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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 =
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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.
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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
B dx.doi.org/10.1021/cm401938f | Chem. Mater. XXXX, XXX, XXX−XXX
Chemistry of Materials Article
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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.
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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.
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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
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