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CoxCu1−xCr2S4 Nanocrystals: Synthesis, Magnetism, and Band


Structure Calculations
Karthik Ramasamy,† Hunter Sims,† Ram K. Gupta,‡ Dhananjay Kumar,§ William H. Butler,†
and Arunava Gupta*,†

Center for Materials for Information Technology, The University of Alabama, Tuscaloosa, Alabama 35487, United States

Department of Chemistry, Pittsburg State University, 1701 South Broadway, Pittsburg, Kansas 66762, United States
§
Department of Mechanical Engineering, North Carolina A&T State University, 1601 East Market Street, Greensboro, North
Carolina 27411, United States
*
S Supporting Information

ABSTRACT: Spin-based transport in semiconductor systems has been proposed as


the foundation of a new class of spintronic devices. For the practical realization of such
devices, it is important to identify new magnetic systems operating at room temperature
that can be readily integrated with standard semiconductors. A promising class of
materials for this purpose is magnetic chromium-based chalcogenides that have the
spinel structure. Nanocrystals of CoxCu1−xCr2S4 have been synthesized over the entire
composition range by a facile solution-based method. While CuCr2S4 is a ferromagnetic
metal, CoCr2S4 is known to be a ferrimagnetic semiconductor. Systematic changes in
the lattice parameter, size, and magnetic properties of the nanocrystals are observed with composition. The nanocrystals are
magnetic over the entire range, with a decrease in the magnetic transition temperature with increasing Co content. Band
structure calculations have been carried out to determine the electronic and magnetic structure as a function of composition. The
results suggest that ferrimagnetic alignment of the Co and Cr moments results in a decrease in magnetization with increasing Co
concentration.
KEYWORDS: chalcospinels, nanocrystals, magnetism, spintronics, band structure

Magnetic materials with diverse electronic transport properties conducting and metallic characteristics and, more importantly,
(metallic, semiconducting, insulating) and sufficiently high to ascertain if TC shifts toward room temperature are feasible in
Curie temperature (TC) are needed for room-temperature this system for practical utilization in spintronic devices. In
operation of spin-based electronic (spintronic) devices.1 In addition, Co1−xCuxCr2S4 exhibits very interesting magneto-
particular, magnetic semiconductors have received much optical properties. For example, the Faraday effect in
attention because of their potential compatibility with existing Co0.7Cu0.3Cr2S4 is found to be 1.5−2 orders of magnitude
semiconductor logic and memory devices. Magnetic semi- larger than in commonly utilized magneto-optic materials.7
conductors generally exhibit spin dependence in the band gaps, Despite their remarkable potential, the syntheses of these
providing in principle an effective means of generating spin- materials have not witnessed much development, particularly in
polarized current for spin-injection or spin-filtering applica- the form of nanostructures and thin films.
tions.2 In view of the high TC requirement, chromium-based Chalcospinel compounds are commonly synthesized at high
chalcogenide spinels (chalcospinels) are potentially attractive temperature by conventional solid-state methods.8 This
candidates. A number of these compounds are ferro/ synthetic process requires extremely long times for proper
ferrimagnetic insulators, semiconductors, or even metals.3 phase-pure synthesis, which severely limits the ability to
The compounds CuCr2S4, CuCr2Se4, and CuCr2Te4 are effectively probe the promising and relatively unexplored
ferromagnetic metals with Curie temperatures of 377, 430, phase space of these compounds. To expedite and exploit the
and 360 K, respectively.4 Furthermore, a number of the promising characteristics of the mixed chalcospinels, there is a
chalcospinels have generated renewed interest in recent years need for synthesizing these materials at nanodimensions as well
because of their unique magnetotransport and magnetodi- as at relatively shorter reaction time scales. One of the major
electric properties. CoCr2S4 has been synthesized in the bulk complications associated with the solution-based synthesis of
and is a ferrimagnetic semiconductor with a critical temperature these complex chalcogenides is the identification of suitable
of around 220−240 K.5 Another ferrimagnetic semiconducting metal and chalcogenide precursors. More importantly, the
chalcospinel, FeCr2S4, exhibits a marked increase in the Curie
temperature when doped with Cu.6 Consequently, a study of Received: June 14, 2013
the relatively unexplored material system Co1−xCuxCr2S4 is Revised: August 8, 2013
important to understand the competition between semi-

© XXXX American Chemical Society A dx.doi.org/10.1021/cm401938f | Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials Article

material of interest, CoxCu1−xCr2S4, is composed of transition using projector-augmented wave (PAW) pseudopotentials generated
metal elements that usually exist in variable oxidation states. by Kresse and Joubert12−14 and a plane-wave cutoff of 280.0 eV. For x
Materials with elements of variable oxidation states are known = 0, 0.5, and 1, we used the primitive 14-atom unit cell of the Fd3m̅
to often produce different stoichiometries that are in a close spinel lattice with a 16 × 16 × 16 Γ-centered k-point mesh integrated
via the tetrahedron method with Blöchl corrections. For x = 0.25 and
thermodynamic stability window.9 Controlling their redox 0.75, it was necessary to increase the unit cell to 56 atoms, and we
behavior to selectively produce phase-pure CoxCu1−xCr2S4 is reduced the number of k-points by half in each direction. HSE06
therefore challenging. We recently reported the size- and shape- calculations were performed in the 14-atom-cell systems on a coarser 8
controlled synthesis of chromium-based chalcospinel nano- × 8 × 8 k mesh that was further reduced by half in each direction for
crystals.10 Advancing on our chalcospinel nanocrystals syn- the computation of the exact exchange. Our PBE+U calculations are
thesis, herein we report the first solution-phase synthesis of conducted via the fully local double-counting correction and the
monodisperse quaternary nanocrystals of CoxCu1−xCr2S4 over simplified Dudarev approach with Ueff = U − J = 3.5 eV for the Cu and
the entire range, along with their detailed magnetic character- Co 3d orbitals and 2.5 eV on the Cr 3d orbitals.15 For CuCr2S4, we use
izations and band structure calculations. a PBE-relaxed structure with a = 9.81 Å and the internal parameter u =


0.258. The structure shrinks somewhat with the introduction of Co,
reducing a to 9.78 Å and u to 0.256. In the 56-atom cell, we examined
EXPERIMENTAL SECTION the effect of different arrangements of the Co and Cu ions at the A
Materials. All chemicals were used as received, and solvents were sites. We found that such disorder does not significantly affect the
electronic properties of the system.


dried in molecular sieves and purged with high-purity argon for 30 min
before use. 1-Dodecanethiol (1-DDT, 98.0%), chromium chloride
(CrCl3·6H2O, 99.5%) were received from Alfa Aesar; anhydrous RESULTS AND DISCUSSION
copper chloride (CuCl2, ≥99.0%), cobalt chloride (CoCl2, ≥99.0%), CoxCu1−xCr2S4 nanocrystals were synthesized by reacting
and octadecylamine (ODA, ≥99.0%) were obtained from Acros chloride salts of copper, cobalt, and chromium with
Organics. Analytical-grade hexane and ethanol were obtained from dodecanethiol in octadecylamine at 360 °C (please see
Aldrich Chemical Co.
Measurements. Transmission electron microscopy (TEM) Experimental Section for detailed synthesis procedure). We
analysis was performed on a FEI-Tecnai, 200 kV microscope equipped found that 1-dodecanethiol as a sulfur source is necessary to
with a charge-coupled device (CCD) camera for scanning transmission form the desired thiospinel compound, not only because it
electron microscope (STEM), high-angle annular dark-field readily forms reactive monomer nuclei but also because it is
(HAADF), and energy-dispersive X-ray (EDX) detectors. TEM miscible with organic capping agents and decomposes at
image nonlinear processing was carried out with Gatan digital relatively high temperatures. However, our attempt at
micrograph version 3.4. Powder X-ray diffraction (XRD) patterns synthesizing CoxCu1−xCr2S4 nanocrystals using other sulfonat-
were recorded on a Bruker D8 instrument equipped with Cu Kα ing agents, such as sulfur in oleylamine and trioctylphosphine
radiation source operated as a rotating anode at 40 kV and 20 mA. sulfide, yielded only secondary impurities.
Scanning electron microscope (SEM) analysis was carried out on a
JEOL 7000 FE instrument equipped with EDX, wavelength-dispersive The crystallinity, phase purity, and CoxCu1−xCr2S4 solid
spectrometry (WDS), electron backscatter diffraction (EBSD), solution formation have been confirmed from powder X-ray
secondary electron (SE), backscattered electron (BE) and trans- diffraction measurements. Figure 1 shows powder X-ray
mission electron (TE) detectors. Magnetic measurements were diffraction patterns of CoxCu1−xCr2S4 nanocrystals synthesized
performed with a superconducting quantum interference device with octadecylamine as capping agent. The major diffraction
(SQUID) with MultiVu software. peaks are indexed as (311), (222), (511), and (440) planes of
Synthesis of CoxCu1−xCr2S4 Nanocrystals. All experiments were fcc-cubic spinel structure with Fd3̅m space group. The
carried out in a fume hood under N2 atmosphere by standard Schlenk diffraction peak positions of CuCr2S4 and CoCr2S4 nanocrystals
techniques. In a typical synthesis of CoxCu1−xCr2S4, respective are in agreement with standard diffraction patterns ICDD 021-
amounts of CuCl2 and CoCl2, mixed with 0.50 mmol of CrCl3·
6H2O and 10 g of ODA, were deaerated at room temperature for 15 0287 and 021-0255, respectively (see Figure S1 in Supporting
min and then backfilled with nitrogen for 15 min. The mixture was Information for crystal structures of CuCr2S4 and CoCr2S4).
subsequently heated to 160−165 °C under vacuum, followed by Furthermore, X-ray diffraction measurements confirmed that
continued heating to 360 °C under N2 atmosphere. In a separate the samples are free from the structurally closely associated
vessel, 2 mL (3 mmol) of 1-dodecanethiol (1-DDT) was heated to CuCrS2 phase, which is obtained when the synthesis is carried
245−250 °C under N2 atmosphere. At 360 °C, 2 mL of the hot 1- out below 360 °C. The calculated lattice constant (a) of
DDT was quickly injected into the metal halide solution, while the CoxCu1−xCr2S4 nanocrystals from X-ray diffraction is 9.922 ±
temperature of the solution was prevented from decreasing below 340 0.004 Å for x = 0 and 9.856 ± 0.003 Å for x = 1. With
°C. The vessel was then quickly reheated to 360 °C and the resulting increasing Co concentration, lattice compression because of the
black mixture continued to be stirred at this temperature for 1 h. After
the mixture was cooled to room temperature, a mixture of hexane (5 smaller ion results in a measurable shift in the diffraction peak
mL) and ethanol (15 mL) was added to precipitate the product. The positions toward higher angles (Figure 1b).
black precipitate was then isolated via centrifugation (7000 rpm). The The morphology and size of CoxCu1−xCr2S4 nanocrystals
washing process was repeated three times to ensure removal of any have been investigated by use of a transmission electron
excess capping agents. Similar experimental conditions were followed microscope (TEM). The TEM images in Figure 2 show
for the synthesis of Co0.8Cu0.2Cr2S4 and CoCr2S4 nanocrystals, but 5 g irregular to nearly cubic morphology over the entire
of octadecylamine was used with a reaction time of 2 h to obtain an composition range with a narrow size distribution. The average
isolable solid sample, which was only a pasty material otherwise. lateral size of the nanocrystals is found to be 20 ± 2 nm for x =
Band Structure Calculations. The electronic and magnetic 0, 19 ± 3 nm for x = 0.2, 8 ± 1.5 nm for x = 0.4, 6 ± 1 nm for x
structure of CoxCu1−xCr2S4 have been calculated within the Perdew−
Burke−Ernzerhof (PBE) generalized gradient approximation of = 0.6, and 3 ± 1 nm for x = 0.7; nanocrystals smaller than 3 nm
density functional theory, as well as its extensions Perdew−Burke− are seen for x = 0.8 and x = 1. The precise size of higher cobalt
Ernzerhof (PBE) + Coulomb (U) and the Heyd−Scuseria−Ernzerhof concentration nanocrystals was not measurable due to their
(HSE06) screened hybrid-functional method.11 All calculations were smallness (additional TEM images are given in Figure S2 in
performed with the Vienna ab-initio simulation package (VASP) code Supporting Information). The significant reduction in the size
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Chemistry of Materials Article

Figure 2. TEM images of CoxCu1−xCr2S4 nanocrystals: (a) x = 0, (b) x


= 0.2, (c) x = 0.4, and (d) x = 0.6.

those observed in TEM images. In some cases, deviation in


chemical composition among particles can lead to this anomaly;
for this, we performed high-angle annular dark-field (HAADF)
image measurement coupled with scanning transmission
electron microscope (STEM) elemental mapping on
Co0.4Cu0.6Cr2S4 samples. HAADF image did not show any
appreciable Z-contrast difference in the nanocrystals, as shown
in Figure S3 in Supporting Information. Moreover, STEM
mapping showed uniform distribution of elements within the
nanocrystals. Apart from crystallite size, inhomogeneous strain
in the crystal lattice is a known factor contributing to X-ray
peak broadening.20 A maximum estimated strain of 1.4% is
obtained for Co0.2Cu0.8Cr2S4 nanocrystals by applying the
Figure 1. (a, top panel) Powder X-ray diffraction (XRD) patterns of Williamson−Hall method (Figure S4 in Supporting Informa-
CoxCu1−xCr2S4 (0 ≤ x ≤ 1) nanocrystals (measured with a Cu Kα tion). Thus, the observed X-ray peak broadening in lower
source on a Bruker D8 instrument). (b, bottom panel) XRD patterns cobalt concentration samples is in part explained by the
of CoxCu1−xCr2S4 (0 ≤ x ≤ 1) nanocrystals as a function of x in the presence of structural defects. Twin boundary defects decrease
region of the (440) peak. the spatial extent of the periodic lattice array contributing to the
coherent scattering of X-rays, thereby making the diffracted size
of CoxCu1−xCr2S4 nanocrystals with increasing cobalt ion of the crystallites smaller than the size of original nanocryst-
concentration may be explained through the hard−soft acid− als.21 The presence of twin boundary defects in our nanocrystal
base (HSAB) concept.16 The sulfonating agent, 1-DDT, is a samples are clearly observed in the high-resolution (HR) TEM
soft base and reacts preferentially with the soft acid copper ion, images in Figure 3a. To further address this issue in detail,
thereby inducing rapid monomer nucleus formation and investigations of different size nanocrystals of a specific
subsequent kinetic-driven growth leading to nanocrystals with concentration are underway.
well-defined size. But the reactivity is lowered when Cu is HRTEM images in Figure 3b−e show the crystalline nature
replaced with Co, which leads to growth of smaller size of the nanocrystals with well-defined lattice fringes. The average
nanocrystals. We have recently observed similar growth lattice distance (d), as determined from multiple lattice fringes
behavior for Cu2CdxZn1−xSnS4 nanorods synthesized from a of individual CoxCu1−xCr2S4 nanocrystals, are 2.96 ± 0.02 Å (x
mixture of alkylthiols.17 Moreover, there is also a possibility that = 0), 2.93 ± 0.02 Å (x = 0.2), 2.90 ± 0.01 Å (x = 0.4), and 2.87
cobalt inhibits growth of nanocrystals by adsorbing on the ± 0.02 Å (x = 0.6), corresponding to the (311) planes of spinel
surfaces as observed in some of the dilute magnetic cubic phase of CoxCu1−xCr2S4. Fast Fourier transform (FFT)
semiconductor systems.18,19 images in insets to Figure 3b,d show bright spots that can be
We have noted a significant deviation between the size of indexed to the (311) planes. The measured lattice distances
nanocrystals measured from TEM images and that calculated from HRTEM images indicate lattice compression with
from the width of X-ray diffraction peaks. To understand this substitution of cobalt ion, which is consistent with the results
behavior, we have carried out scanning electron microscope obtained from the X-ray diffraction measurements. Elemental
investigation on a large quantity of sample from various runs, compositions of the CoxCu1−xCr2S4 nanocrystals, determined
which reproducibly provided nanocrystals of size similar to from SEM-EDX and TEM-EDX analysis, are found to be close
C dx.doi.org/10.1021/cm401938f | Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials Article

Figure 3. (a) HRTEM image of CuCr2S4 and Co0.2Cu0.8Cr2S4


nanocrystals with arrows indicating twin boundary defects. (b−e)
HRTEM images of CoxCu1−xCr2S4 nanocrystals: (b) x = 0, (c) x = 0.2,
(d) x = 0.4, and (e) x = 0.6. (Inset, b) (top) Low-magnification image
of single nanocube and (bottom) corresponding FFT image. (Inset, d)
FFT image.
Figure 4. (a) Magnetization (M) versus temperature (T) measure-
ments on CoxCu1−xCr2S4 nanocrystals with applied field of 1 T. (b)
to the expected compositions. Complete analysis results and Magnetization (M) versus magnetic field (H) measurements on
representative SEM-EDX spectra of CuCr2S4, Co0.4Cu0.6Cr2S4, CoxCu1−xCr2S4 nanocrystals at 5 K. (Inset) M−H loops at 200 K.
and CoCr2S4 nanocrystals are provided in Figure S5 and Table
S1 in Supporting Information.
The magnetic properties of CoxCu1−xCr2S4 nanocrystals have magnetization values of CoxCu1−xCr2S4 nanocrystals for higher
been analyzed by use of a SQUID magnetometer. Magnet- cobalt concentrations is partially due to size effect, since the
ization (M) as a function of applied magnetic field (H) has sizes of Co0.8Cu0.2Cr2S4 and CoCr2S4 nanocrystals are much
been measured at 5 and 200 K, in order to identify the effect of smaller than for the other compositions. In very small magnetic
A-site cobalt substitution on the saturation magnetization and nanocrystals, the number of spins on the surface exceeds the
coercivity values of CoxCu1−xCr2S4 nanocrystals (Figure 4). number of spins forming the core of the particles (∼43% of the
The M−H loops of CoxCu1−xCr2S4 nanocrystals at 200 K show atoms are on the surface for a 3 nm cubic spinel nanocrystal),
superparamagnetic behavior up to x values of 0.6, whereas which would significantly affect the magnetization value of the
higher cobalt concentration (x = 0.8 and 1) samples show nanocrystals. In addition, defects at cation and anion sites and
paramagnetic behavior. However, the nanocrystals at 5 K broken bonds at the nanocrystal surface with resulting
behave as relatively soft ferromagnets up to x = 0.6 with uncompensated spins can also reduce the net magnetization
coercivity values of ∼520 Oe for x = 0.1, ∼510 Oe for x = 0.2, and changes in magnetic behavior.22 However, our magnetic
∼530 Oe for x = 0.4, and ∼620 Oe for x = 0.6, with measurements did not show any significant changes in magnetic
superparamagnetic behavior for x = 0.8 and 1 (Figure 4b). The behavior other than the expected superparamagnetism. The
measurement also indicate that the magnetization of none of decrease in magnetic moment with increasing cobalt ion
the samples saturates, even with an applied field of 5 T. This concentration is expected and is ascribed to the presence of a
observation is consistent with our previous report on CuCr2S4 large opposing moment at the Co site.5a
nanocrystals.10a The highest magnetization values measured at Furthermore, we have carried out magnetization measure-
5 K are 34.7 emu/g for x = 0.1, 34.0 emu/g for x = 0.2, 33.4 ment as a function of temperature with an applied field of 1 T
emu/g for x = 0.4, and 31.7 emu/g for x = 0.6. However, the on CoxCu1−xCr2S4 nanocrystals, to obtain the Curie transition
value is significantly reduced to 7.49 emu/g for x = 0.8 and temperature (TC). The measurement results in Figure 4a show
further down to 3.81 emu/g for x = 1. The observed drop in a systematic decrease in the transition temperature with
D dx.doi.org/10.1021/cm401938f | Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials Article

increasing cobalt ion concentration. The transition temper-


atures deduced from the measurements are ∼265 K for x = 0.1,
∼250 K for x = 0.2, ∼245 K for x = 0.4, ∼240 K for x = 0.6,
∼180 K for x = 0.8, and ∼160 K for x = 1. The TC value of
CoCr2S4 nanocrystals is somewhat lower than the reported bulk
value of 221 K.5 The observed trend in the reduction of Curie
temperature with increasing cobalt substitution is consistent
with the estimated values from our band structure calculations
(Supporting Information). This observation could also be the
result of a size effect. Overall, our results indicate that the Curie
temperature of the CoxCu1−xCr2S4 system can be above room
temperature for lower concentrations of cobalt and with growth
of larger nanocrystals. We have additionally performed field-
cooled (FC) and zero-field-cooled (ZFC) measurements with
an applied field of 100 Oe to determine the superparamagnetic
blocking temperature (TB) values as a function of Co
concentration. The blocking temperature values obtained
from the FC−ZFC measurements (Figure S6) are provided
in Table S2 (see Supporting Information).
In order to better understand the magnetic characteristics, we
have calculated the electronic and magnetic structures of
CoxCu1−xCr2S4 within the PBE generalized gradient approx-
imation to density functional theory as well as its extensions,
PBE+U and the HSE06 screened hybrid-functional method.11
We find that a ferrimagnetic configuration is preferred for x > 0
with the Co moments aligned with one another and opposing
the Cr moments. In CoCr2S4, this leads to a net moment of
Figure 5. Density of states for CoxCu1−xCr2S4 nanocrystals with (a) x
about 3μB per formula unit. Considering the total cell moments,
= 1, (b) x = 0.5, and (c) x = 0 by use of PBE+U (left) and HSE06
partial densities of states, and effects of crystal field splitting, we (right). The qualitative band structure is the same with both methods,
can assign three majority t2g electrons to each Cr3+ ion and five giving a majority gap 0.2−0.3 eV smaller than the minority gap. (Red,
minority d and two majority eg electrons to each Co2+ ion. With majority spins; green, minority spins).
no minority electrons on the Cr sites and a full minority Co 3d
shell, the dispersive states in the vicinity of the spin-down gap
are pure S p at the valence band maximum and Cr d above the
gap, while the relatively flat states surrounding the spin-up gap
are a mixture of TM d and S p states. As expected, PBE finds
that the partially filled Co and Cr d states lie across the Fermi
level, while PBE+U and HSE06 are able to correctly predict the
presence of a gap in both channels. As can be seen in Figure 5a,
the majority gap is about 0.5 and 1.4 eV in PBE+U and HSE06,
respectively, while the minority gap is found to be slightly
larger, 0.8 eV in PBE+U and 1.6 eV in HSE06. The hybrid-
functional results are in reasonable agreement with the Figure 6. (a) UV−vis spectra of CoCr2S4 nanocrystals. (Inset)
measured optical gap of CoCr2S4 nanocrystals (Figure 6). Photograph of dispersed sample used for UV−vis measurement. (b)
However, the measured band gap of CoCr2S4 nanocrystals is Energy versus absorption plot of CoCr2S4 nanocrystals.
larger than the band gap value (0.9 eV) reported for bulk
CoCr2S4, which indicates the quantum confinement effect in narrow and move toward lower energy as x approaches 1 (but
CoCr2S4 nanocrystals.23 At the other extreme (x = 0; that is, note that this is accompanied by a slight shift to higher energies
CuCr2S4), our results suggest that the Cr ions provide about in the minority states that cross the Fermi energy). This
three electrons in the majority t2g bands, but the cell moment is observation does not contradict the previous report, where the
only about 5.1μB per formula unit, reflecting the induced composition-dependent transition occurs only at finite temper-
opposing moment in the rest of the cell and the partially filled ature (all of our calculations are performed at zero temper-
bands. In the intermediate systems, one can observe in Figure ature).20 Perhaps some charge-ordering or other charge
5b that the hybridization states at the Fermi level seen in reorganization among the Cu and Co ions occurs at higher
CuCr2S4 remain, pushing the energy gap to higher energy and temperatures, leading to the creation of a semiconducting gap.
retaining the parent compound’s metallic character. This effect The origin of the ferromagnetic exchange between Cr ions in
persists at all Co:Cu ratios considered in this work, and CoCr2S4 arises from a competition between the antiferromag-
increasing U on the transition metal sites does not drive the netic t2g−t2g interaction between the edge-sharing octahedral
orbital to integer occupation and half-metallicity. and ferromagnetic t2g−eg interactions in 90° Cr−S−Cr groups,
It is interesting to note that our band structure calculations as given by the Goodenough−Kanamori−Anderson (GKA)
did not detect any metal−semiconductor transition as a rules.24 In this case, as is typical of thiospinels, the interaction
function of composition except at x = 1. However, the states between Cr and Co is more complex due to the mixing of
at the majority valence band maximum become increasingly several orbitals arising from the 124° Cr−S−Co angle. The
E dx.doi.org/10.1021/cm401938f | Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials


Article

GKA rules do not give a clear prescription here, but it has been CONCLUSIONS
noted that, in such systems, there is a critical angle dividing In summary, nanocrystals of chalcospinel CoxCu1−xCr2S4 have
antiferromagnetic from ferromagnetic interactions.25 It is well- been synthesized over the entire composition range utilizing a
known that, in most spinels with magnetic A- and B-site ions, facile hot-injection method. The synthesis process yields nearly
the A−B exchange is antiferromagnetic, so we can conclude cube-shaped particles for all compositions. The particle size is
that this critical angle must be greater than 124° in this case. observed to decrease with increasing cobalt ion concentration.
This exchange picture cannot be directly applied to CuCr2S4 The reduction in magnetic transition temperature and
(nor for any composition with x < 1), as the system is now magnetization with increasing cobalt concentration are found
metallic, and the idea of virtual electron transfers leading to to follow the same trend. Band structure calculations and
indirect exchange may no longer apply. The Cr t2g states are optical measurements have estimated the metallic ferri/
nearly identical at x = 0 and x = 1, so this part of the ferromagnetic behavior in CoxCu1−xCr2S4 (x = 0−0.8)
explanation likely still holds. However, the Cu d bands are less compositions, whereas CoCr2S4 is a semiconducting ferrimag-
localized than those of Co, and this itinerant exchange net. This simple solution-state synthesis process is promising
interaction is likely responsible for the difference in Curie for the synthesis of a variety of other chromium-based
temperature between the two cases. sulfospinel compounds.


A full understanding of the exchange coupling and Curie
temperature in a transition metal oxide or chalcogenide ASSOCIATED CONTENT
requires a detailed analysis of the interactions between all
near-neighbor transition metal (TM) sites.25 However, a
*
S Supporting Information

qualitative analysis of the local orbital structure coupled with Six figures, showing crystal structures of CuCr2S4 and CoCr2S4,
simple total energy comparisons of ferromagnetic (FM) and additional TEM images, HAADF images, Williamson−Hall
antiferromagnetic (AF) configurations (among the Cr ions) can plot, SEM-EDX graphs, and ZFC and FC magnetic measure-
yield useful insight. We have performed such calculations using ments; and two tables, listing SEM-EDX data and magnetic
the same PBE+U setup employed in studying the electronic parameters (PDF). This material is available free of charge via
the Internet at http://pubs.acs.org.


structure, computing the exchange energy per Cr ion ΔECr =
(EAF − EFM)/NCr for 56-atom x = 0, 0.5, and 1.0 unit cells,
AUTHOR INFORMATION
where NCr is the number of Cr ions per cell. We consider C-
type antiferromagnetism for the purposes of our energy Corresponding Author
comparisons. *E-mail agupta@mint.ua.edu.
In CuCr2S4, we find that the FM configuration is lower in Notes
energy than the AF configuration by 351 meV, giving ΔECr = The authors declare no competing financial interest.
79.6 meV. If we compare this to the value calculated for CrO2
in Ref 26 (about 150 meV/Cr), we can estimate that the Curie
temperature for this material should fall between 200 and 250
■ ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
K. We note that, unsurprisingly, the induced moments spread under Grant CHE-1012850


throughout the cell on the Cu and S sites vanishes in this fully
compensated configuration. When x = 0.5, we are faced with REFERENCES
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