Journal of Alloys and Compounds 421 (2006) 19–23

Impurity band effect on TiCo1−xNixSb conduction: Donor impurities

Yu. Stadnyk a,∗ , V.A. Romaka b,c , M. Shelyapina d , Yu. Gorelenko a ,
L. Romaka a , D. Fruchart e , A. Tkachuk a , V. Chekurin b
a Ivan Franko L’viv National University, Kyryl and Mefodiy Str. 6, 79005 L’viv, Ukraine
b Ya. Pidstryhach Institute for Applied Problems of Mechanics and Mathematics,

Academy of Science of Ukraine, Naukova Str. 3b, 79053 L’viv, Ukraine

c National University “L’vivska Politehnika”, Bandera Str. 12, 790013 L’viv, Ukraine
d L.V. Fock Institute of Physics, St. Petersburg State University, Ulyanovskaya Str. 1,

Petrodvorets, 198505 St. Petersburg, Russia

e Laboratoire de Cristallographie, CNRS, BP 166, 38042 Grenoble Cedex 9, France

Received 27 July 2005; received in revised form 3 November 2005; accepted 7 November 2005
Available online 15 December 2005

Abstract
The role of the donor impurity band in the conduction of highly doped and compensated intermetallic semiconductors with MgAgAs type of
structure was investigated. A simulation of the electronic structure for TiCo1−x Nix Sb semiconducting solid solution was carried out. A scheme of
the impurity band transformation in TiCoSb semiconductor due to donor impurities doping was advanced. A conduction transition from activated
to metallic type when the TiCo1−x Nix Sb solid solution composition changes was observed. This conduction transition is associated with the
Anderson-type transition.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Semiconductor; Impurity band; Donors; Electrical conduction; Intermetallic solid solution

1. Introduction doped by acceptor impurities, and enable us to observe the

insulator–metal conductivity transition, predicted by theoreti-
This work is dedicated to the attractive role of the impurity cal calculations, which is the Anderson-type transition [22–24].
bands on electrical conduction of semiconducting intermetallic In Ref. [25] we have proposed a new approach to evaluate the
compounds with MgAgAs type of structure. It is based on a experimental data on the compounds with MgAgAs structure
comparison of our results and many experimental and theoreti- type. The essence of our approach consists in the simultaneous
cal investigations on electron and crystal structures, resistivity, consideration of the peculiarities in highly doped and compen-
Hall coefficient and thermopower behaviors, optical properties, sated semiconductors [26] and local disorders in the crystal
heat capacity, EPR spectra, magnetization and magnetic suscep- structure, especially in cases of the semiconducting intermetallic
tibility of the ternary M(Co;Ni)(Sn;Sb) intermetallics (M = Ti, solid solutions [27].
Zr, Hf), and their solid solutions series [1–21]. It is known that conduction of semiconductors is determined
The study of the influence of acceptor impurities, by the compensation degree, which in turn gives a location of
with different concentrations (NA ) from NA = 3.5 × 1020 to the Fermi level (EF ). Determination and ability to change the
5.3 × 1021 cm−3 on electrical transport properties in n-ZrNiSn location of the Fermi level in the TiCoSb semiconductor form
and the calculated density of states in Zr1−x Scx NiSn alloys also an important practical task, because this compound and the
enable us to propose a scheme of impurity acceptor band trans- related solid solutions based on the ternary TiCoSb compound
formation. In contrast, the MgAgAs type semiconductors were are one of the most perspective novel thermoelectric materials
[28–30].
The structure disorders in the MgAgAs type compounds
∗ Corresponding author. [3], caused by the fluctuations in doping by charged impuri-
E-mail address: stadnyk [email protected] (Yu. Stadnyk). ties (1019 –1021 cm−3 ), which specify both the appearance of

0925-8388/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.11.008
20 Yu. Stadnyk et al. / Journal of Alloys and Compounds 421 (2006) 19–23

the impurity levels in the band-gap [26] and the localized states
in the band of continuous energies, separated by the mobility
edge [27]. These localized states strongly influence the kinetic
characteristics of the semiconducting materials. To separate the
effects associated with the impurity band we shall compare
the presented experimental data with the electronic structure
calculations using Green’s functions in the coherent potential
approximation [31] for the TiCoSb compound.
The presented work is the second part of our previous pub-
lication [23] and it is devoted to the study of the donor impuri-
ties influence on transport properties of the MgAgAs structure
type intermetallic semiconductors. In this work we investigate
the behaviors of conduction, Seebeck coefficient and magnetic
susceptibility of TiCoSb doped with the donor impurities via
substitution of Co (3d7 4s2 ) by Ni (3d8 4s2 ) atoms and subse-
quent formation of the TiCo1−x Nix Sb solid solution. Donor con-
centration (ND ) changed from ND = 1.9 × 1020 cm−3 (x = 0.01) Fig. 2. The dependence of conductivity σ, Seebeck coefficient S, magnetic sus-
ceptibility χ at 80 K and calculated density of states on Fermi level (insert) vs.
to ND = 3.8 × 1021 cm−3 (x = 0.2). The samples synthesis, heat composition of TiCo1−x Nix Sb.
treatment, X-ray phase analysis, the measurements of the elec-
trical resistivity (ρ), Seebeck coefficient (S) in relation to copper
and magnetic susceptibility by Faraday method (χ) in the tem- shown that for TiCoSb (x = 0) ε1 ≈ 176 meV, and ε2 ≈ 9 meV.
perature range 80–380 K were described in Ref. [32]. The Seebeck coefficient changes with temperature quasi-linearly
[32].
2. Results and discussion For sample with x = 0 at T < 100 K the Seebeck coefficient
has a slight positive value (Fig. 2). Otherwise the thermopower
X-ray analysis confirmed the pure single-phase state of all has negative values at higher temperatures for the TiCoSb com-
TiCo1−x Nix Sb (x = 0–0.2) solid solution samples. They crys- pound. The rest of the samples have a negative thermopower
tallize in the MgAgAs structure type (F 4̄3m space group). in the whole temperature range investigated. The sign reversal
The crystal structure refinement of TiCo0.99 Ni0.01 Sb and from positive to negative testifies that the investigated TiCoSb
TiCo0.95 Ni0.05 Sb showed the atomic distribution belongs to the compound contains uncontrolled impurities and has hole-type
MgAgAs structure type, in which the 4(a) 0 0 0 positions have conduction.
been occupied by a statistical mixture of Ni and Co atoms The doping of semiconductors by the donor impurities with
[32]. ND = 1.9 × 1020 cm−3 (x = 0.01) results in a reconstruction pro-
The ln ρ (T−1 ) dependence for TiCo1−x Nix Sb at x ≤ 0.01 cess in the impurity band. Changes in the compensation degree
seems as being typical for semiconductors (Fig. 1). At x > 0.01 and location of the Fermi level as well as change in the band
the thermally activation parts in the ρ(T) plots disappear and dimension and its location relative to the top of the continuous
the curves show metallic-like behaviors. The ln ρ (T−1 ) plot for energies band lead to a change of the conduction mechanisms of
TiCoSb sample is distributed in both high- and low-temperature the semiconductor. The Fermi level has to be placed on the bot-
activation parts. These parts we associate with electron activa- tom of the impurity band at full semiconductor compensation.
tion from the Fermi level in the conduction band (ε1 ) and into the EF will drift across the impurity band towards the conduction
mobility edge of the conduction band (ε2 ). The calculations have band at overcompensation (increasing of x). The decrease of the
activation energy ε1 from 9 meV (x = 0) to 3.5 meV (x = 0.01)
indicates a displacement of the Fermi level relative to the mobil-
ity edge of the conduction band (EC ) via a change of the
compensation degree of the semiconductor. Fig. 2 shows that
decreasing χ(x) (χ is proportional to N(EF )) and increasing
S(x) (S is proportional to kB T/EF ) occurs in the same concen-
tration range (x = 0–0.05). Whereas the investigated samples
are paramagnets, the observed simultaneous behaviors of S(x)
and χ(x) in the concentration range ND = (1.9–9.5) × 1020 cm−3
(x = 0.01–0.05) indicates decreasing a density of states at the
Fermi level. This is caused by change in compensation degree
of the semiconductor with following overcompensation from
p-type to n-type conduction. The latter gives rise to a shift
motion of the Fermi level from the bottom of the impurity band
Fig. 1. Temperature dependence of electrical resistivity (ln ρ vs. reciprocal tem- towards the conduction band (case of high n-type compensation
perature) for TiCo1−x Nix Sb solid solution (x: 1, 0; 2, 0.01; 3, 0.03; 4, 0.05). of semiconductor) up to its top (case of low compensation) when
 Yu. Stadnyk et al. / Journal of Alloys and Compounds 421 (2006) 19–23 21

increasing the donor concentration [26]. We assume that in this

concentration range the Coulomb gap disappears because occu-
pation of all states in the impurity band occurs. The impurity
band overlaps with the mobility edge of the conduction band
and the Fermi level becomes fixed by EC at the density of states
minimum. For sample with x = 0.01 at T ≥ 270 K a contribution
of the band carriers becomes appreciably high and at T ≥ 300 K
conduction metallization is observed and the raise in ρ(T) is
determined by band scattering mechanisms (Fig. 1). That is since
at x = 0.01, at specified values of temperature, the quantity of free
electrons with sufficiently high mobility become high enough,
and these carriers may play a considerable role in the electrical
conduction of these semiconductors. Therefore, the values of
the conductivity in that concentration range increase roughly by
three orders. Fig. 3. The scheme of reconstruction of the impurity band in the TiCoSb com-
At ND > 9.5 × 1020 cm−3 (x > 0.06) an increase of χ(x) and pound doped by donor impurities. The broken line in (c) shows a virtual location
of the Coulomb gap which is disappeared at high donor impurities concentra-
σ(x) is observed with a simultaneous decrease of the Seebeck tions.
coefficient at different compositions of the n-TiCo1−x Nix Sb
solid solution. These are associated both with the appearance and In analogy with semiconductors with MgAgAs structure type
increase in concentration of free electrons and increasing density doped with acceptor impurities [22–25], we propose a model of
of states at the Fermi level in the conduction band (above EC ) as reconstruction of the impurity band in the TiCoSb compound
well. The conduction of n-TiCo1−x Nix Sb exhibits metallic-like doped with the donor impurities of different concentrations
behavior. (Fig. 3).

Fig. 4. The partial and the total density of states for TiCo1−x Nix Sb solid solution samples.
22 Yu. Stadnyk et al. / Journal of Alloys and Compounds 421 (2006) 19–23

Fig. 4 shows the results of calculations of the partial den- agreement between theoretical calculations and experimental
sity of states for each component of the TiCo1−x Nix Sb solid data concerning the transition from activation- to metallic-type
solution alloys and the total density of states at the various x conduction indicates the trustworthiness of our model for recon-
values. The border ternary TiCoSb and TiNiSb compounds for struction of the impurity band as result of doping with donor
the TiCo1−x Nix Sb solid solution series are semiconductors with impurities in semiconducting intermetallic TiCo1−x Nix Sb solid
a narrow forbidden gap. In contrast to the TiCoSb compound solution.
with a Fermi level situated in the band-gap, EF in TiNiSb lies in
the conduction band. So the TiCoSb conduction would be of an
Acknowledgments
activated nature and its resistance will be determined by the rela-
tionship between the donor and acceptor impurities, while the
This work was supported by the National Academy of
TiNiSb compound conduction shows metallic-like behavior and
Science of Ukraine (grant 0102U000454) and by Ukrainian
is determined by the electron charge carriers in the conduction
Ministry of Education and Science (grants 0103U001887,
band.
0104U002297) and ECO-NET (grant 08133 RA).
Fig. 4 shows that the electron density, above the Fermi level,
consists mainly of Ti d-states, while the valence band is deter-
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