbers) each about 1.5 mm thick using wire cutting.
The crystal structure and the chemical composition were controlled at the cleavage surfaces of
wafers by X-ray fluorescence microanalysis using the scanning electron microscope LEO SUPRA
50VP (Germany) with the INCA Energy microanalysis system (Oxford Instruments, England). It is
shown that within the experimental error, all samples have good uniformity. Concentration of Sc
impurity exponentially increases (y≤0.02) from the end of ingot to its beginning (from the sample 3
to the sample 26) and there are no noticeable inclusions of secondary phases in the samples.
To investigate the galvanomagnetic effects, samples in the form of rectangular parallelepipeds
with typical dimensions of 4.0×0.7×0.7 mm3 were cut from the wafers using an electric discharge
machine. Then the samples were etched in a solution of bromine in hydrobromic acid and carefully
washed in ethyl alcohol and distilled water. Temperature dependences of the resistivity ρ and the
Hall coefficient RH (4.2≤T≤300 K, B≤0.07 T) were measured by four-probe dc technique. Taking
into account paramagnetic character of magnetization and absence of anomalous Hall effect in PbTe
with transition metal impurities [1,3,4], the free electron concentration in the samples at T=4.2 K
was determined as n=1/e|RH|. To perform magnetic measurements, samples were cleaved from
wafers at the liquid-nitrogen temperature and are shaped close to rectangular parallelepipeds 50-100
mg in weight. Temperature and magnetic field dependences of magnetization (2.0≤T≤300 K, B≤9
T) were studied using the PPMS-9 vibrating sample magnetometer (Quantum Design, USA).
Kinetics of free electron concentration and Fermi level pinning with doping
It is found that all samples of Pb1-yScyTe are characterized by n-type conductivity. Temperature
dependences of the resistivity ρ and of the Hall coefficient RH have “metallic” character: as the
temperature grows, the resistivity increases by more than an order of magnitude, the Hall coefficient
remains practically unchanged. As the scandium concentration increases, the resistivity and the Hall
mobility µH=|RH|/ρ at low temperatures decrease by approximately 2 orders of magnitude, while
absolute value of RH decreases by almost 4 orders of magnitude, that correspond to the monotonous
growth of the free electron concentration n=1/e|RH| from 1016 cm-3 to 1020 cm-3 (Fig. 1). In heavily
doped alloys (y>0.01) electron concentration tends to saturation, indicating the pinning of the Fermi
level by the Sc resonant impurity level located inside the conduction band.

Fig. 1. Free electron concentration and Fermi Fig. 2. Model of the electronic structure
energy at T=4.2 K as functions of scandium rearrangement of Pb1-yScyTe alloys with
impurity content in Pb1-yScyTe. increasing impurity concentration.
 Solid State Phenomena Vols. 233-234 99

To determine the position of the scandium resonant level ESc with respect to the bottom of the
conduction band, we calculate the dependence of the Fermi energy on the impurity content from the
free electron concentration using the six-band Dimmock dispersion relations for IV-VI
semiconductors with two different sets of parameters presented in [5]. The Fermi energy with
respect to the conduction band bottom Ec increases gradually and tends to saturate at approximately
280 meV above the conduction band bottom (inset in Fig. 1).
To explain the kinetics of the free electron concentration and of the Fermi energy in Pb1-yScyTe
with doping, we use the model of electronic structure rearrangement similar to the mentioned above
model suggested earlier for PbTe doped with another TM impurities (Cr, Ti) inducing resonant
levels in the conduction band (Fig. 2). According to this model doping with scandium leads to the
appearance of the donor resonant level ESc, to the gradual population of empty band states (initially
in the valence band and then in the conduction band) with electrons and, finally, to the pinning of
the Fermi level by the resonant impurity level which energy may be estimated as ESc≈Ec+280 meV.

Magnetic Field and Temperature Dependences of Magnetization

In lightly doped samples the magnetic field and temperature dependences of magnetization M
contain two principle contributions: temperature-independent diamagnetic contribution of the host
semiconductor lattice typical of PbTe-based alloys [1,4] and paramagnetic Curie-Weiss contribution
(T<50 K) probably due to the presence of magnetic Sc2+ ions (Fig. 3,4). An increase of the
scandium content leads to the appearance and gradual increase of additional linear in field and
temperature-independent paramagnetic share. Taking into account an essential (from 1016 cm-3 to
1020 cm-3) rising of the free electron concentration along the ingot, one can suppose that this
contribution may be connected with the paramagnetism of free electrons. In the samples from the
middle part of the ingot the pronounced oscillations of magnetization (the de Haas–van Alphen
effect) indicating a high structural perfection of the alloys was observed (curves 10, 20 in Fig. 3).
The electron concentrations calculated from the periods of oscillations in inverse magnetic field are
satisfactorily coinciding with values determined from the Hall coefficient at low temperatures.
To determine the concentration of magnetically active ions in the samples its contribution to the
magnetization is extracted by subtracting temperature independent diamagnetic and paramagnetic

Fig. 3. Magnetic field dependences of Fig. 4. Temperature dependences of magneti-

magnetization for Pb1-yScyTe (4–26 – serial zation corrected for the lattice diamagnetic
numbers of the samples). share and for the free electron paramagnetic
share for Pb1-yScyTe samples (4–26).
100 Achievements in Magnetism

(MD and MP) contributions from the experimental data. Then the approximations of M(B) and M(T)
dependences by the theoretical curves were performed using the modifying Brillouin function:

 2 J + 1  2 J + 1 gJµ B B  1  1 gJµ B B  
M ( B, T ) − M D − M P = N Sc 2+ gJµ B  cth  − cth  

(1)
 2 J  2 J k B (T − T )
0  2 J  2 J k B (T − T )
0 

where MD=χ0B, MP=PB, NSc2+ is the concentration of magnetic scandium ions with J=S=1/2 and
g=2, T0 is the Curie temperature.
Using χ0, P, NSc2+ and T0 as adjustable parameters, good agreement of theoretical dependences
(lines in Fig. 3,4) with experimental data was achieved. It is shown that Curie temperatures in the
samples are in the range from –3 to +1.5 K, which is indicative of the paramagnetic nature of the
interaction between magnetic centers. The concentration of magnetic ions is in the range (0.8–
10)×1018 cm–3 and remains significantly (by more than an order of magnitude) less than the
concentration of scandium impurity in the whole range of the impurity content. In general, this
result contradicts the model of the electronic structure rearrangement of the alloys with doping. The
reasons for this are not clear yet. However, it may be noted that in samples with maximal impurity
concentration some increase in the concentration of magnetic ions (up to 1019 cm-3) possibly
associated with the pinning of the Fermi level by the scandium resonant level was observed.

Summary
Obtained experimental results allow us to conclude that with the increase of Sc impurity content
in the Pb1-yScyTe, the free electron concentration at low temperatures increases monotonically and
tends to saturation at n≈1020 cm-3 due to the pinning of the Fermi level by the scandium-induced
resonant level. From the dependence of the free electron concentration on Sc content, using the six-
band Dimmock dispersion relations, the dependence of the Fermi level versus Sc concentration is
calculated and the energy of the Sc resonant level relative to the conduction band bottom is
estimated (ESc≈Ec+280 meV). Experimental results are explained using the model of the electronic
structure rearrangement with doping similar to the model suggested earlier for PbTe doped with
another TM impurities inducing resonant levels inside the conduction band.
The magnetization M of Pb1-yScyTe alloys contain three principle contributions: temperature-
independent diamagnetic contribution of the host semiconductor lattice typical of PbTe-based
alloys, low temperature paramagnetic Curie-Weiss contribution probably due to the presence of
magnetic Sc2+ ions and temperature-independent paramagnetic contribution of free electrons.
Approximations of M(B) and M(T) dependences by the Brillouin function are performed and main
magnetic parameters of the alloys are obtained. Experimental results are discussed in the framework
of the electronic structure model, assuming varying magnetic activity of Sc ions with doping.
This work was partially supported by the RFBR (Project No. 11-02-01298).

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