Iron and Chromium Intercalated Niobium and Tantalum

Disulfides: Structure and Magnetism.

Lilia S. Xie, Samra Husremovic, ́Oscar Gonzalez, Isaac M. Craig, and D. Kwabena Bediako*

Citation: https://doi.org/10.1021/jacs.1c12975
J. Am. Chem. Soc. 2022, 144, 9525−9542.
Submitted by: 521CY1019
NUNAVATH RAMAKRISHNA.

Abstract: The arrangement and magnetic properties of transition metal dichalcogenides

(TMDs) can be modified by inserting spin-bearing transition metal centers. This modification
is influenced by factors such as the structure of the host material, the type of inserted element,
and the level of insertion, and any disorder in the inserted element. These different factors affect
interactions leading to a wide range of collective electronic and magnetic behaviours. The
unique magnetic and electrical characteristics exhibited by these systems make them promising
candidates for controlling magnetism in solid-state materials and developing spin-based
electronic devices. In this Perspective, we focus on Fe and Cr intercalated NbS2 and TaS2 to
provide an overview of the magnetism observed in intercalated TMDs. These four different
materials within this family exhibit an array of magnetic properties. These properties include
the ability to rapidly switch between states, magnetic switching driven by current, and the
presence of chiral spin patterns. In each analysis, we delve into the factors contributing to these
electronic phases. We consider aspects such as composition, bonding, electronic structure, and
magnetic anisotropy to explain their causes.

Keywords: Transition metal dichalcogenide (TMDs), Ferromagnetism, Anti Ferromagnetism

Intercalation, Crystal and electronic structure, Spin canting.

INTRODUCTION: Transition metal dichalcogenides (TMDs) are two-layer materials

composed of transition metals and bridging chalcogenides. These layers stack together through
weak van der Waals interactions, along the c-axis. This structure allows for the intercalation of
species, including transition metals, into the interfaces formed by van der Waals forces. 1-4 In
some cases, intercalation occurs due to a driven charge transfer reaction, where the intercalating
species' electrons are moved to the host material's conduction band. As a result, the solid

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consists of charged intercalants embedded within an electron-doped host lattice.5-7. Magnetic
order over long distances can be achieved by inserting local magnetic moments into the lattice
of open-shell intercalants.8,9 Interest in this family of materials as adjustable platforms for
investigating the interaction between composition, structure, and magnetism has long been
stimulated by the diversity of possible intercalants and host lattices. Exchange interactions and
magnetic correlations are significantly influenced by differences in the types of defects and
domain structures present in these intercalated compounds, as has recently been discovered,10-
13
resulting in complex magnetic phase spaces. Among the known magnetic intercalated TMDs,
Fe- and Cr intercalated NbS2 and TaS2, depending on the identity and stoichiometry of the
intercalant, materials display a wide range of behaviours. Their characteristics, which include
rapid magnetization switching,14,15 low-current electrical switching of antiferromagnetic
states,16 and chiral spin textures,17 have positioned these materials as interesting options for
electrical technology based on spin (spintronics). This Perspective seeks to present an overview
of the magnetic characteristics of Fe- and Cr-intercalated NbS2 and TaS2, as well as to draw
linkages between magnetic order and basic changes in electronic structure that may guide
future research on these systems. For example, the Fe-intercalated compounds have stronger
spin-orbit coupling (SOC) because of the unquenched orbital angular momentum of the Fe 2+
centers, which accounts for significant differences in the properties of Fe- and Cr-intercalated
systems. As a result, the magnetic anisotropy of Fe-intercalated TMDs differs significantly
from that of Cr-intercalated analogs: in the Fe-based derivatives, the c axis is the easy axis of
magnetization, whereas it is the hard axis in the Cr-based compounds. Other effects, such as
varying SOC magnitudes from the NbS2 and TaS2 host lattices, result in further differences in
each of the intercalated compounds.

It has been demonstrated that FexNbS2 exhibits spin glass behaviour that couples and coexists
with local AFM (Antiferromagnetic) domains,18,19 while CrxNbS2 and CrxTaS2 both show chiral
spin nature.

RESULTS AND DISCUSSION:

INTERCALATION INTO NbS2 AND TaS2: The coordination of the transition metal in NbS2
and TaS2, like in many other TMDs, can be either octahedral (Oh) or trigonal prismatic (D 3h).
These polytypes are found in several arrangements. This perspective will focus only on the 2H
polytype of these materials, where all of the metal centers have D3h coordination, as this is the
polytype that has been investigated the most in terms of intercalation. The polytype, which

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crystallises in the P63/mmc space group, is designated as 2H because each hexagonal unit cell
contains two layers. In the vdW interface, the 2H polytype has both octahedral and tetrahedral
interstitial sites (Figure 1), but the crystal structures of Fe- and Cr-intercalated NbS2 and TaS2
compounds, as determined by experiment, indicate that intercalants only occupy the octahedral
sites.

Figure 1. In the native structures of 2H TMDs, intercalants can occupy tetrahedral (left) and
octahedral (right) interstitial vacancies.

ELECTRONIC STRUCTURE: The NbS2 and TaS2 host materials' metallic nature can be
explained by a straightforward electron counting scheme. Formally, we anticipate that the
effective charge on the chalcogen centers will be −2, which will give the transition metals a +4
oxidation state and a d1 electron configuration. The trigonal prismatic coordination
environment divides the Nb or Ta d orbitals into two parts using crystal field theory as a first-
order approximation. a1 ′ (dz 2), e′ (dx 2 −y 2, dxy), and e″ (dxz, dyz) sets, in order of increasing
energy. Therefore, one electron from Nb or Ta goes into a band with primarily d z 2 character,
resulting in a partially filled band at the Fermi level (Figure 2).

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Figure 2. The density of states of (unintercalated) 2H-NbS2 or 2H-TaS2 is represented
qualitatively, with the predominant parentage of states labeled. The Fermi level is above the
the dz 2 band.

SUPERLATTICE STRUCTURES: At specific compositions of intercalated TMDs with the

formula TxMS2, crystallographic super lattices are seen, created by the periodic arrangement
of the intercalants into octahedral interstitial sites. In particular, when M = Nb or Ta, complete
superlattices with x = 1/ 4 and x = 1/3 form for CrxMS2 and FexMS2. When x = 1/4 and a lattice
constant a0 is used, a supercell with a′ = 2a0 occurs. In this situation, the supercell's a and b axes
correspond with the parent TMD's original axes, and the parent TMD's space group, P63/mmc,
is kept. When x = 1/3, a supercell with a′ = 3a0 is produced, with the a and b axes rotated by 30
degrees relative to each other, Unlike the parent TMD 2a0 × 2a0 superlattice, the √3a0 × √3a0
superlattice is non-centrosymmetric, with space group P6322. One of the most significant
differences between these structures is the centrosymmetric character of the 2a0 × 2a0
superlattice and the non-centrosymmetric nature of the √3a0 × √3a0 superlattice, in addition to
the unique electron filling levels suggested by their respective compositions. The lack of
symmetry inversion profoundly affects the magnetic properties of materials TxMS2 with x ≈
1/3, the Dzyaloshinskii−Moriya (DM) interaction arises from the lack of inversion symmetry
in the √3 × √3 superlattice, resulting in spin canting and chiral magnetic ground states.15
Crucially, the images displayed in Figure 3 depict the ideal superlattices anticipated at the
precise stoichiometries of x = 1/3 and 1/4 in these intercalated TMDs.

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Figure 3. (a−c) Structures of two layers of an unintercalated 2H-MS2 primary TMD with a
constant lattice a0; T1/4MS2 with an a′ = 2a0 supercell; and T1/3MS2 with an a′ = √3a0 supercell,
all viewed along the c crystallographic axis. (d−e) Illustrations of the structures of T1/4MS2 and
T1/3MS2 viewed parallel to the c crystallographic axis along [2110] and [1010], respectively.
The slabs in (e) are defined as cuts of the (2110) plane in the [1010] direction, indicated on the
right.

Arise of magnetic behaviour: The type of long-range magnetic ordering in a material is

established by the interchange correlations amongst the material's unpaired electrons. Direct
superexchage, heisenberg interactions and the RKKY (Ruderman−Kittel−Kasuya−Yosida)
interactions are two examples that may take place in solid-state materials.16

IRON-INTERCALATED NIOBIUM AND TANTALUM SULFIDES: In spite of FexNbS2

and FexTaS2 are isostructural and isoelectronic, they exhibit distinct magnetic state at ground
level. For x < 0.4 composition FexTaS2 show ferromagnetic behaviour, while Fe xNbS2 exhibit
antiferromagnetic property. Magnetic properties of Fe xNbS2 and FexTaS2 change with small
variations in composition for x = 0.25, and 0.33. samples with uniform 2 × 2 or √3 × √3
superlattices exhibit sharp magnetic transition. 17

CHROMIUM-INTERCALATED NIOBIUM AND TANTALUM SULFIDES: Cr (x =

0.33) of NbS2 and TaS2 have √3 × √3 superstructures and noncentrosymmetric structures like

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other T0.33MS2. The Cr counterparts have a magnetic easy plane in the ab plane, in contrast to
the Fe intercalated counterpart, which has an easy axis along c. Spin canting comes from DM
interaction that competes with ferromagnetic ordering due to the absence of inversion
symmetry. Because of this, chiral magnetic states are present in both Cr (x = 0.33) of NbS 2
and TaS2 making them interesting materials to examine unique spin textures.

Figure 4. Schematic diagram revealing how DM and ferromagnetic interactions interact in a

chiral helimagnet; these magnetic interactions cause a distinctive angle to form between
adjacent spins.

Outlook: Depending on the intercalant and host lattices identities, as well as the exact
intercalation stoichiometry, samples Fe and Cr intercalated NbS2 and TaS2 display fascinating
magnetic behaviours. To better understand these compounds, various analyses have formed,
such as direct measurement of magnetic, electrical, and thermal properties; spectroscopic
analysis of the electronic structure; imaging methods like TEM, Lorentz TEM, and MFM; and
first-principals calculation. However, there are still plenty of interesting research directions to
pursue. Here is a summary of important queries and interesting possibilities.

a) Further investigation of exchange interactions: RKKY is supported as the main

exchange mechanism mediating magnetic order by reports on some materials in this
family, such as Fe1/4TaS2. Further research on several materials, like Fe1/3TaS2 and
Cr1/3NbS2, has shown more intricate connections between the magnetic properties and
electronic structure. According to certain theories, the √3 × √3 superlattice's inversion
symmetry breaking and higher intercalation density in the x = 1/3 system lead to
stronger hybridization between the Fe intercalants and the TaS 2 host lattice than in the
x = 1/4 system. Further comprehension of the role intercalant electronic states play in
the interaction between itinerant bands and localized spins, however, may open up new
possibilities for adjusting the magnetic characteristics of this kind of material.

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 b) Precise determination of stoichiometry and superlattice structure: The intercalation
quantity can significantly affect magnetic characteristics, as demonstrated by minor
variations from x = 1/4 in FexTaS2 and x = 1/3 in FexNbS2. Nevertheless, not all research
has used elemental analysis methods, including electron energy loss spectroscopy and
energy-dispersive X-ray spectroscopy, to examine exact compositions. Understanding
the relationship between electrical and magnetic characteristics and accurate
composition may lead to improved uniformity and repeatability, as well as a more
thorough comprehension of how stoichiometry affects magnetic properties.

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