Materials Today Chemistry 38 (2024) 102134

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Materials Today Chemistry

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Thickness dependent nanoscale magnetism in two-dimensional manganese

telluride (MnTe)
Surbhi Slathia a, Manoj Tripathi b, **, Raphael Tromer c, Chinmayee Chowde Gowda a,
Prafull Pandey d, Douglas S. Galvao c, ***, Alan Dalton b, ****, Chandra Sekhar Tiwary a, e, *
a
School of Nano Science and Technology, Indian Institute of Kharagpur, West Bengal, 721302, India
b
Department of Physics and Astronomy, University of Sussex, Brighton, BN1 9RH, United Kingdom
c
Applied Physics Department, State University of Campinas, Campinas, SP, 13083-970, Brazil
d
Materials Engineering, Indian Institute of Technology Gandhinagar, Gujarat, 382055, India
e
Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, West Bengal, 721302, India

A R T I C L E I N F O A B S T R A C T

Keywords: Magnetism from two-dimensional (2D) materials has received significant attention and admiration due to their
Magnetism unique electronic and magnetic properties owing to quantum confinement, such as spin-orbit coupling, magnetic
2D materials anisotropy, and emergent magnetic orders, leading to behaviors and properties not observed in bulk materials.
Manganese telluride
One of the crucial gaps that need to be addressed is deciphering the ordering of magnetic behavior with the
Magnetic force microscopy
Density functional theory
thickness of manganese dichalcogenides, manganese telluride (MnTe). The present work explores the pivotal role
of thickness in modulating the magnetic properties of 2D MnTe, obtained using liquid-phase exfoliation tech­
niques. Intriguing magnetic and electronic properties have been observed in MnTe thinner than 5 nm. Our
experimental findings and density functional theory (DFT) calculations revealed the transition from anti-
ferromagnetic characteristics to ferromagnetic behavior for one to two layers and then back to anti-
ferromagnetic behavior for thicknesses larger than 5 nm. These results demonstrate the existence of thickness-
dependent transitions in magnetic ordering and anisotropy for the 2D materials. The experimental results, in
conjunction with theoretical modeling, unravel useful insights into the implications of magnetic 2D MnTe for
emerging technologies driven by nanoscale magnetism, such as spintronics and quantum computing. The out­
comes from the present work open new possibilities for developing memory devices with enhanced functionality
and efficiency.

1. Introduction for dimensions less than or equal to two with sufficiently short-range
interactions [2]. However, it has been extensively misinterpreted that
In modern science, magnetism in two dimensional (2D) materials has the magnetic order is absent in two-dimensional materials. On the
recently become one of the most promising research fields due to its contrary, this theorem does not apply to any spin system with a different
diverse applications, from spintronics to medical science. The theoret­ anisotropy. The concurrent progress in thin film growth resulted in the
ical foundation of magnetism in 2D materials was pioneered by Onsager first thin film magnets in the 1970s–1990s [3] and following the dis­
in 1944, demonstrating that an Ising magnet with a monolayer thickness covery of graphene in 2004, the research on 2D magnetism has been
can have a long-range ordered state through a phase transition [1]. Two rapidly advancing. A previous study on graphene reported that its
decades later, the Mermin-Wagner theorem was published, stating that functionalized monolayers can exhibit magnetism. This is due to the
at finite temperatures, it is impossible to break continuous symmetries presence of a single π state at the Fermi level if the pz orbital in graphene

* Corresponding author. Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, West Bengal, 721302, India.
** Corresponding author.
*** Corresponding author.
**** Corresponding author.
E-mail addresses: M.Tripathi@sussex.ac.uk (M. Tripathi), galvao@ifi.unicamp.br (D.S. Galvao), A.B.Dalton@sussex.ac.uk (A. Dalton), chandra.tiwary@metal.
iitkgp.ac.in (C.S. Tiwary).

https://doi.org/10.1016/j.mtchem.2024.102134
Received 27 March 2024; Received in revised form 19 May 2024; Accepted 23 May 2024
Available online 28 May 2024
2468-5194/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
S. Slathia et al. Materials Today Chemistry 38 (2024) 102134

is removed. Thus, Coulombic repulsion prevents two electrons with the magnetic ordering in MnTe had changed from two to five layers. The
same spin from filling the space in the π state, resulting in a net magnetic DFT studies also showed the change in the spin-up and spin-down
moment [4]. In addition to looking for materials with desirable qualities arrangement in the case of monolayer, three and six layers. It was
for certain applications, two-dimensional material exploration is noted that monolayer exhibited antiferromagnetic behavior, while two,
necessary to uncover potentially new and fascinating physical phe­ three, and four layers displayed ferromagnetic ordering similar to
nomena. Like graphene, other 2D materials are currently also being experimental results. Similarly, thickness-dependent transitions were
explored due to their distinct properties [5] for different applications, observed in nanoscale conductivity by C-AFM, where the point contact
such as flexible electronics [6], catalysis [7,8], energy storage and between tip and sample changed from non-ohmic to ohmic with an
conversion devices [9], and spintronics. Thus, efforts are being made to increased number of layers. This research is crucial for systems based on
induce magnetism in these materials through different approaches, such spintronics, including spin-based transistors, magnetic random-access
as doping [10], defects [11], functionalization [4], etc. A previous memory, and other devices that process and store information using
density functional theory (DFT) study showed that a ground state the spin of electrons.
transition from a non-magnetic to a ferromagnetic state can be achieved
by applying a tensile strain of 6.6 % at 232 K Ci temperature Tc in a 2. Material and methods
hydrogenated MoS2 monolayer [12]. Daqiang Gao et al. experimentally
demonstrated that intrinsic ferromagnetism was induced in 2.1. Synthesis and instrumentation
fluorine-adsorbed MoS2 nanosheets with a saturation magnetization of
~0.06 emu g− 1 at room temperature and a magnetoresistance of 4.1 % The Flame melting technique was used to produce manganese
[13]. Thickness-dependent magnetic behavior of monolayers of CrI3, a telluride (MnTe) alloys, while ultra-pure argon was continuously pum­
2D material exhibiting ferromagnetic behavior, was also reported [14]. ped into the process. A mixture of 10 g of Mn and Te was melted in a 10
Among various TMDs, the newly obtained non-layered 2D materials mm quartz tube. Since the melting point of the alloy is 1170 ◦ C and
are being explored due to their isotropic chemical bonding along three tellurium has a boiling point of 988 ◦ C, therefore sustaining the sample
dimensions, which results in massive unsaturated dangling bonds, at temperature 950 ◦ C for a long period assures that the elements are
thereby enhancing the surface properties of the materials, which is a well mixed. To verify uniformity, the samples were remelted two to
feature rarely observed in layered materials [15]. Moreover, it has been three times. The prepared samples were cooled using argon flow.
revealed that these dangling bonds on the surface of non-layered ma­ Further, the vacuum-packed bulk MnTe was heated in a high-
terials showed compatibility with common substrates, such as silicon temperature furnace by gradually increasing the temperature up to
[16]. Several techniques have been implemented to produce 2D 900 ◦ C. This temperature was maintained for up to 10 h before furnace
non-layered materials, like the template-directed synthesis method [17], cooling. For preparing 2D MnTe, 1 g of the bulk powdered sample was
van der Waals epitaxial (vdWE) method [18]. However, the liquid phase dispersed in 300 ml of propane-2-ol solvent and bath sonicated for 4 h.
exfoliation (LPE) method has been rarely explored to synthesize 2D The dispersed solutions were kept at rest for about 24 h at room tem­
non-layered structures because of their strong in-plane and out-of-plane perature and the supernatants were collected, dried at 60 ◦ C on a hot
anisotropic characteristics. Fortunately, there are a few inorganic plate and were used for further analyses.
non-layered crystalline materials especially those having chained The diffraction patterns and crystalline phase data of bulk and 2D
structures like tellurium (Te) and selenium (Se) which exhibit anisot­ MnTe samples were obtained using Bruker’s D8 Advance XRD, which
ropy between inter and intra-chains [19] and hence give the possibility has Cu-kα radiation with a wavelength (λ) of 1.5406 Å and operating
to create 2D non-layered structures. configurations of 40 kV voltage and 40 mA current. The high-angle
MnTe, a non-van der Waals TMDs member having a hexagonal angular dark field scanning transmission electron microscopy (HAADF
Nickel arsenide (NiAs) - type structure is antiferromagnetic at room STEM) was utilized with FEI, Themis 60-300, and FEI-CETA 4k × 4k
temperature in its bulk form, as reported in 1963 from neutron camera to investigate topographical, compositional, and crystalline
diffraction studies [20]. Mn-based TMDCs are fascinating as they exhibit characteristics. An x-ray photoelectron spectroscopy (XPS) Thermo­
a synergy between their semiconducting and magnetic behavior [21, Fisher Scientific Nexsa was employed as a source of Al-Kα radiation (λ =
22], which is needed for the next generation of optical and quantum 1486.71 eV) to examine the oxidation states and composition of the
information devices, as well as for ultra-thin electronics [23]. As a samples. A WiTec UHTS Raman spectrometer 300 VIS, Germany, with
semiconductor, the increased spin-orbit coupling can result in an excitation wavelength of 532 nm, was used to investigate the room-
out-of-plane magnetic anisotropy. Additionally, it occasionally results in temperature Raman spectra.
spin-orbit torque, which can be effectively utilized to control the Magnetic force microscopy, I–V measurements, potential mapping,
magnetization of certain materials [24,25]. The presence of heavy atoms and nanoscale imaging were all done with atomic force microscopy
in TMDs results in a strong spin-orbit coupling. On the other hand, Mn (AFM). These measurements were carried out at room temperature using
has five 3d electrons that fill d-levels and add a magnetic moment of 5 μB the Bruker Dimension Icon instrument with a relative humidity of ~35
per unit cell. When bonded to chalcogenides, these electrons can %. To reduce the environmental noise and vibrations from the building,
contribute to the induction of magnetism through intralayer exchange the AFM was placed on top of an anti-vibration stage in an insulated box.
couplings and/or super-exchange interactions [26,27]. For MFM measurements, a cobalt-chromium coated Bruker magnetic
Recently, we investigated 2D MnTe structures and its magnetic exchange scanning probes (MESP) on the tip apex (rectangular, nominal
behavior at different temperatures [28]. A transition in the magnetic radius: 35 nm, frequency: 75 KHz and spring constant: 3.0 N/m) was
behavior from antiferromagnetic to paramagnetic was observed, as well used and Platinum/Iridium (Pt/Ir) coated SiN tip (triangular, nominal
as increased magnetic saturation values for the 2D MnTe in comparison radius: 25 nm, frequency 70 KHz and a spring constant of 0.4 N/m) was
to their bulk counterpart. Therefore, it would be interesting to used for C-AFM measurements. Peak force Kelvin probe force micro­
comprehend how the magnetic behavior changes and whether the scopy (KPFM) was carried out to measure the surface potential of the
thickness plays any role in this transition from the bulk to the 2D ones. In MnTe surfaces. The conductive AFM probe (model: PFQNE_Al, Bruker)
the present work, we used magnetic force microscopy (MFM) and was used for the investigation in two pass modes at ambient conditions.
conductive atomic force microscopy (C-AFM) to study the nanoscale In the first mode of operation, the topography of the MnTe landscapes
magnetic and electrical behavior of mechanically synthesized 2D man­ was measured, and in the second mode, the conductive tip apex was
ganese telluride (MnTe) structures obtained using scalable LPE tech­ lifted (lift-up) based on topographical information to measure the con­
niques. It was observed that when thickness increased above 5 nm, a tact potential difference (CPD, V), referred as a surface potential map.
shift from the negative to the positive phase occurred, indicating that the The external gold surface (reference from Bruker) is used to calculate the

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S. Slathia et al. Materials Today Chemistry 38 (2024) 102134

work function of the cantilever [29]. structures through Density Functional Theory (DFT) simulations. We
adopted standard DFT methodology, using common semi-local approx­
2.2. Theory methodology imations for the exchange-correlation energy, including the Perdew-
Burke-Emzerhof (PBE) functional and the semi-local generalized
We investigated the magnetic properties of two-dimensional MnTe gradient approximation (GGA) [30]. The electronic band structural and

Fig. 1. The Structural and morphological Characteristics of MnTe. (a) A Schematic of formation of 2D MnTe using liquid exfoliation method; (b) XRD spectrum of
bulk and exfoliated MnTe; (c) XPS spectra of 2D MnTe; (d) Te 3d and Mn 2p XPS spectrum; (e) Raman spectra of 2D MnTe, and (f) TEM image of exfoliated MnTe
(insets showing FFT patterns of different crystallographic plane orientations showing dspacing of 0.33 nm and schematic arrangement of Mn and Te atoms).

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structural stability of MnTe have already been investigated in reference 646.69 and 659.15 eV correspond to the Mn 2p3/2 and 2p1/2 of Mn4+
[28], in which it was calculated the corresponding phonon spectra and ions, respectively [37]. With a ΔSO value of 10.53 eV, the prominent
ab initio molecular dynamics (AIMD) simulations different temperatures doublets in the Te 3d spectra at 573.08 eV and 583.61 eV, correspond to
were used (0 and 800 K) to address structural and electronic features. Te 3d5/2 and Te 3d3/2, respectively. The small peaks at 576.2 eV and
The simulations were carried out for the most commonly observed 586.73 eV are due to a trace of Te–O bonding [38]. Using a laser exci­
structure in experiments, which is the 2D MnTe structure obtained by tation of 532 nm, the Raman spectroscopy analysis of the exfoliated
cleaving the crystal along the [001] direction. Due to the existence of MnTe is illustrated in Fig. 1e. The Te phonon mode (A1) is shown by the
d electrons, a DFT + U method was used for the magnetic simulations, peak at 92 cm− 1 [39]. The transverse optic (TO) and longitudinal optic
with the Hubbard value chosen to be 4 eV. The chosen U value was (LO) modes of MnTe, respectively, are responsible for the peaks at 112
determined through a procedure described in S. B. Hu et al. [31], testing cm− 1 and 147 cm− 1, which validate the production of MnTe [40,41].
the U values across the range from 1 to 6 eV. The electronic bandgap Based on the findings of S. Ghosh et al. the peak detected at 197 cm− 1 is
values and the valence states slightly change as a function of U, while consistent with the MnTe-like LO2 mode [42]. The HAADF TEM image of
moderate changes in the conduction bands were observed. 2D MnTe is shown in Fig. 1f. The different crystallographic plane
The energy cutoff was established at 300 Ry, and an 8 × 8 × 1 orientation can be observed where smaller bright dots correspond to Mn
Monkhorst-Pack grid method was used. The adopted convergence cri­ atoms and the insets show the FFT pattern having zone axis as (0 1 0),
terion was when forces on each atom were less than 0.01 eV/Å. The confirming the hexagonal structure [43]. The schematic arrangements
following expression was used to calculate the magnetic order of each of Mn and Te atoms can be seen in Fig. 1f, where Mn and Te atoms are
structure: marked in dark red and green color, respectively. The interplanar dis­
tance of 0.33 nm was calculated using the plot profile mapping of lattice
ΔE = Eferro − Eantiferro (1)
fringes.
where ΔE negative/positive indicates the ferro/antiferro configuration. The two-pass tapping and lift mode is used to study the magneto­
We also estimated the force to exfoliate one layer from 2D-MnTe, static interactions between the CoCr-coated magnetic tip and the stray
considering different thicknesses. We used the same methodology magnetic fields from 2D MnTe. The force gradient of the stray field is
described in reference [32]. We consider for each case, the layer at the detected by sliding the magnetized tip at a constant lift height of 20 nm,
surface is displaced from the equilibrium configuration using a value of as depicted in Fig. 2a. The magnetized tip apex is equipped with a
0.2 Å. For each distance value, we perform a single point calculation and flexible cantilever that scans the surface to obtain the topographic image
calculate the total energy ΔETot variation between the initial and current of the 2D MnTe in the first pass. During the second pass, the tip is lifted
configuration. Then, the adhesion force Fadhesion is obtained from the at a constant height to detect the magnetic response by examining the
following expression: cantilever’s phase shift or frequency shift under the influence of the
surface of the sample. Fig. 2b shows the topographic image of 2D MnTe
dΔETot having varying thicknesses of 3, 4, and 7 nm. In the present investiga­
Fadhesion = (2)
dΔr tion, change in phase shift (i.e., the difference in the phase angles be­
tween freely suspended and under magnetic gradient) is used to measure
where Δr is the variation between the initial and current position of the
the magnetic response. The down shift in the scale bar in the cantilever
exfoliated layer. All calculations were made considering spin polariza­
phase (i.e., < 0o) indicates that the magnetic sensor is attracted towards
tion configurations.
the magnetic domains from the sample, Fig. 2c. Nevertheless, electro­
static repulsion is prevalent for the positive values of the phase shifts (for
3. Results and discussion
> 0o) [44]. The phase image corresponding to the topographic image is
shown in Fig. 2c and the respective line profile is plotted in Fig. 2d. It is
The schematic representation of the synthesis of 2D MnTe from the
interesting to observe that a thickness of 4 nm of MnTe sheets exhibits
bulk sample using ultra sonication is shown in Fig. 1a. X-ray diffraction
intense negative phase shift. In contrast, the thicker flake revealed a
patterns and transmission electron microscopy (TEM) images reveal the
positive phase shift (Fig. 2e). Thus, our results indicate that thickness
structural characteristics of bulk and the morphology of exfoliated
variations in the 2D MnTe alter the response towards the magnetic
MnTe, respectively. The diffraction pattern of bulk and 2D MnTe, as
sensor, which supports the previous studies for unraveling magnetic
indexed in Fig. 1b, shows the polycrystalline bulk MnTe with a hexag­
characteristics of MnTe confined to the two dimensions scale limit [28].
onal structure, P63/mmc group symmetry, and having lattice parameters
It has been reported that in exfoliated MnTe sheets, the interplanar ex­
a = b = 4.23 Å, and c = 5.95 Å. The peaks well matched with the JCPDS
change interactions are limited due to weak dipolar interactions. Due to
card no. 03-065-5009 and 01-086-1022. Chemical and crystallographic
a lack of exchange interactions between planes among the magnetic Mn
structural instabilities are caused due to Te/Mn ion migration and Mn
ions, the exfoliated MnTe sheets produce a paramagnetic response,
oxidation, occasionally leading to the formation of MnO and MnTe2
while the weak dipolar interactions result in a random orientation of
impurity phases [33]. Similar peak positions were obtained for the 2D
magnetic moments [45].
MnTe spectra, nevertheless the intensities varied. The chemical
We made a comparative study of the 2D MnTe phase shift results
composition of the exfoliated MnTe was confirmed from the XPS anal­
with a previously reported work of Li, Hai et al. [44] on investigating
ysis shown in Fig. 1c. The results concur with the MnTe thin film values
graphene and MoS2 nanosheets using MFM as shown in Fig. 2f. In the
that have been previously reported [34]. Fig. 1d shows a typical XPS
case of graphene, only the monolayer showed a negative phase shift,
spectrum of Mn 2p and Te 3d core-level, acquired from the MnTe sur­
whereas in MoS2 nanosheets, increasing magnetic response up to a
face. The prominent peak doublets at 641.13 and 653 eV, correspond to
certain thickness of 16 nm was observed, which decreased when the
2p3/2 and 2p1/2 of Mn3+ ions, respectively, in the Mn 2p band and are
thickness was further increased. In the case of MnTe, a similar pattern
indicative of Mn–Te bonding having the spin-orbit splitting energy
was observed, with the negative phase shift appearing at thicknesses up
(ΔSO) 11.87 eV. Regardless of the crystal structure of Mn chalcogenides,
to 4 nm, and beyond it, there was a positive phase shift indicating a
the binding energy value of about 641.13 eV is consistent for divalent
non-magnetic regime. It is to be noted that all the measurements were
manganese bonds to chalcogen atoms [35,36]. The peak at 653 eV
taken using the same tip apex to avoid any variation in the magnetic
resulted most likely from a plasmon loss satellite of the major compo­
responses caused by different tip geometries.
nent of the original Mn 2p3/2 line overlapping with the Mn 2p1/2 peak.
The magnetic response of the cantilever is strongly influenced by the
This effect typically arises in metals from the comparatively high con­
magnetic gradient from the surface, which is validated through the
centration of free carriers (holes) in MnTe. The two small peaks at

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Fig. 2. MFM measurements of 2D MnTe. (a) Schematic of magnetic tip scanning the 2D MnTe in MFM; (b) Topographical image of 2D MnTe sheet showing different
thickness of 3 nm, 4 nm and 7 nm; (c) The corresponding phase image of 2D MnTe sheet at a lift height of 20 nm; (d) & (e) The phase line profiles corresponding to
Fig. 2c; (f) A comparison of 2D MnTe phase shift results with a previously proposed study of graphene and MoS2 [44]; (g) & (h) The topographical and phase image of
2D MnTe sheet at a lift height of 5 nm; and (i) The phase line profile corresponding to Fig. 2h.

scanning at a lower lift height of 5 nm, see Fig. 2g and h. The phase line was used. Fig. 3i and j are the topographical and tunneling AFM (TUNA)
profile is shown in Fig. 2i. Although a sharper contrast has been current maps of 2D MnTe. It is observed that the thicker flakes have a
observed, the results are convoluted with the surface electrostatic higher current value, whereas less thick flakes show lesser current,
response. Therefore, a separate measurement has been carried out to which can be due to the substrate effect on flakes with less thickness
unravel the surface potential using non-magnetic metallic coating of a [49]. I–V curves were plotted against different thicknesses, as shown in
tip apex through kelvin probe force microscopy (KPFM), Fig. 3. The Fig. 3k. It is observed that at a thickness less than 5 nm, the tip and
electrostatic response of the surface is investigated through contact nanoflake surface made non-ohmic point contact in the voltage range
potential difference (CPD, V) (Fig. 3a and b) and adhesion force map ±0.5 V and for a thickness of 10 nm and above, the point contact be­
(nN) as shown in Fig. 3e and f. The CPD values are taken at a finite tween the tip and sample was ohmic. Thus, the conductivity of nano­
vertical separation from the surface, similar to the MFM two-passes sheets changes from different energy band gaps of semiconductors with
mode of operations, while the adhesion force map reflects the surface variations in thickness.
chemistry under direct contact with the metallic tip, similar to force- Density functional theory (DFT) has been used to unravel useful in­
distance spectroscopy [46,47]. There is a direct relation between the sights for the thickness-based analyses of MnTe. Fig. 4 shows that in
adhesion force distribution towards metallic sensors based on charge varying layer numbers, the charges tend to be localized at Mn atoms,
distribution over the MnTe sheets at different thicknesses. The adhesion because of their electron acceptor characteristics, as observed in other
force decreases with the thickness, while contact potential difference similar structures [50]. In the case of a single layer, we observed that the
(CPD) increases, Fig. 3c–g. It indicates the presence of static charges at spin-up and spin-down charges are precisely opposite and localized
higher thickness decreases the contact area of the tip apex or repelling around the interleaved Mn atoms. In these configurations, the
the cantilever [29]. The surface potential map adds the crucial infor­ anti-ferromagnetic arrangement cancels out the spin up and down,
mation of work function (eV) at different thicknesses, revealing a higher resulting in a positive value for ΔE, as seen in Fig. 4d.
concentration of hole carriers at thicker MnTe sheets, Fig. 3d. Thus, Interestingly, as Fig. 4d shows, we observed an antiferro to ferro
MnTe shows the typical screening effect at different thicknesses as other transition from one to two layers (up to four layers), where the system
TMDS where a larger electron accumulation at the thin layer is indicated only exhibits charge for spin-up configurations. The three layers depic­
by the work function values decreasing with thickness [48]. ted in Fig. 4b are comparable to the charge distribution for two and four
To investigate the current (nA) transport in 2D MnTe, C-AFM, which layers. As seen in Fig. 4d, where the ΔE values became again positive, we
is an essential characterization technique for electrical measurements, see a new transition in the system tuning from ferro (four layers) to

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Fig. 3. KPFM and PF QNM measurements of 2D MnTe. (a) and (b) Topographical image and CPD images of 2D MnTe; (c) and (d) The respective graphs of varying
thickness and CPD value as a function of flake thickness (the inset shows the plot between thickness and work function (eV)); (e) and (f) The height sensor and
adhesion images at different thicknesses, respectively; (g) and (h) The graphs showing different thickness and adhesion force response with respect to the varying
thicknesses (inset depicts a plot of thickness (nm) vs adhesion force (nN); (i) Topographic image of 2D MnTe from C-AFM measurements; (j) Image profile of TUNA
current obtained at different thicknesses, and; and (k) The I–V curve obtained by varying DC sample bias ± 0.5 V.

antiferro configuration from five layers till the bulk case. As a result, the compute the adhesion force, we instead take into consideration a few
distribution of charges varies based on the number of layers in relation different configurations in an attempt to gather some information that
to different thicknesses. We observe that beyond a certain thickness could support the experimental observations. The adhesion force is
value, the spin-down charges begin to accumulate significantly on the derived from expression 2, where the total energy was obtained by doing
surface, tending to cancel out the inner charges of the opposite spin. This a single-point calculation for each separation between the exfoliated
explains that from five layers onwards, up to the case of infinite layers layer and the remaining system. The force is obtained by rescaling the
for the bulk, the opposite-spin charges cancel each other out, and the energy equation as a function of separation, with the initial energy set to
system is consistently antiferromagnetic, as observed in the MFM zero. The adhesion force was obtained for one layer extracted from a
experiment. Also, Bulk MnTe is an A-type AFM semiconductor. It is re­ system with eight, twelve, and sixteen layers.
ported that it has parallel spins in each basal plane, which are antipar­ Fig. 5a presents the energy variation behavior, and Fig. 5b shows the
allel to its adjacent layer [51]. Therefore, the net magnetic moment of change in adhesion force as a function of layer distance separation. We
the bi-layer MnTe gets nullified by cancelling the effect of spins from observe a small variation between eight and twelve layers, where the
each layer. Thus, the net magnetic moment of the MnTe varies adhesion force is nearly constant throughout all distances examined.
depending on the number of MnTe layers, showing the trend of alternate However, we found that the adhesion force decreases as the number of
negative-positive-negative. layers reaches sixteen. We observed this behavior for adhesion as a
Since it is unambiguously impossible to precisely replicate the same function of thickness in the experimental measurements shown in the
scale thickness sizes of about 10 nm as done experimentally, in order to inset of Fig. 3h. As discussed in the experimental section, this behavior

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S. Slathia et al. Materials Today Chemistry 38 (2024) 102134

Fig. 4. Results from DFT simulations for 2D-MnTe with different layers. (a) to (c) The spin distribution for one, three, and six layers of MnTe, and; and (d) The energy
variation from one layer to bulk. The Mn and Te atoms are indicated by purple and grey colors, respectively. Spin-up is displayed in red color and spin-down is
displayed in blue color.

layers, producing different adhesion forces. Thus, our DFT results are
consistent with the proposed hypothesis from the experimental analysis
discussed above for the 2D MnTe structures. Another aspect is as the
number of layers increases, the structure becomes stiffer, also contrib­
uting to a decrease in the adhesion force. We would like to stress that,
although several cases of similar behaviors are reported in the literature,
this is not the general behavior of 2D magnetic systems but just the re­
sults of each material’s specific electronic structure and/or spin popu­
lation balance.

4. Conclusions

In summary, our investigations into the magnetic transition taking

place from bulk to 2D MnTe have revealed an intricate relationship
between dimensionality and magnetism which was also confirmed using
DFT simulations. As the thickness of the 2D MnTe flakes increased, a
positive phase shift was observed, that indicates the MFM probe expe­
rienced a force of repulsion from the sample surface. Therefore, the less
Fig. 5. (a) The energy variation as a function of the distance between the thick flakes show more pronounced magnetic behavior than the thicker
exfoliated layer from the initial and current position; and (b) Change in adhe­ ones. The surface potential mapping, in conjunction with adhesion
sion force calculated by expression 2 as a function of the distance. force, reveals the different distribution of charge carriers at variable
thicknesses owing to the screening effect. In C-AFM measurements, it is
where the adhesion force decreases as a function of layer number is due observed that at a thickness of less than 5 nm, the tip and nanoflake
to the charge rearrangement for different layer number and size, as we surface made non-ohmic point contact in the voltage range ±0.5 V and
see in Fig. 4a–c. This causes different charge interactions between for a thickness of 10 nm, the point contact between the tip and sample

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was ohmic. The DFT calculations showed that the magnetic transition [5] S. Manzeli, D. Ovchinnikov, D. Pasquier, O.V. Yazyev, A. Kis, 2D transition metal
dichalcogenides, Nat. Rev. Mater. 2 (2017) 17033, https://doi.org/10.1038/
occurred due to the change in the spin direction/polarizations of the
natrevmats.2017.33.
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