Physica B 520 (2017) 116–122

Contents lists available at ScienceDirect

Physica B
journal homepage: www.elsevier.com/locate/physb

Semiconducting-metallic transition of singlecrystalline ferromagnetic Hf- MARK

doped CuCr2Se4 spinels
⁎
E. Maciążeka, , E. Malickaa, A. Gągorb, Z. Stokłosac, T. Grońd, B. Sawickid, H. Dudad,
A. Gudwańskia
a
University of Silesia, Institute of Chemistry, ul. Szkolna 9, 40-006 Katowice, Poland
b
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław, Poland
c
University of Silesia, Institute of Material Science, ul. 75 Pułku Piechoty 1A, 41-500 Chorzów, Poland
d
University of Silesia, Institute of Physics, ul. Uniwersytecka 4, 40-007 Katowice, Poland

A R T I C L E I N F O A BS T RAC T

Keywords: Chalcogenide spinels show a variety of physical properties and are very good candidates for electronic and high-
Chalcogenides frequency applications. We report the measurements of magnetic susceptibility, magnetic isotherm, electrical
X-ray diffraction conductivity, thermoelectric power and calculations of the superexchange and double-exchange integrals made
Magnetic properties for singlecrystalline Cu[CrxHfy]Se4 spinels. The results showed a ferromagnetic order of magnetic moments
Exchange constants
below the Curie temperatures of 390 K and, an increase in the splitting of the zero-field cooled and field cooled
Electrical properties
susceptibilities with increasing Hf-content below the room temperature suggesting a slight spin-frustration and
a rapid transition from semiconducting to metallic state at room temperature. A quantitative evaluation of the
exchange Hamiltonian showed that the total hopping integral rapidly decreased and the bandwidth of the 3d t2g
band due to Cr3+ and Cr4+ ions strongly narrowed from 0.76 eV for y = 0 to 0.28 eV for y = 0.14. The narrowing
of this band appears to be responsible for semiconducting properties of the Hf-doped CuCr2Se4 spinels below
the room temperature.

1. Introduction ferromagnetic through ferrimagnetic up to spin-glass like behavior, and

CuCr2Se4 belongs to the group of chalcogenide spinels with a
general formula CuCr2X4 (where X = S, Se, Te). They all exhibit
metallic conductivity and ferromagnetic properties with high Curie
temperatures: TC = 380 K [1,2], 420 K [1,3] and 326 K [4] for sulphur,
selenium, and tellurium compounds, respectively. The metallic con-
ductivity and the ferromagnetic properties are attributed to mixed
valence state of chromium ions [5]. All these compounds crystallize in a
normal spinel structure, space group Fd3m with copper ions located in
one eight of the tetrahedral interstices and chromium in half of
octahedral ones. The crystal lattice is rich in unoccupied cation
positions and these compounds are characterized by an ease of
substitution by another element in a wide concentration range. In
our previous investigations, our most interesting results for indium [6–
9], cobalt [10–13] and vanadium [14,15] were described. The sub-
stitution of indium ions occurred to have a strong impact on the
magnetic and electrical properties. The presence of chromium instead
caused a decrease in saturation magnetic moments and maintained the
cubic structure. Incorporation of copper instead caused changes from
the crystal structure was lowered to tetragonal one [6–8]. The
octahedral coordination of In3+ keeps metallic conductivity, while the
tetrahedral coordination brings semiconducting properties [9]. Cobalt
occupies both interstices. The admixture into the single lattice Cux
CoyCrzSe4 is rather low (up to y = 0.23), however the changes in
properties are significant. The compound with a large amount of cobalt
showed ferrimagnetic and n-type semiconducting properties [10–12].
In the case of the polycrystalline Cu1−xCoxCr2Se4 spinel series the
compounds were obtained in the whole concentration range. In due
measure of substitution a change of crystal structure (for monoclinic),
the electrical properties showed the polaron type conductance with low
activation energy [13]. According to magnetic properties of the single-
and polycrystals of CuCr2Se4 doped with vanadium, very strong
weakening of magnetic interactions and a decrease in the Curie
temperature to TC = 193.2 K and paramagnetic Curie-Weiss tempera-
ture to θCW = 207 K occurred in the CuCr1.6V0.4Se4 compound [14,15].
Simultaneously, in the same compound a slight decrease in the effective
magnetic moment μeff = 5.85 μB/f.u. is observed in comparison to the
effective magnetic moment of 5.22 μB/f.u. that comes from the spin-

⁎
Corresponding author.
E-mail address: Ewa.Maciazek@us.edu.pl (E. Maciążek).

http://dx.doi.org/10.1016/j.physb.2017.05.049
Received 28 February 2017; Received in revised form 12 May 2017; Accepted 25 May 2017
Available online 27 May 2017
0921-4526/ © 2017 Elsevier B.V. All rights reserved.
E. Maciążek et al. Physica B 520 (2017) 116–122

only value for 3d3 Cr3+ and 3d2 V2+ ions. It may suggest that the Table 2
chromium ions create a mixed valence band. In this compound, a p- Crystal data, data collection and refinement results for the hafnium doped CuCr2Se4
spinels for all structures: Cubic, Fd−3m, Z = 8. The experiments were carried out at
type electrical conductivity and negative magnetoresistance were
297 K.
observed.
The interest in sulfuric spinels CuCr2S4 (Al.,Ga) and selenide Crystal data
CuCr2Se4 is also connected with the search for new materials, which
Chemical formula Cu[Cr1.81Hf0.14] Cu[Cr1.87Hf0.09] Cu[Cr1.93Hf0.06]
generate electric energy directly from the heat or can fulfill a role of a
Se4 Se4 Se4
thermal pump. Thermoelectric generators can be used also, among Mr 500.27 492.68 490.45
others, in the space exploration area and as nuclear power generators a (Å) 10.36850 (15) 10.3584 (3) 10.35172 (15)
in space probes [16,17]. CuHf2Se4 is not present in crystallographic V (Å3) 1114.67 (5) 1111.41 (10) 1109.27 (5)
databases [18]. For comparison, CuHf2S4 crystallizes in a normal spinel μ (mm−1) 36.00 35.10 34.72
Crystal size (mm) 0.28 × 0.21 × 0.21 × 0.18 × 0.29 × 0.22 ×
type structure and does not show magnetic anomalies. Moreover, the
0.13 0.11 0.15
crystal structure and magnetic properties of quaternary compounds of u 0.25744(5) 0.25752(4) 0.25745(4)
Cu[Cr1−xHfx]2S4 were studied successfully in the whole concentration
range [2]. All compounds were obtained in a spinel-type structure, the Data collection
Tmin, Tmax 0.019, 0.077 0.037, 0.094 0.014, 0.069
lattice parameter increases with the increased in the hafnium content,
No. of measured, 2590, 84, 83 2717, 86, 85 2721, 87, 87
and the Curie-Weiss law is obeyed. When the hafnium content independent and {I > 2σ(I)} {I > 2σ(I)} {I > 2σ(I)}
increases, the ferromagnetic interactions decrease and the spin-glass observed reflections
or paramagnetic behavior can occur. A spin crossover was also found Rint 0.045 0.046 0.056
for powders with x = 0.5–0.7 at 160 K. (sin θ/λ)max (Å−1) 0.659 0.660 0.661

This paper presents details of single crystal growth and the results
Refinement
of structural studies as well as the effect of the Hf4+ doping on the R[F2 > 2σ(F2)], 0.023, 0.074, 0.016, 0.052, 0.017, 0.053,
electrical and magnetic properties, including the exchange constant wR(F2), S 1.32 1.26 1.37
calculations. No. of reflections 84 86 87
Δρmax, Δρmin (e Å−3) 1.08, −1.05 0.44, −0.94 0.41, −0.76

2. Experimental
2.1. Synthesis
Single crystals of the (Cu)[Cr2−xHf3x/4]Se4 system were grown by
vapor transport in closed quartz ampoules with anhydrous chromium
chloride, CrCl3 (purity 95%), - as a transport agent. Binary selenide
CuSe, elemental hafnium (purity 98%) and selenium (purity 99.99%)
were used as the starting materials. The binary selenide CuSe was
synthesized from elemental copper (purity 99.99%) and selenium
(purity 99.99%). The stoichiometric mixtures of the elements were
pulverized in an agate mortar and sealed in evacuated quartz ampoules.
After the heating at 1073 K for 10 days, the selenide was ground in an
agate mortar and the X-ray powder analysis showed that the products
contained only the synthesized phase. Mixtures of the starting materi-
als with CrCl3 were sealed in quartz tubes (length ~200 mm, inner
diameter d = 20 mm) and evacuated to ~105 mbar. These ampoules
were heated in a horizontal zone furnace to about 1123 K at the
solution zone, maintaining a temperature gradient of 120 K along the
ampoule. After 21 days, the furnace was cooled to room temperature.
Single crystals of an octahedral shape with well-formed regular (111)
faces had the edge lengths of 1–4 mm.
The chemical composition of the crystals was determined using an
energy-dispersive X-ray fluorescence spectrometer (EDXRF) described
in details in [19,20]. The results of are given in Table 1. Table 1 shows
that with the increasing hafnium ion content, the number of cationic
vacancies increases, which may affect strongly the electrical properties
and slightly less the magnetic ones.
2.2. Single-crystal X-ray diffraction
XRD data were collected using an Xcalibur-Sapphire1 diffract-
Table 1
The chemical composition of the single crystals of (Cu)[Cr2−xHf3x/4]Se4 in % (m/m).
Compound Cu Cr Hf
(Cu)[Cr1.93Hf0.06]Se4 12.97 20.50 2.18
(Cu)[Cr1.87Hf0.09]Se4 12.92 19.85 3.26
(Cu)[Cr1.81Hf0.14]Se4 12.73 18.91 5.0
ometer operating in κ-geometry, equipped with a two-dimensional
CCD detector and an Mo Kα radiation (0.71073 Å) source. Data were
measured in the ω-scan mode with Δω = 1.0°. The CrysAlis PRO
software was used for the data collection and processing (CrysAlis PRO,
Rigaku OD, 2015, 1.171.38.34a). The structures were refined using
full-matrix least-squares methods with SHELXL2014/7. The absorp-
tion was corrected by numerical methods based on Gaussian integra-
tion over a multifaceted crystal model. An empirical absorption
correction using spherical harmonics, implemented in SCALE3
ABSPACK scaling algorithm, was also applied. The refinement was
done on 8 parameters. The dopant concentrations, used in the final
structure models, were estimated from the X-ray fluorescent spectro-
scopy (EDXRF) method. It is worth noting that the obtained values
corresponded well with the refined dopant amounts, basing on the
electron density from the X-ray diffraction only. Table 2 presents the
results of the data collection and refinement together with the
description of the crystals.
2.3. Electrical and magnetic measurements
The static dc magnetic susceptibilities (χ) were measured in two
different cooling modes in the temperature range of 10 – 400 K. In the
zero-field cooled (ZFC) mode, the sample was first cooled down in the
absence of an external magnetic field and then investigated while
heating in a given magnetic field H = 100 Oe. The field-cooled (FC)
mode usually followed the ZFC run when the same magnetic field was
set at high temperatures and the measurements were performed with
decreasing temperature. For both modes, the cooling process always
started from the paramagnetic state. The Curie temperature (TC) was
determined as a temperature corresponding to the extreme of dχ/dT
vs. T. The magnetization isotherms were measured at 10, 77 and 300 K
in applied external fields up to 10 kOe. For these purposes, a Quantum
Design Physical Properties Measurement System (QD-PPMS) was
used. The high-temperature expansion of the magnetic susceptibility
measurements in the range of 370 – 500 K were performed using a
Se
Faraday type Cahn RG automatic electrobalance. The effective mag-
64.35 netic moment was determined using the equation:
63.97 3kB C
μeff = ≅ 2.828 C [21,22], where kB is the Boltzmann constant,
63.36 NA μB2
NA is the Avogadro number, μB is the Bohr magneton and C is the

117
E. Maciążek et al.
molar Curie constant. In the studied spinels which are strongly
ferromagnetic, the small contribution of magnetic susceptibility in-
dependent on the temperature have been omitted [23].
The electrical conductivity σ(T) of the studied compounds has been
measured by means of the dc method using a KEITHLEY 6517B
Electrometer/High Resistance Meter. The activation energy, Ea, was
determined from the formula: σ = σ0exp(-Ea/kBT), where σ0 is the
reference conductivity. The thermoelectric power, S(T), was measured
in the temperature range of 300–600 K with using a Seebeck Effect
Measurement System (MMR Technologies, Inc., USA). The electrical
and thermal contacts were made from a silver lacquer mixture
(Degussa Leitsilber 200).
3. Results and discussion
3.1. Crystal structure and cation distribution
The chromium-based CuCr2Se4 is a normal spinel which crystallizes
in the face-centered cubic structure of Fd−3m space group. The copper
ions occupy tetrahedrally coordinated A sites of Td symmetry, whereas
the chromium ions are located in the octahedral B interstices of D3d
symmetry. The dilution of the Cr-subarray brings in a minor expansion
of the unit cell which results from a difference in the ionic radii of Cr3+
(61.5 pm) and Hf4+ (76 pm) (Table 2) [24]. The internal parameter u
related to the Se2- position (u, u, u) determines the Cr-Se-Cr angles
which are crucial for understanding of the magnetic interactions
[25,26]. In the hafnium-doped crystals, hafnium substituted for
chromium as in the CuCr2S4 [27]. The Cr and Hf atoms are distributed
randomly in the octahedral sites. Table 3 in supplementary materials
shows the interatomic distances and angles. The increase in the
hafnium content leads to a successive increase in the cubic lattice
parameter and an increase in the Cr–Se and Cu–Se bonds length (see
Table 3). The Cr-Se-Cr angles are equal within the error limit.
3.2. Magnetic properties
The results of the magnetic measurements of Cu[CrxHfy]Se4 are
shown in Figs. 1 and 2 and in Table 4. The temperature dependences of
the ZFC and FC dc magnetic susceptibility overlapped for the
CuCr1.93Hf0.06Se4 (Fig. 1a) and showed an increase in the splitting of
the ZFC and FC susceptibilities with the increasing Hf-content below
the room temperature (Figs. 1b and c). This may suggest that the
higher content of the hafnium ion in the sample causes a slight
reorientation of the spins, leading to a state of frustration. This
frustration may be associated with the appearance of a number of
clusters in which the magnetic moments are oriented randomly. In this
content range of the hafnium ions up to 0.14, the single-crystalline
selenium spinels are strong ferromagnets with the Curie temperature
TC = 399, 392 and 390 K for CuCr1.93Hf0.06Se4, CuCr1.87Hf0.09Se4 and
CuCr1.81Hf0.14Se4, respectively. A stronger effect was observed in the
polycrystalline spinel series of Cu(Cr1−xHfx)2S4, wherein with increas-
Table 3
Selected geometric parameters (Å, °).
Cu[Cr1.81Hf0.14]Se4
Cu—Se 2.3784 (10) Cr—Sei
Crii—Se—Criii 93.46 (3)
Cu[Cr1.87Hf0.09]Se4
Cu—Se 2.3775 (7) Cr—Sei
Crii—Se—Criii 93.49 (2)
Cu[Cr1.93Hf0.06]Se4
Cu—Se 2.3747 (7) Cr—Sei
Crii—Se—Criii 93.46 (2)
(i) x+1/4, y+1/4, -z+1; (ii) -x+3/4, -y+3/4, z; (iii) -x+3/4, y, -z+3/4.
Physica B 520 (2017) 116–122
ing x - the ferromagnetic properties weakened gradually from a
predominant ferromagnetic (x ≤ 0.45), a spin-glass (0.50 ≤ x ≤ 0.70),
finally to a simple paramagnetic behavior (x ≥ 0.90) [2]. The
temperatures TC, θCW and the effective magnetic moment μeff
(Fig. 1d, Table 4) decrease as the Hf content increases, indicating a
slight influence of the Hf substitution on the long- and short-range
magnetic interactions. A slight increase in the spin-frustration up to
280 K with the increasing hafnium ion content associated with slight
weakening of both long and short-range magnetic interactions may
result from the increase in the length of the Cr-Se bonds (Table 3). A
similar behavior was found in MnCr2O4 nanoparticles in which a
reduction in direct magnetic interactions in the octahedral site with the
increasing lattice expansion was observed [28].
Magnetic isotherms (M – H curves) in the magnetic field up to
10 kOe for all studied single crystals at several temperatures, i.e. 10, 77
and 300 K are depicted in Fig. 2a–c, respectively. All samples reached
the magnetic saturation, Ms, above 2 kOe indicating that the Cr atoms
have a spin of Cr3+ valence state below T < TC. The saturated moment
is expected to be 3 μB per Cr-atom at 10 K. As the temperature
increases the saturation moment Ms decreases gradually according to
the theory of molecular field for spin S = 3/2. Also the Ms decreases as
the y increases (Table 4), because the hafnium ion is nonmagnetic.
3.3. Electrical properties
The measurements of the electrical conductivity, σ(T), and thermo-
electric power, S(T), are shown in Figs. 3 and 4, respectively. The σ(T)
for all studied single crystals showed a rapid transition from a
semiconducting to a metallic state at room temperature (Fig. 3). The
electrical conductivity is increased by two orders of magnitude with the
increasing hafnium ions in the sample in the content range of 0.06–
0.14 (Fig. 3). Metallic conduction and ferromagnetic order are char-
acteristic for the CuCr2Se4 matrix [25–27]. These unique properties
were explained by the Lotgering model [11,12], which assumed that
the copper atoms are monovalent and each Cu+ ion caused a change of
valence Cr3+ → Cr4+ of one Cr3+ to attain the overall neutrality in the
compound. If the p band of the anion is full, then the interactions
between Cr3+ and Cr4+ must be ferromagnetic [13] and the mixed
valence band of the chromium ions [Cr3+, Cr4+] is the main source of
the p-type metallic conductivity [12]. A substitution of the Cr3+ ion in
the matrix with the Hf4+ ion having a much larger radius (76 pm [24])
could cause the appearance of a narrow energy gap. Below the room
temperature, the current carriers are poorly thermally activated with
the activation energy of 1.4 meV. This unexpected behavior is char-
acteristic for all studied single crystals and contrasts with the conduc-
tion of the CuCr2Se4 matrix [25,26], although in both cases, the band
mechanism of electrical conductivity is the same. For comparison, in
the oxide compounds, the semiconducting-metallic transition is usually
explained using the variable range hopping mechanism [29], a
localized state (semiconductor) and a delocalized state (metallic) [30].
The values of the thermoelectric power, S(T), in the temperature
range of 300–600 K (Fig. 4) are typical for metallic conductors. Indeed,
in this temperature range the Hf-doped CuCr2Se4 spinels are con-
2.5173 (5) ductors, and below the room temperature, they are semiconductors
(Fig. 3). Below 460 K, the majority of the carriers are holes (p-type
conduction), which originate from the band of the mixed-valence
2.5142 (4) chromium ions [Cr3+, Cr4+] [31]. Above this temperature, there is a
higher concentration of electrons (n-type conduction), which may
originate from the anionic vacancies [32]. In general, the higher the
content of hafnium ions, the greater the presence of the p-type
2.5132 (4)
conduction.
118
E. Maciążek et al.
Fig. 1. Dc magnetic susceptibility χ (a, b, c) and inverse magnetic susceptibility 1/χ (d) vs. temperature T recorded at H = 100 Oe for Cu[CrxHfy]Se4. The solid (black) line, (T-θ)/C,
indicates a Curie-Weiss behavior.
4. Magnetic interactions
4.1. Chromium content calculations
The superexchange and double exchange interactions are the most
important magnetic interactions in spinels. The latter is usually
connected with the metallic conductivity. To study an effect of these
interactions on the electrical and magnetic properties described above,
the exchange constants were calculated. From the magnetization
depicted in Fig. 5, it follows that the hafnium ion does not contribute
in to the magnetic moment as it is a transition metal. Thus, to
determine the exchange constants of the superexchange and double
exchange interactions, an estimation of the Cr3+ and Cr4+ portions is
necessary. Portions x3 and x4 of the chromium ions Cr3+ and Cr4+,
respectively, were calculated from the saturation magnetization Ms:
Ms = 2(g3 S3 x3 + g4 S4 x4 )
(1)
taking into account the following normalization condition: x3 + x4 = 1,
where Ms is the experimental value of the saturation magnetization, S3
= 3/2 is the spin of Cr3+ ion, S4 = 1 is the spin of Cr4+ ion and g3 = 2.0
and g4 = 1.86 are the Landé factors for Cr3+ and Cr4+ ions, respectively.
The results of the above calculations are depicted in Fig. 5. An
increase in the hafnium content y is accompanied by: (1) an increase in
the concentration of the Cr3+ ions from 0.51 to 0.59 passing through a
maximum of 0.76 for x3 = 0.06, (2) a dramatic decrease in the
concentration of the Cr4+ ions from 0.49 to 0.41 passing through a
minimum of 0.24 for x4 = 0.06 and (3) a stabilization of the double-
119
Physica B 520 (2017) 116–122
exchange interaction between the Cr3+ and Cr4+ ions. It means that in
the Cu[CrxHfy]Se4 spinel system, the superexchange interaction dom-
inates and the double-exchange interaction plays a significant role with
increasing hafnium content, which is visible in the increase in the
electric conductivity (Fig. 3). The procedure, which allows to calculate
the superexchange and double-exchange integrals using the exchange
Hamiltonian is described in the Appendix A, and the calculation results
are given in Table 5.
4.2. Calculation results
The results of the exchange constant calculations presented in
Table 5 showed that with the increasing hafnium content y: (1) the
contribution of the superexchange interaction, θse, to the Curie–Weiss
temperature θCW shows a maximum of 200 K for y = 0.06, (2) the
contribution of the double exchange interaction, θde, to the Curie –
Weiss temperature θCW shows a local minimum of 188 K for y = 0.09
and increases to 198 K for y = 0.14, (3) and the total hopping integral,
B, as well as the Wd bandwidth of the 3d t2 g band due to Cr3+ and Cr4+
ions decrease. It means that the presence of the Hf4+ ions in the
octahedral sites narrows the Wd bandwidth of the mixed valence [Cr3+,
Cr4+] band, ultimately weakening the double exchange mechanism,
responsible for the metallic conductivity. It is also visible in more
quickly decreasing values of integrals of the double exchange (both
positive baa and bab) than of the superexchange (positive Jaa and
aa
negative Jab). The effective exchange constants Jeff ab
and Jeff for the first
two coordination spheres are positive and negative, respectively, and
E. Maciążek et al. Physica B 520 (2017) 116–122

Fig. 3. Electrical conductivity (lnσ) vs. inverse temperature (103/T) for the Cu[CrxHfy]
Se4 spinels.

Fig. 4. Thermoelectric power S vs. temperature T for the Cu[CrxHfy]Se4 spinels.

Fig. 2. Magnetization M vs. magnetic field H at 10 (a), 77 (b) and 300 K (c) for the
Cu[CrxHfy]Se4 spinels.

Table 4
Magnetic parameters of the Cu[CrxHfy]Se4 spinels: C is the Curie constant, TC and θCW
are the Curie and Curie-Weiss temperatures, respectively, μeff is the effective magnetic
moment, Ms is the saturation magnetization. The magnetic parameters of the CuCr2Se4
spinel are taken from Ref. [25] for comparison.

y x C (emu K/mol) TC (K) θCW (K) μeff (μB/f.u.) Ms (μB/f.u.)

0 2.00 2.704 416 436 4.650 4.760

0.06 1.93 3.261 399 391 5.107 5.459
0.09 1.87 3.065 392 386 4.951 5.404
0.14 1.81 2.859 390 380 4.782 5.065

aa
the absolute value of Jeff is almost five times larger than Jeff
ab
. The Fig. 5. Magnetization Ms and concentrations of the chromium ions x3 (Cr3+) and x4
relevant calculated exchange constants [12,14,15] of the parent (Cr4+) vs. hafnium content y for the Cu[CrxHfy]Se4 spinels.
CuCr2Se4 metallic ferromagnet [25] are collected in Table 5 for
comparison. The high and comparable values of the effective exchange
aa
constant Jeff with the prevalence of the double exchange component

120
E. Maciążek et al. Physica B 520 (2017) 116–122

Table 5
aa ab
Calculated magnetic parameters: X, θse, θde, B, Wd, Jaa, Jab, baa, bab, Jeff and Jeff of the Cu[CrxHfy]Se4 spinel system. The calculated magnetic parameters of the CuCr2Se4 matrix are
taken from Ref. [12,14,15] for comparison.

y (Co3+) x3 (Cr3+) x4 (Cr4+) X θse (K) θde (K) B (K) Wd (eV) Jaa (K) Jab (K) baa (K) bab (K) aa
Jeff (K) ab
Jeff (K)

0 0.512 0.488 2.896 90 340 4391 0.76 63.9 −9.65 332.65 65.53 466.51 −83.05
0.06 0.763 0.237 3.335 200 191 1900 0.33 63.2 −8.31 143.95 28.79 405.23 −68.48
0.09 0.739 0.261 3.293 198 188 1776 0.31 62.1 −8.15 134.55 26.91 398.55 −66.66
0.14 0.590 0.410 3.033 182 198 1619 0.28 61.5 −8.23 122.65 24.53 398.70 −63.16

explain well the observed the semiconductor-metal transition for the conductivity were observed. The main conclusion is that even a small
studied spinel regardless of the amount of the substituted hafnium. admixture of hafnium ions narrowing of the Wd bandwidth of the
chromium ions [Cr3+, Cr4+] strongly affects the electrical properties of
5. Conclusions the Cu[CrxHfy]Se4 spinels.

Summarizing, the Hf-doped CuCr2Se4 single crystals were char- Acknowledgments

acterized by X-ray, dc magnetic, electrical conductivity and thermo-
electric power measurements as well as a quantitative evaluation of the
exchange Hamiltonian. In the hafnium ion content range of 0.06–0.14,
the ferromagnetic order of magnetic moments below the Curie
temperatures of 390 K, a rapid transition from semiconducting to
metallic state at room temperature and the majority of the p-type
This work was partly supported by Ministry of Science and Higher
Education (Poland) and funded from science resources: No. 1S-0300–
500-1–05-06. The authors are also grateful to the team workshop of
the Institute of Physics (University of Silesia) for providing practical
and technical assistance.

Appendix A

The exchange constants of superexchange and double exchange interactions between the first two coordination spheres were calculated using the
exchange Hamiltonian as follows:
H = Hse + Hde (2)
where:
→→
Hse = −∑ Jij Si ⋅ Sj ,
i, j
i≠j (3)
n+ m+ m+ n+
represents the superexchange Cr -Se-Cr and Cr -Se-Se-Cr interactions [31] with the integrals Jij and caa=6 and cab=12 numbers of nearest
→ →
neighbours in the first and second Cr-Cr coordination spheres, respectively. The spins Si and Sj are considered as the quasiclassical vectors.
1 →→
Hde = − 6 x3 x4 ∑ bij Si ⋅ Sj ,
i, j
i≠j (4)
represents the double exchange interactions [33] with being the concentration of chromium ions, which is normalized in such way that x3+x4=1, and
bij is the hopping integral between the atomic t2 g states |i > and |j > for neighbours < i,j > . We take the band factor as ∼x3·x4 corresponding to
probability of finding one atom in the state Cr3+ and the neighbouring one in the state Cr4+. The number 1/6 in the double exchange Hamiltonian
→→
(4) is a constant of a bilinear term Si ⋅ Sj in the case of spin 1 [33].
According to the Hamiltonian (2) the effective exchange constants [31] for the first two coordination spheres are:
aa 1
Jeff = Jaa caa + 6 baa caa x3 x4 , (5)
ab 1
Jeff = Jab cab + 6 bab cab x3 x4 . (6)
The Jaa and baa and Jab and bab integrals for the first two coordination spheres, respectively, are calculated from the high temperature expansion
of the magnetic susceptibility [31]. The contributions to the paramagnetic Curie-Weiss temperature coming from the separate mechanisms of the
superexchange and double exchange interactions as follows [34]:
θCW = θse + θde (7)
where θCW is the paramagnetic Curie-Weiss temperature (from experiment), θse is the superexchange contribution to θCW and θde is the double
exchange contribution to θCW. The above contributions [31,34] read:
2
θse = 3 X ∑ Jp cp ,
p (8)
1
θde = 6 Xx3 x4 ∑ bp cp ,
p (9)

121
E. Maciążek et al. Physica B 520 (2017) 116–122

where ∑p Jp cp = θCu was taken from Ref. 28 and equal to 90 K for the CuCr2Se4 ferromagnet, which means only the pure superexchange
contribution, B = ∑p bp cp is the total hopping integral for the first and second coordination spheres and X is a mixture of spins due to the presence
of Cr3+ and Cr4+ ions. A summation over p means the summation over the consecutive coordination spheres, each of them containing cp neighbours
of a given central atom. We should set:
X = x3 S3 (S3 + 1) + x4 S4 (S4 + 1). (10)
Finally, Eq. (7) can be written:
2 1
θCW = 3 XθCu + 6 Xx3 x4 B, (11)
with the following superexchange and double exchange contributions to θCW, respectively:
2
θse = 3 XθCu, (12)
1
θde = 6
Xx3 x4 B. (13)
3+ 4+
Eq. (11) allows to estimate the mixed valence (Cr ,Cr ) bandwidth Wd of the 3d t2 g band from the relation [31]:
Wd = 2B. (14)
Taking into account the estimated values of θse from Eq. (12) and the experimental values of the Curie temperature TC, the superexchange Jaa
and Jab integrals for the first two coordination spheres we can calculate with the aid of the Holland and Brown equations [35]:
θse = 5(3Jaa + 18Jab ), (15)

TC = 5(Jaa –2Jab ). (16)

The double exchange baa and bab integrals [31] can be calculated from the equation:
B = 6baa + 36bab , (17)
where baa stands for the contribution from the 6 nearest neighbours and bab stands for the contributions from the 36 second nearest neighbours and
from the Lotgering [25] considerations:
baa = 5bab (18)
The calculated magnetic parameters: θse, θde, B, aa
Wd, Jaa, Jab, Jab, baa, bab, Jeff , ab
Jeff are collected in Table 5.

Appendix A. Supporting information

Supplementary data associated with this article can be found in the online version at doi:10.1016/j.physb.2017.05.049.

References S. Mazur, R. Sitko, Philos. Mag. 90 (2010) 1525.

[1] F.K. Lotgering, Sol. State Com. 2 (1964) 55–56.
[2] F. Kariya, K. Ebina, K. Hasegawa, K. Koshimizu, K. Hondou, S. Ebisu, S. Nagata, J.
Sol. State Chem. 182 (2009) 2018.
[3] T. Saha-Dasgupta, Molly De Raychaudhury, D.D. Sarma, Phys. Rev. B 76 (2007)
054441.
[4] T. Suzuyama, J. Awaka, H. Yamamoto, S. Ebisu, M. Ito, T. Suzuki, T. Nakama,
K. Yagasaki, S. Nagata, J. Sol. State Chem. 179 (2006) 140.
[5] F.K. Lotgering, R.P. van Stapele, J. Appl. Phys. 39 (1967) 577.
[6] I. Okońska-Kozłowska, E. Maciążek, K. Wokulska, J. Heimann, J. Alloy. Compd.
219 (1995) 97.
[7] E. Maciążek, H. Duda, T. Groń, A. Kita, T. Mydlarz, J. Alloy. Compd. 442 (2007)
183.
[8] H. Duda, E. Maciążek, T. Groń, S. Mazur, A.W. Pacyna, A. Waśkowska, T. Mydlarz,
A. Gilewski, Phys. Rev. B 77 (2008) 035207.
[9] E. Maciążek, T. Groń, H. Duda, A. Waśkowska, I. Jendrzejewska, E. Malicka,
E. Augustyn, S. Mazur, J. Alloy. Compd. 480 (2009) 60.
[10] T. Groń, E. Maciążek, J. Heimann, J. Kusz, I. Okońska-Kozłowska, K. Bärner,
Ch Kleeberg, Phys. B 254 (1998) 84.
[11] T. Groń, J. Kusz, K. Bärner, E. Maciążek, I. Okońska-Kozłowska, Sol. State Phenom.
67–68 (1999) 341.
[12] T. Groń, S. Mazur, H. Duda, J. Krok-Kowalski, E. Maciążek, J. Alloy. Compd. 467
(2009) 112.
[13] E. Maciążek, A. Molak, T. Goryczka, J. Alloy. Compd. 441 (2007) 222.
[14] E. Malicka, T. Groń, D. Skrzypek, A.W. Pacyna, D. Badurski, A. Waśkowska,
[15] E. Malicka, H. Duda, T. Groń, A. Gągor, S. Mazur, J. Krok-Kowalski, J. Phys. Chem.
Sol. 73 (2012) 262.
[16] G.J. Snyder, T. Caillat, J.P. Fleurial, Phys. Rev. B 62 (2000) 10185.
[17] G.J. Snyder, T. Caillat, J.P. Fleurial, Mat. Res. Innov. 5 (2001) 67.
[18] Powder Diffraction, ICDD database, pdf2.
[19] R. Sitko, B. Zawisza, E. Malicka, Spectrochim. Acta B 63 (2008) 1303.
[20] R. Sitko, B. Zawisza, E. Malicka, Spectrochim. Acta B 64 (2009) 436.
[21] T. Groń, J. Krok-Kowalski, H. Duda, T. Mydlarz, A. Gilewski, J. Walczak, E. Filipek,
K. Bärner, Phys. Rev. B 51 (1995) 16021.
[22] J. Krok-Kowalski, T. Groń, J. Warczewski, T. Mydlarz, I. Okońska-Kozłowska, J.
Magn. Magn. Mater. 168 (1997) 129.
[23] T. Groń, A.W. Pacyna, E. Malicka, Sol. State Phenom. 170 (2011) 213.
[24] R.D. Shannon, Acta Crystallogr. A 32 (1976) 751.
[25] F.K. Lotgering, Proceedings of the International Conference on Magnetism,
Nottingham, 1964 (Institute of Physics, London, p.533, 1965.
[26] F.K. Lotgering, R.P. van Stapele, Solid State Commun. 5 (1967) 143.
[27] T. Groń, H. Duda, J. Warczewski, Phys. Rev. B 41 (1990) 12424.
[28] R.N. Bhowmik, R. Ranganathan, R. Nagarajan, Phys. Rev. B 73 (2006) 144413.
[29] R.N. Bhowmik, G. Vijayasri, J. Appl. Phys. 114 (2013) 223701.
[30] R.N. Bhowmik, Mater. Res. Express 1 (2014) 015903.
[31] J. Krok, J. Spałek, S. Juszczyk, J. Warczewski, Phys. Rev. B 28 (1983) 6499.
[32] T. Groń, Philos. Mag. B 70 (1994) 121.
[33] M. Cieplak, Phys. Rev. B 18 (1978) 3470.
[34] J. Krok-Kowalski, J. Warczewski, J. Mag. Mag. Mater. 83 (1990) 485.
[35] W.E. Holland, H.A. Brown, Phys. Status Solidi A 10 (1972) 249.

122