NANOMATERIALS

- Abhinav Shete
UG (2nd Year)
 STRUCTURE OF
• 𝑀𝑜𝑆 is characterized by a layered structure across all its forms, wherein a plane of
molybdenum atoms is situated between planes of sulfide ions, constituting a
monolayer of 𝑀𝑜𝑆 . The bulk configuration of 𝑀𝑜𝑆 comprises stacked monolayers
held together by weak van der Waals interactions.
• Crystalline 𝑀𝑜𝑆 exhibits two distinct phases: 2H-𝑀𝑜𝑆 and 3R-𝑀𝑜𝑆 , denoting
hexagonal and rhombohedral symmetry, respectively. In both phases, each
molybdenum atom occupies the center of a trigonal prismatic coordination sphere
and forms covalent bonds with six sulfide ions. The sulfur atoms, exhibiting
pyramidal coordination, are bonded to three molybdenum atoms. Notably, both the
2H and 3R phases of 𝑀𝑜𝑆 display semiconducting properties.
Ball-and-stick model of the part of the crystal structure of molybdenite, 𝑀𝑜𝑆 .
 PROPERTIES OF
• 2H 𝑀𝑜𝑆 , in its bulk form, is characterized as an indirect band gap semiconductor
with an energy gap of approximately 1.2 eV. The material's unique layered structure
lends itself to a variety of applications, including photocatalysis, solid-state
lubrication, hydrogen storage, and utilization in lithium-ion batteries. Composed of
covalently bonded S–Mo–S planes, the bulk 2H 𝑀𝑜𝑆 forms 2D layers held together
by weak van der Waals forces, allowing for exfoliation into minimum resolvable
monolayers through externally applied forces. These monolayers exhibit intriguing
properties, such as enhanced charge carrier mobility near highly permittive
boundaries, distinct mechanical behavior along the plane compared to the bulk, and
a high surface-to-volume ratio advantageous for sensing applications.
• The band gap of 2D 𝑀𝑜𝑆 flakes increases with decreasing crystal thickness,
reaching approximately 1.9 eV for a monolayer. This reduction in thickness also
induces a transition from an indirect to a direct band gap due to the hybridization
between 𝑝 orbitals of sulfur atoms and d orbitals of molybdenum atoms. This shift
leads to a pronounced photoluminescence (PL) effect in monolayer 𝑀𝑜𝑆 .
• Recent research by Stengl and Henych has highlighted a novel optical phenomenon
where small lateral dimensions of 2D 𝑀𝑜𝑆 nanoflakes produce strong luminescence
under UV light. This luminescence is attributed to the quantum confinement effect
across the 2D planes. These distinctive properties make 2D 𝑀𝑜𝑆 flakes highly
appealing for the development of high-performance optical devices, including
optical sensors, modulators, solar cells, and light-emitting diodes (LEDs).
 BRILLOUIN ZONE
• As an approximate model, assume a one-dimensional crystal where
0, 0 ≤ 𝑥 ≤ 𝑎
𝑉 𝑥 ={
𝑉 , −𝑎 ≤ 𝑥 ≤ 0
and where 𝑎 = 𝑎 + 𝑎 is the period of the lattice. This is known as the Kronig–Penney
model.
We can write down the wavefunction in the following period, 𝑎 ≤ 𝑥 ≤ 𝑎 + 𝑎, as
𝜓 𝑥 = 𝐴𝑒 + 𝐵𝑒 𝑒 , 𝑎 ≤ 𝑥 ≤ 𝑎,

= 𝐷𝑒 + 𝐵𝑒 𝑒 , 𝑎 ≤ 𝑥 ≤ 𝑎 + 𝑎.
Solving the Schrodinger’ equation in this case gives the following relation:
1
𝑘= 𝑐𝑜𝑠 𝑟 𝐸
𝑎
Since cosine is an even function, −k will also be a solution. By increasing E by a small
amount and checking the value of r (E), we can generate the plot of allowed and
unallowed energy bands.
The various sections of wavenumber space are divided into what are called Brillouin
zones, with the range
𝜋 𝜋
− ≤𝑘≤
𝑎 𝑎
denoting the important first Brillouin zone.
Within the Brillouin zone, a constant-energy surface represents the loci of all the
𝑘 −points (that is, all the electron momentum values) that have the same energy.
 ABSORPTION SPECTRA
The excitonic peaks observed at 670 nm and
610 nm in 2D 𝑀𝑜𝑆 nanosheets with substantial
lateral dimensions are attributed to the K point
of the Brillouin zone. The peaks around ∼400
nm and 450 nm are associated with direct band
edge recombination. Upon subjecting the
solution to 5 hours of sonication, a slight blue
shift is noted in the optical absorbance peaks
at 400 nm and 450 nm. Additionally, after
filtration, the distinct peaks at 610 nm and 670
nm, characteristic of large 𝑀𝑜𝑆 nanosheets,
vanish, indicating the complete removal of 2D
nanosheets from the solution. UV-vis absorption spectra of MoS2 solution with
large-sized MoS2 nanosheets (red line), small-sized
MoS2 nanosheets (black line) and MoS2 QDs (blue
line), respectively.
• Simultaneously, the optical absorption of quantum dots (QDs) shows a noticeable
blue-shift compared to the nanosheets, a phenomenon attributed to the quantum size
effect in QDs.
• For 𝑀𝑜𝑆 quantum dots, the quantum size effect causes the energy levels associated
with electronic transitions to be quantized. The quantization of energy levels affects
the absorption and emission of photons.
• In 𝑀𝑜𝑆 QDs, the confined charge carriers have quantized energy levels, and
transitions between these levels result in the absorption or emission of photons.
• The quantized energy levels lead to transitions occurring at higher energies,
corresponding to shorter wavelengths in the electromagnetic spectrum.
• Since shorter wavelengths are associated with higher energy, the observed shift is
towards the blue region of the spectrum, hence termed a "blue shift."
 PHOTOLUMINESCENCE OF
• In semiconductors, the destiny of photogenerated electron-hole pairs is influenced
by traps and recombination processes.
• Nanoclusters, due to a significant number of surface atoms, exhibit a preponderance
of dangling bonds and defects, leading to the formation of surface states.
• Adsorbed impurities can introduce additional surface states, acting as traps or
recombination sites.
• Unpurified 𝑀𝑜𝑆 clusters showed photoluminescence dominated by surface
recombination, with PL observed at considerably longer wavelengths than
absorption thresholds.
• Surface states, dangling bonds, and defects contribute to trapping or recombination
of electron-hole pairs.
• Chromatographic purification of 𝑀𝑜𝑆 clusters has
significantly improved the quality of PL spectra.
• Purification has enabled the observation of both
band-edge (direct) and surface electron-hole
recombination.
• Essentially, no PL is expected or observed at the
smallest, or indirect, gap of 𝑀𝑜𝑆 .
• Excitation at 450 nm results in a single PL peak at 520
nm, associated with surface recombination.
• Excitation at 348 nm leads to a PL spectrum with two Optical absorption and PL spectra of 3.0
nm MoS2 clusters. The two PL spectra
overlapping peaks. were measured for excitation
wavelengths of 450 and 348 nm. The 348
• The more intense peak at 420 nm corresponds to nm PL spectrum is decomposed into its
two components.
direct band (K) edge recombination.
• Decomposition of the PL spectrum reveals a second,
less intense peak at around 520 nm, associated with
surface states recombination.
• The PL spectrum for 450 nm excitation and the less
intense peak at 520 nm for 348 nm excitation are both
associated with surface states recombination.
• Earlier measurements on unpurified samples showed
intense luminescence primarily due to surface
recombination.

Optical absorption and PL spectra of 3.0

nm MoS2 clusters. The two PL spectra
were measured for excitation
wavelengths of 450 and 348 nm. The 348
nm PL spectrum is decomposed into its
two components.
 BAND DIAGRAM
• The 𝑀𝑜𝑆 monolayer is a direct band gap
semiconductor with a maximum of the valence and
minimum of the conduction band (VBMAX/CBMIN)
located at the Kk-point of the BZ. The direct gap is
1.79 eV and the indirect gap is 2.03 eV
• Bulk MoS2 is an indirect band gap semiconductor
with direct K → K (1.74 eV) and indirect Γ → 𝐾 (0.65
eV) gaps.
• VBMAX and CBMIN at the Kk-point are located 0.19
eV above and 0.05 eV below the energies at the Γ The band structure of the electron levels for a
single MoS2 monolayer (red lines—valence
and Qk-points, respectively. band; blue lines—conduction band). The
green lines show the top (bottom) valence
(conduction) bands in bulk MoS2.
 EXCITON AND TRION
• An electron and an electron hole that are attracted to each other by the Coulomb
force can form a bound state called an exciton. It is an electrically neutral
quasiparticle that exists mainly in condensed matter, including insulators,
semiconductors, some metals, but also in certain atoms, molecules and liquids. The
exciton is regarded as an elementary excitation that can transport energy without
transporting net electric charge.
• A trion is a localized excitation which consists of three charged particles. A negative
trion consists of two electrons and one hole and a positive trion consists of two holes
and one electron. The trion itself is a quasiparticle and is somewhat similar to an
exciton, which is a complex of one electron and one hole.
 INDIRECT-TO-DIRECT-GAP
TRANSITION
• In two-dimensional (2D) materials, interlayer coupling and interaction, determined
by the number of layers and the stacking configuration, are crucially important to
govern the crystal symmetry and the electron Coulomb interactions, resulting in
novel quantum phenomena.
• Bilayer transition metal dichalcogenides (TMDs) have been predicted to be a 2D
system for exploring exotic physical properties dependent on interlayer coupling
through modulating the interlayer distance and stacking order.
• The twisted bilayer 𝑀𝑜𝑆 structures exhibit a unique three-fold symmetric flower-like
shape.
• These artificial twisted bilayer 𝑀𝑜𝑆 flowers display strong direct bandgap-like
photoluminescence (PL) emission and intense monolayer-like optical properties,
especially away from the flower center. In contrast, MoS2 flowers with no twist (0°) or
maximum twist (60°) retain an indirect gap feature with weakened PL intensity.
• The transition from indirect to direct bandgap in the twisted 𝑀𝑜𝑆 flowers is
attributed to the expanded interlayer spacing caused by the spiral growth of the
second flower-like layer with a twist relative to the first layer. This expanded
interlayer distance leads to interlayer decoupling, a decrease in effective masses of
electrons and holes, and consequently, an indirect-to-direct gap transition. Density
functional theory (DFT) calculations support the experimental findings, explaining
the enhanced PL intensity and single-layer behaviors in twisted MoS2 flower
patterns.
• A larger interlayer spacing results in a more delocalized nature of electrons between
layers. This delocalization reduces the effective mass of electrons. The effective mass
is essentially a measure of how much the electron behaves like a free electron in a
vacuum.
• A reduced effective mass means that electrons respond more readily to external
forces, making them easier to accelerate and move.
• In the context of excitons and trions, a lower effective mass makes it easier for an
electron to combine with a hole to form an exciton. However, it also means that the
resulting charged exciton (trion) is less stable because the electron can move more
freely and be easily separated from the hole.
• The increased mobility of the electron can lead to a higher probability of the trion
dissociating into a free electron and hole, reducing the charged exciton population.
• The interlayer spacing in materials affects the interactions between adjacent layers
and the confinement of charge carriers.
• An expanded interlayer spacing results in weaker interactions between layers,
leading to a more delocalized behavior of charge carriers (electrons and holes).
• In the context of excitons, the increased interlayer spacing may contribute to a larger
spatial extent of the exciton wavefunction.
• A larger spatial extent allows for a greater probability of electron-hole pairs being
separated, resulting in an increased density of neutral excitons.
• The neutral excitons, not having an additional charge, are more stable than charged
excitons (trions) and are less prone to dissociation.
• In a material with a direct band gap, the minimum energy required for an electron to
transition from the valence band to the conduction band occurs with no change in
momentum. This means that the electron can absorb or emit a photon and move
directly between the bands without needing a change in its momentum.
• In contrast, in a material with an indirect band gap, such transitions involve a change
in both energy and momentum, often requiring the participation of a phonon.
• In the presence of spatially separated neutral excitons and weakened Coulomb
binding, the inhibition for direct transitions between the valence and conduction
bands is reduced.
• The weakened Coulomb binding means that the electron and hole are not strongly
bound, making it easier for the electron to transition directly to the conduction band
without immediate recombination.
• The reduction in the inhibition for direct transitions, facilitated by the increased
population of spatially separated neutral excitons and weakened Coulomb binding,
contributes to the material transitioning from an indirect band gap to a direct band
gap.
• The material becomes more favorable for direct electronic transitions, where
electrons can move to the conduction band without a simultaneous change in
momentum.
 REFERENCES
• https://pubs.rsc.org/en/content/articlelanding/2015/RA/C5RA19201C#cit23
• https://pubs.acs.org/doi/10.1021/nn4041987
• https://en.wikipedia.org/wiki
• J.P. Wilcoxon, P.P. Newcomer, G.A. Samara, Synthesis and optical properties of MoS2
and isomorphous nanoclusters in the quantum confinement regime, J. Appl. Phys. 81
(1997) 7934–7944.
• https://www.sciencedirect.com/science/article/pii/S0038109812000889#br000055
• https://pubs.rsc.org/en/content/articlelanding/2023/nr/d3nr00477e#:~:text=The%2
0indirect%2Dto%2Ddirect%2D,effective%20mass%20of%20the%20electrons.
15-01-2024