Large Optical Kerr Nonlinearity in Titanium

Carbide MXene-VS2 Hybrid

Vinod Kumar,† Aditya Sharma,‡ Pratap Mane,¶ Brahmananda Chakraborty,§,∥

Chandra S. Rout,⊥ and K. V. Adarsh∗,†

†Department of Physics, Indian Institute of Science Education and Research, Bhopal

462066, India
‡Centre for Nano and Material Sciences, Jain (Deemed-to-be University), Jain Global
Campus, Kanakapura Road, Bangalore 562112, India
¶Seismology Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India
§High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research
Centre, Trombay, Mumbai 400085, India
∥Homi Bhabha National Institute, Mumbai 400085, India
⊥Centre for Nano and Material Science, Jain University, Jain global campus, Jakkasandra,
Ramanagaram, Bangalore 562112 India

E-mail: adarsh@iiserb.ac.in

Abstract
Nonlinear optical responses or Kerr nonlinearity of materials are of significant importance
in developing modern photonic and optoelectronic devices. Optical Kerr nonlinearity induced
by strong optical excitation in hybrid material can offer a larger amplitude, potentially helpful
in optical switching/limiting, all-optical signal processing, and quantum information. Here, we
demonstrate a remarkable, manifold increase in the magnitude of the third-order nonlinear optical
response (Kerr nonlinearity) of the donor-acceptor Ti3 C2 Tx (MXene)-VS2 hybrid in the strong
coupling regime compared to control systems in the femtosecond domain. Interestingly, we ob-
served a transition from reverse saturable absorption to saturable absorption and a change from
self-focusing to self-defocusing in the nonlinear optical behavior when moving from the MXene-
VS2 hybrid to control systems. Our four-level rate-equation model encapsulates the underlying
physics governing the unprecedented ultrafast nonlinear optical response observed in hybrid. The
enhanced Kerr nonlinearity of the hybrid is ascribed to charge transfer between MXene and VS2 .
Besides, First-principles calculations and the Bader charge study unveil strong electronic coupling
within the hybrid system, where the transfer of electrons from MXene to VS2 corroborated through
measurements of the steady-state and time-resolved photoluminescence. Finally, benefitting from
the high third-order nonlinear response, we present a propitious application of MXene-VS2 hybrid

1
 as an ultrafast optical limiter based on liquid cells for optoelectronic sensors with an onset thresh-
old of 0.6 mJ cm−2 and differential limiting transmittance of 0.46.
KEYWORDS: MXene-VS2 hybrid, charge transfer, saturable absorption, reverse saturable ab-
sorption, self-focusing, self-defocusing, optical limiter
INTRODUCTION
Nonlinear optics has emerged as an extensive area of
research in modern science since the innovation of the
laser in the 1960s. The nonlinear optical interaction
of light with the material itself guides several fasci-
nating scientific phenomena, such as optical switch-
ing and limiting, 1,2 harmonic generation in optically
active materials, 3 optical parametric oscillation, 4 op-
tical data storage, 5 and quantum information pro-
cessing. 6 In addition, the nonlinear optical implica-
tions also guide many worthwhile functional appli-
cations, such as super-continuum generation through
photonic crystal, 7 frequency combs generation in op-
tical cavities, 8 laser-based gas sensing, 9 molecular fin-
gerprinting, 10 and telecommunications through opti-
cal fibres. 11 However, despite extensive endeavor and
several years of progress in this arena, third-order
nonlinear optics for photonic devices have yet to be
understood fully due to the deficiency of materials
with extremely large nonlinear responses. It is al-
ways desirable to have materials with large third-
order optical response (Kerr-nonlinearity) at low op-
tical power, inherently fast response time, and an
extended dynamic range to develop next-generation
optical devices. 12,13 The Kerr-nonlinearity is repre-
sented as changes in the imaginary and real parts of
the nonlinear susceptibility and embodies nonlinear
absorption and refraction, respectively. The former
resembles intensity-dependent changes in material ab-
sorption, and the latter corresponds to the variation in
the phase of propagating waves within the material,
which can lead to either positive nonlinearity (self-
focusing) or negative nonlinearity (self-defocusing) of
the optical field. 14 Hence, the quest for materials with
large Kerr nonlinearity is one of the main goals of
nonlinear optics. However, traditional materials of-
ten exhibit weak nonlinear optical responses, even
in intense optical fields. Therefore, such constraints
call for alternative approaches to enhance the nonlin-
ear responses of prevailing materials. One promising
strategy is to acquire large ultrafast Kerr nonlinear-
ity through photoinduced charge transfer of a donor-
acceptor pair hybrid at the nanoscale interface. Also,
recent studies ascertained that the interactions on a
nanoscopic scale at interfaces can significantly mod-
ify the optoelectronic and chemical characteristics of
a hybrid system. 15–17 For instance, we have recently
reported the enhanced nonlinear optical response in
VSe2 -rGO 18 and SWCNT-VSe2 nanohybrid, 19 which
are approximately 10 times larger than their con-
2
stituent systems. Besides, several other hybrids
also showed an improved nonlinear optical response,
such as MoSe2 /GO, 20 hybrids of gold nanoparticles
with CdSe/WS2 and Ge2 4Se7 6, 21–23 Graphene/MoS2
heterostructure 24 and inorganic-organic halide per-
ovskites, 25 etc. However, the majority of these hy-
brids display nonlinear response in the picosecond and
nanosecond pulse regimes with slow transfer rates. So,
finding appropriate donor-acceptor materials that can
operate in femtosecond pulse regimes with fast charge
transfer rates is a fundamental task.
To address this emerging challenge, we pro-
pose the hybrid of Ti3 C2 Tx (MXene) and VS2 ,
one of the transition metal dichalcogenides (TMDs).
Meanwhile, MXenes represent a category of ma-
terials consisting of metal carbides and metal ni-
trides characterized by their two-dimensional (2D)
layered structure. 26 The standard formula for MX-
ene is Mn+1 Xn Tx (n = 1, 2, 3). Where M stands for
an early transition metal, X denotes either nitrogen or
carbon, and Tx is attributed to surface terminations
such as -F, -OH, or -O. MXenes are generally pro-
duced by selectively etching the intermediate A layers
from a MAX phase (where A belongs to group IIIA
or IVA elements). This process involves using fluorine
etchants, such as lithium fluoride (LiF) or hydrofluo-
ric acid (HF). 27 On the other hand, among the TMDs,
a highly abundant and low-cost VS2 bids an excellent
prospect to develop as a better-performance nonlinear
optical material for photonics owing to its substantial
surface area featuring extremely active sites at the
edges, along with remarkable mechanical strength of
unique 2D layered structure. 28,29 Individually, MX-
enes and VS2 have device-beneficial nonlinear optical
properties with lower magnitudes. 30,31 Incorporating
VS2 with MXene thus could be an effective strategy to
improve the Kerr nonlinearity or device performance
further. Recent studies demonstrated efficient charge
transfer in MXene-VS2 hybrid, highlighting their use-
fulness in energy storage devices. 29 So far, active con-
trol of optical Kerr nonlinearity mediated by charge
transfer remains largely unexplored. In this article,
we illustrate an unprecedented or manifold increase in
the magnitude of the absorptive and refractive parts
of the ultrafast third-order nonlinear optical response
of the MXene-VS2 hybrid at 800 nm excitation wave-
length compared to control systems in the femtosec-
ond regime. For example, we demonstrate a large
reverse saturable absorption (RSA) coefficient (β) of
(150 ± 16) × 10−3 cm GW−1 and the nonlinear refrac-
tion (n2 ) of (94 ± 9) × 10−6 cm2 GW−1 , these findings
are at least one order of magnitude greater than those
observed in the control systems. This strongly en-
hanced Kerr nonlinearity in the hybrid is ascribed to
the charge transfer phenomenon between MXene and
VS2 . Notably, we have observed a transition from
RSA to saturable absorption (SA) in the imaginary
part and a change from self-focusing to self-defocusing
in the real part of nonlinear optical behavior when
moving from hybrid to control systems. Our four-level
rate-equation model effectively encapsulates the un-
derlying physics responsible for the unprecedented ul-
trafast nonlinear optical response observed in the hy-
brid system. First-principles calculations and Bader
charge study unveiled a strong electronic coupling in
the hybrid where electrons are transferred from MX-
ene to VS2 . Further, this charge transfer is corrobo-
rated through the measurements of steady-state and
time-resolved photoluminescence (PL) with a trans-
fer rate of (7.3 ± 0.5) × 108 s−1 . By utilizing the
strong RSA of our hybrid system, we have success-
fully fabricated a high-performance ultrafast optical
limiter based on liquid cells with imperative charac-
teristic device parameters, including an onset thresh-
old of 0.6 mJ cm−2 and a minimal limiting differential
transmittance of 0.46. These device performance pa-
rameters surpass several benchmark optical limiters
observed in the femtosecond domain.
RESULTS AND DISCUSSION
Figure 1 displays the schematic of the synthesis
procedure of control VS2 sheets and strongly cou-
pled Ti3 C2 Tx (MXene)-VS2 hybrid by hydrothermal
Figure 1: Schematic showing the details of sample preparation of control VS2 sheets and Ti3 C2 Tx
(MXene)-VS2 hybrids by hydrothermal method.
3
methods, and the details are presented in description
S1 in the Supporting Information.
High magnification field emission scanning elec-
tron microscopy (FESEM) measurements investigated
the morphological description of MXene, VS2 , and
MXene-VS2 hybrid. Figure 2a offers an understand-
ing of the uniform layered, sheet-like morphology of
VS2 from a particular angle, indicating layer-by-layer
growth in the range of 0.2 to 0.5 µm in size. No-
tably, the gaps observed between the layers indicate
the presence of substantial ion transport sites. Fig-
ure 2b displays the FESEM image of MXene flakes
showing uniformly etched layers, indicating substan-
tial active sites to hold ions. Figure 2c illustrates
how the MXene-VS2 hybrid exhibits the crumbling
of VS2 into small sheets that assemble on or in be-
tween the MXene flakes to inhibit restacking in con-
trast to the control VS2 sheets. The Powder X-ray
diffraction (PXRD) pattern of the hybrid and con-
trols are displayed in Figure S1. The PXRD pat-
tern of the MXene exhibits a distinct peak at 8.83◦
correlates with the (002) plane. The observed shift
of this diffraction peak towards lower angles signifies
the successful etching of the Al layer from Ti3 AlC2
(MAX). 29,30 Moreover, the PXRD pattern of VS2
in Figure S1 illustrates the hexagonal structure with
the P 3m1 space group. The distinctive peaks at
15.2, 35.8, 45.4, 57.3, 58.2, and 69.4◦ resemble (001),
(101), (102), (110), (103), and (201) lattice planes, re-
spectively, which completely match with the JCPDS
card no. 01-89-1640. 32 Additionally, the PXRD pat-
tern of the MXene-VS2 hybrid depicts the dominant
characteristic (002) peak of MXene. Notably, this
peak has shifted towards the lower angle from 8.9◦ to
Figure 2: High magnification FESEM images of (a) etched Ti3 C2 Tx (MXene) flakes (b) VS2 sheets (c)
MXene-VS2 hybrid (d) FT-IR spectrum of VS2 , MXene, and MXene-VS2 hybrid.
6.7◦ , owing to the widening of the interlayer spacing
due to the deposition of VS2 sheets either between or
on top of the MXene flakes, effectively inhibiting the
tendency for restacking. Nevertheless, the exposure
of a wide peak near 27.9◦ in the MXene-VS2 hybrid
because of the expanded interlayer spacing of con-
trol VS2 . 33 Figure 2d displays the FT-IR spectrum
of control VS2 , MXene, and MXene-VS2 hybrid. The
V4+ oxidation state is corroborated by S−V−S and
V=S peaks at 674 and 976 cm−1 in control VS2 , re-
spectively. The lack of prominent peaks of functional
groups sustains the purity of MXene. 34 Additionally,
the C−F bond in MXene exhibits a modest character-
istic stretched band vibration at a wavelength of 1232
cm−1 , further supporting its low fluorine concentra-
tion. 34 Due to the presence of MXene in the hybrid,
there is a change in bending vibrations from control
VS2 to hybrids, from 674 to 520 cm−1 for the S−V−S
band and from 976 to 988 cm−1 for the V=S band.
As a result, the S−V−S and V=S bands have widened
in hybrids, indicating that MXene functional groups
have attached to the doubly bridged (S2− ) doubly
bonded (S2− ) species. 32
Figure 3a (top panel) shows the Raman spectrum
of the MXene having characteristics peaks at 153,
201, 277, 406, 510, and 623 cm−1 . The intense peak
4
at 153 cm−1 might ascribed to the existence of oxy-
gen species in MXene. The less prominent peaks at
201, 277, 406, 510, and 623 cm−1 indicate the forma-
tion of MXene. The energy-gap modes of the in-plane
Ti−OH and Ti−O surface functional groups existing
in the MXene 35 are ascribed to the peak at 406 cm−1 .
Figure 3a (middle panel) displays the Raman spec-
trum of control VS2 , showing the characteristic peaks
at 140, 189, 282, 405, 690, and 990 cm−1 . The charac-
teristic peaks at 282 and 405 cm−1 are ascribed to the
in-plane E12g and out-of-plane A1g vibration modes,
respectively, emerging from S atoms connected to V
atoms. 36 Figure 3a (bottom panel) shows the Raman
spectrum of the MXene-VS2 hybrid, where the char-
acteristic peaks of both control materials are clearly
discernible within the hybrid. Strikingly, we find that
the characteristic peak at 510 cm−1 in MXene is red-
shifted to 525 cm−1 in the hybrid, indicating a strong
electronic coupling of VS2 with MXene. Figure 3b
presents the UV-Vis (200-800 nm) optical absorption
spectra of MXene, VS2 , and MXene-VS2 hybrid. As
shown, MXene absorbs a broad spectrum from 200
to 800 nm with a characteristic absorption peak near
200 nm, which is consistent with previous reports. 31
Moreover, VS2 displays an absorption onset at 500
nm with two distinct peaks at 262 and 350 nm in the
Figure 3: Raman spectrum of (a) MXene (top), VS2 (middle) and MXene-VS2 hybrid (bottom) (b)
Ground state optical absorption spectrum of MXene, VS2 and MXene-VS2 hybrid. (c) PL spectra
of MXene and MXene-VS2 hybrid. The PL intensity experiences a significant reduction and exhibits
a redshift of 13 nm in the hybrid compared to MXene, suggesting the occurrence of efficient charge
transfer between MXene and VS2 .

UV-Vis region. The absorption spectrum of the hy-
brid can be examined as a combination of signals from
each control system; the intensity of the characteris-
tic absorption signal significantly weakened and red-
shifted in the MXene-VS2 hybrid compared to con-
trol VS2 (see Figure S2), signifying strong coupling
between MXene and VS2 . Further, we provide the
results of the photoluminescence (PL) measurements
of the MXene and MXene-VS2 hybrid shown in Fig-
ure 3c to explore the charge transfer process between
MXene and VS2 . The MXene shows high photolumi-
nescence with a broad peak centered at 480 nm under
360 nm excitation. Strikingly, the PL intensity experi-
ences a substantial reduction and a noticeable redshift
by 13 nm in the hybrid compared to MXene, indicat-
ing close integration and interaction between the MX-
ene and VS2 , suggesting an efficient charge transfer.
Because the electronic wavefunctions of MXene and
VS2 overlap, the potential barrier is made sufficiently
low to allow for charge transfer during photoexcita-
tion. The red shifting and quenching of the PL peak
are caused by the changing density of states brought
about by mixing electronic states at the interface. 37
It has been shown that charge transfer interac-
tions at the interfaces significantly change the opto-
electronic and chemical characteristics of the hybrid.
For instance, when the VSe2 is hybridized with the re-
duced graphene oxide (rGO) 18 and single-wall carbon
nanotube (SWCNT), 19 an amazing enhancement in
the nonlinear optical response is produced. Similarly,
large improvements in third-order nonlinearity have
also been noted in hybrids such as MoSe2 /graphene
oxide 20 , AuNP/Ge24 Se76 , 23 Graphene/MoS2 , 24 and
Graphene/WX2 (X = S, Se, and Te) 38 systems.
Therefore, the charge transfer process in MXene-VS2
hybrid could be expected to play a crucial role in en-
hancing the ultrafast third-order nonlinear optical re-
sponse. To investigate the third-order nonlinear op-
tical response, we have employed the open and close
aperture Z-scan method with a 120-femtosecond laser
pulse at 800 nm excitation. All the samples have been
diluted in distilled water, having a linear transmit-
tance of 60%.
The open aperture Z-scan symmetric transmission
results of the MXene-VS2 hybrid and controls are dis-
played in Figure 4a at a peak intensity of 90 GW

5
Figure 4: The normalized transmittance measured as a function of position under 800 nm excitations
with a moderate peak intensity of 90 GW cm−2 . (a) Open aperture (c) Close aperture Z-scan results
of MXene, VS2 , and MXene-VS2 . (b) Schematic diagram of a four-level model for the charge transfer
mechanism. (d) Variation of the Imaginary, and (e) Real part of the nonlinear susceptibility with the
input intensity. (f) The decay lifetimes of MXene and hybrid were determined through time-resolved
PL spectroscopy.

cm−2 . Under this moderate peak intensity, the Z-scan
peak-shape result of the hybrid possesses a very large
RSA, which contrasts sharply with the SA of the con-
trol systems due to charge transfer. The observed SA
behaviour of MXene can be explained by considering
a plasmon-induced augmentation in the ground state
absorption at 800 nm. In MXenes, oscillations of the
free carrier are more advantageous at higher wave-
lengths >1130 nm, 39 and the depletion of the ground
state population is more prominent at 800 nm, leading
to an increase in nonlinear transmittance at higher in-
tensity and results in SA 39 (absorption progress is dis-
played in Figure S6a). The SA response exhibited by
the control VS2 can be explained through the modu-
lation of its band structure induced by the presence of
atomic deficiencies involving either vanadium (V) or
sulphur (S) elements and the coexistence of both semi-
conducting and metallic states within the layered two-
dimensional (2D) materials 40,41 (see description S6).
As well, in both cases, the peak intensity is inadequate
to produce the excited state absorption cross-section
(σES ) surpassing the ground state absorption cross-
section (σGS ) (see Table 1), which supports the SA
of control systems. 18,19,42 Conversely, the giant un-
precedented RSA of hybrid is ascribed to the charge
transfer from MXene to VS2 . To explain the RSA
phenomenon in the MXene-VS2 hybrid, we have de-
signed a minimal four-level model depicted in Figure
4b. Our model’s phenomenology comprises a signif-
icant optical transition in MXene, a significant opti-
cal transition in VS2 , and the charge transfer process
from the photo-excited state in MXene to the ground
state in VS2 . Upon photoexcitation, donor MXene ex-
periences single photon absorption and transfers the
excited electrons to the V0 state of the acceptor VS2 .
From V0 , it absorbs additional photons and drives to
the excited state Vn ; such a charge transfer process
results in the RSA (detail in description S7). The
measured open aperture Z-scan experimental data are
fitted with nonlinear light propagation equations 19,20
(see description S3), and extracted RSA coefficient
(β) and saturation intensity (Is ) are tabulated in Ta-
ble 2. It is evident from this observation that the
β of (150 ± 16)× 10−3 cm GW−1 for the hybrid
is 30 times and approximately 19 times higher than
the corresponding value for MXene and VS2 , respec-
tively. Our intensity-dependent Z-scan measurements
and σES display a monotonic rise with peak intensity,
adding to the experimental support for the RSA of
the hybrid (see Table 1 and Figure S4c). Addition-
ally, it reinforces the idea that charge transfer occurs
within the MXene-VS2 hybrid.
The sign and value of the nonlinear refractive in-
dex (n2 ) have been estimated using the closed aper-
ture Z-scan technique by putting an aperture before
the detector so that transmission decreases to 1/3 of

6
Table 1: The calculated σGS and σES for MXene, VS2 , and MXene-VS2 hybrid under 800 nm excitation.

Sample Intensity σGS σES

GW cm−2 (10−20 cm2 ) (10−20 cm2 )
MXene 30 1.5 ± 0.4 0.7 ± 0.2
90 2.2 ± 0.5 1.1 ± 0.3
150 3.5 ± 0.7 1.6 ± 0.5
VS2 30 1.0 ± 0.2 0.5 ± 0.1
90 1.6 ± 0.4 0.9 ± 0.3
150 2.4 ± 0.6 1.5 ± 0.6
MXene-VS2 30 2.5 ± 0.8 6.2 ± 1.0
90 3.8 ± 1.0 8.6 ± 1.5
150 5.4 ± 1.6 15.0 ± 3.0

the incident intensity of the laser beam. 19 Figure 4c The optical nonlinear susceptibility of the materials
depicts the close aperture Z-scan result of the hy- is expressed as
brid and control systems at a pump intensity of 90
(3) (3)
GW cm−2 . The nonlinear refraction traces for Con- χ(3) = χR + ιχI (1)
trol MXene and VS2 display an initial peak in prefo-
(3) (3)
cal transmittance followed by a subsequent valley in Imaginary parts (χI ) and Real (χR ) of optical non-
post-focal transmittance, constituting the character- linear susceptibility (χ(3) ) are associated with the β
istic Z-scan signature of a negative refractive index and n2 respectively, which are expressed as 46
or self-defocusing nature of the material. 18,43 These
negative nonlinear refractive index for MXene and (3) c2 n20 m
χI (esu) = 2
β( ) (2)
VS2 can be ascribed to bound carriers induced by 240π ω W
nonresonant excitation since the thermal effects are (3) cn20 m2
negligible in femtosecond excitation. 43 Conversely, we χR (esu) = n 2 ( ) (3)
120π 2 W
observe a crossover, i.e., an initial valley in prefo-
cal transmittance followed by a subsequent peak in where c stands for the speed of light, n0 represents
post-focal transmittance, constituting the character- the linear refractive index, and ω is the frequency of
istic Z-scan signature of a positive refractive index or laser radiation. In our case, n0 = 1.34. 47 The cal-
self-focusing nature of the material. 19,44 This positive culated imaginary part and real part value of third-
nonlinear refractive index for the hybrid can be cred- order susceptibility at 90 GW cm−2 are tabulated in
ited to the effects induced by free carriers, given that Table 2. Figure 4d,e depicts a monotonic increase in
the intense incident intensity is sufficient to generate the imaginary and real parts of the optical nonlinear
these free carriers. 43–45 Additionally, the estimated n2 susceptibility as the peak intensity increases, respec-
values using equation S4 43 within the description S3 tively (Table S3), which also supports the notion of
are listed in Table 2. We found that the n2 value of effective charge transfer occurring at the interface of
(94 ± 9)×10−6 cm2 GW−1 for the hybrid is an order the MXene-VS2 hybrid.
of magnitude higher than the control systems, partic- At this juncture, it is crucial to prove that the
ularly approximately 12 times (8 ± 0.7)× 10−6 cm2 observed unprecedented large RSA is a direct result
GW−1 for MXene and 19 times of (5 ± 0.4) × 10−6 brought on by the charge transfer process between the
cm2 GW−1 for VS2 . Furthermore, the increased dis- donor MXene and acceptor VS2 . To achieve this, we
parity between the peak and valley in the Z-scan trace have established a crucial criterion for the occurrence
suggests higher n2 values for the MXene-VS2 hybrid. of RSA is that the value of σES must surpass that of
the value σGS . It is important to note that failure to

Table 2: Third order nonlinear parameters: RSA coefficient (β), saturation intensity (Is ), refractive
index (n2 ) along with imaginary and real parts of third-order susceptibility at 800 nm.

Sample β Isat n2 IMχ(3) Reχ(3)

(10 cm GW−1 )
−3
(10 GW cm−2 )
2
(10 cm2 GW−1 )
−6
(10−15 esu) (10−13 esu)
MXene −(5.0 ± 0.6) 68 ± 6 −(8.0 ± 0.7) 9.1 ± 2.0 3.6 ± 1.8
VS2 −(8.0 ± 0.5) 58 ± 3 −(5.0 ± 0.4) 14.6 ± 5.0 2.3 ± 1.4
MXene-VS2 150 ± 16 6.0 ± 0.5 94 ± 9 274 ± 38 42.8 ± 6.0

7
Figure 5: Optimized structure of (001) plane (a) VS2 (b) MXene-VS2 hybrid, Yellow, Red, Cyan,
and Violet indicate S, V, C and Ti atoms, respectively. (c) TDOS for VS2 and MXene-VS2 hybrid
(d) PDOS for S 3p orbital of VS2 and MXene-VS2 hybrid (e) PDOS for Ti 3d orbital of MXene and
MXene-VS2 hybrid. (f) The charge density picture illustrates the difference in charge between MXene
and hybrid with an isovalue of 0.07e. The yellow region represents VS2 gaining charge, while the blue
region represents MXene losing charge.

meet this criterion will result in the material exhibit-
ing SA instead. 19,42 We satisfied the condition σES >
σGS by enabling the charge transfer from MXene to
VS2 in the MXene-VS2 hybrid, apparent from the cal-
culated data tabulated in Table 1. In this way, we can
acquire RSA in substances only exhibiting SA. For in-
stance, VS2 displays SA that can be made composite
with electron-donating MXene to yield RSA. These
findings certify the unprecedented nonlinear optical
response exhibited by the MXene-VS2 hybrid results
from the phenomenon of charge transfer.
We conducted time-resolved PL spectroscopy to
further understand the charge transfer process. Fig-
ure 4f presents the time-resolved PL spectra of MXene
and MXene-VS2 hybrid under 298 nm excitation. The
decay kinetics were well fitted, exploiting an exponen-
tial decay model, 48 and the corresponding parameters
were tabulated in Table S4. Compared to the aver-
age PL lifetime (τave ) of the control MXene at (4.58
± 0.05) ns, the PL lifetime declined to (1.06 ± 0.01)
ns for the MXene-VS2 hybrid. The notably shorter
average PL lifetime observed in the MXene-VS2 hy-
brid in comparison to the control MXene suggested
an efficient charge transfer between MXene and VS2 ,
similarly noted in other hybrid materials. 18,19,48 The
charge transfer rate and efficiency were calculated to
be 7.3 ×108 s−1 and 77 % using the expressions kET =
1 1 τM Xene−V S2
τM Xene−V S - τM Xene and efET = 1 - τM Xene , re-
2 have calculated the charge transfer using Bader charge
spectively. 48
To realize the charge-transfer mechanism theoret-
ically, we performed first-principles DFT simulations
using VASP. 49–51 Details of the calculations are pre-
sented in the method section. For the MXene-VS2
hybrid, we have taken the monolayer corresponding
to the MAX phase plane (002) of MXene. The opti-
mized structure of the VS2 and hybrid (001) plane is
presented in Figure 5a,b, respectively. The MXene-
VS2 hybrid consists of two monolayers, one with VS2
supercell of dimension 3×3 under periodic boundary
conditions, below which the MXene layer of dimen-
sion 3×3 with interlayer separation of 3.5Å was po-
sitioned. To understand the net effect of hybridiza-
tion qualitatively between MXene and VS2 , we have
presented the total density of states (TDOS) for the
VS2 (001) layer and the MXene-VS2 hybrid displayed
in Figure 5c. This shows an enhancement of states
over the entire range of the valence band due to the
addition of MXene to VS2 . For visualization of or-
bital interaction and charge contribution that hap-
pened after hybridization, we have plotted the par-
tial density of states (PDOS) for S 3p orbital of
VS2 and Ti 3d orbital of MXene as shown in Fig-
ure 5d,f, respectively. For the S 3p orbital of VS2 ,
states are sharply enhanced below the Fermi level af-
ter hybridization. While for Ti 3d orbital, there is
an overall decrease of states for the MXene-VS2 hy-
brid. To comprehend it in a quantitative manner, we

8
Figure 6: (a) The schematic depicts the liquid cell-based optical limiter device with a 1 mm path length
containing MXene-VS2 in distilled water having linear transmission of approximately 60%. Lower-
intensity beams pass through the device in the linear zone (green). Whereas exceeding the threshold
(red region), the system serves as an optical limiter attenuating high-intensity beams. (b) Normalized
transmittance versus input intensity. (c) Output fluence versus input fluence.

partitioning. 52 The Bader charge study indicates that
in MXene-VS2 hybrid, VS2 has a gain of 6.9e charge
from the MXene. So, this agrees with our qualitative
PDOS analysis, concluding that the charge transfer
mechanism follows the path from MXene to VS2 . For
a more visual interpretation of the charge transfer,
we present the charge density picture illustrating the
difference in charge density between MXene-VS2 and
MXene in Figure 5f. The yellow region signifies the
charge-gaining VS2 , while the blue region represents
the charge-losing MXene.
The remarkable advancements in the Kerr nonlin-
earity of hybrid material signify their promising po-
tential for use as an ideal optical limiter. To illustrate
this, we have fabricated an ultrafast optical limiter
based on the liquid cell with a path length of 1 mm,
utilizing aqueous MXene-VS2 as its optical-limiting
medium. Figure 6a presents a schematic of our de-
vice, which exhibits a linear transmittance of approx-
imately 60%. We illustrated the capabilities of our op-
tical limiting device, employing two key parameters:
i) Onset Threshold (FON ), described as the input in-
tensity at the point where the normalized transmit-
tance begins to depart from linearity 18,42 (Figure 6b).
′
ii) Limiting Differential Transmittance (Tdif f ), mea-
sured as the derivative of output intensity with respect
to input intensity at higher intensity 18,19 depicted in
Figure 6c. An ideal case of optical limiter should pos-
′
sess a remarkably low FON and a minimal Tdif f . The
′
determined value of FON = 0.6 mJ cm−2 and Tdif f
of 0.6 was superior to numerous benchmark optical
limiters. We present a performance evaluation of our
device with other optical limiters within their respec-
tive wavelength region in Table 3. Notably, our de-
vice establishes a new standard for optical limiting in
the femtosecond domain. An added advantage of our
liquid-based optical limiters is their self-healing capa-
bility, allowing extensive dynamic ranges constrained
solely by the extent of damage sustained by the cell
windows.

9
 ′
Table 3: Onset threshold (FON ) and differential transmittance (Tdif f ) are compared to those of various
benchmark optical limiters.
′
Systemsm Wavelength Linear T. FON Tdif f References
(nm) (mJ cm−2 )
MXene-VS2 800 60 0.6 0.46 Present Work
C60 532 63 65 - Ref 2
VSe2 -rGO 534 65 2.5 0.42 Ref 18
SWCNT-VSe2 800 70 4 0.54 Ref 19
SWCNT-VSe2 900 66 3 0.53 Ref 19
AuNP-rGO 532 70 50 0.3 Ref 42
ReS2 1064 90 700 0.64 Ref 53
SiO2 -Se 800 85 54 - Ref 54
CdS nanoparticles 532 70 300 0.56 Ref 55

CONCLUSIONS phology at a voltage of 30 kV. Perkin Elmer Instru-

In summary, we have demonstrated unprecedented or
manifold enhancement in the magnitude of the ab-
sorptive and refractive parts of the ultrafast third-
order nonlinear optical response (Kerr nonlinearity)
in donor-acceptor Ti3 C2 Tx (MXene)-VS2 hybrid due
to synergistic charge transfer. We showed a transition
from RSA to SA in the imaginary part and a change
from self-focusing to self-defocusing nature in the real
part of nonlinear optical behavior when moving from
MXene-VS2 hybrid to control systems. Our four-
level rate equation model encapsulates the underlying
physics behind the charge transfer. First-principles
calculations and Bader charge study revealed strong
electronic coupling in the MXene-VS2 hybrid where
electrons are transferred from MXene to VS2 , con-
firmed through the measurement of steady-state and
time-resolved photoluminescence. Moreover, we have
successfully fabricated an optical-limiting device ex-
hibiting crucial device parameters (FON = 0.6 mJ
′
cm−2 and Tdif f = 0.46) comparable to numerous es-
tablished benchmark optical limiters operating within
the femtosecond domain. Our findings offer new per-
spectives on tuning Kerr nonlinear responses, poten-
tially contributing to the advancement of all-optical
photonic devices designed for optical limiting and
switching.
EXPERIMENTAL METHODS
Material characterizations.
We employed Powder X-ray diffraction (PXRD) to
analyze the crystalline structure of the control MX-
ene, VS2 , and the MXene-VS2 hybrid. The measure-
ments were conducted using a Rigaku Ultima IV X-
ray diffractometer with Cu Kα radiation (λ = 0.154
nm) and Ni-filter. Field Emission Scanning Elec-
tron Microscopy (FESEM) from JEOL (model JSM-
7100F) was utilized to characterize the surface mor-
ment used Fourier transform infrared spectroscopy
(FT-IR) to assess the IR scheme from 4000 to 500
cm−1 . The Raman spectra were obtained utilizing a
high-resolution (∼ 1 cm−1 ) Horiba Lab RAM spec-
trometer with a 632.8 nm excitation wavelength from
a He-Ne laser.
Z-scan Measurement.
The Kerr nonlinearity of the MXene-VS2 hybrid and
control samples was studied via the open and close
aperture Z-scan technique. The femtosecond excita-
tion wavelength of 800 nm, 1kHz, and 120 fs pulses
were used in the measurement. The experimental
setup and detail are illustrated in description S3
within the Supporting Information.
Computational Detail.
For first-principle density functional theory (DFT)
simulations, we employed the Vienna ab initio sim-
ulation package (VASP). 49–51 Further, to consider
the ion-electron interaction, we have employed the
projector-augmented wave (PAW) method. 56 The
generalized gradient approach (GGA) of the Perdew-
Burke-Ernzerhof (PBE) functional 57 was used to
characterize the electron-electron exchange correla-
tion. The Grimme’s dispersion corrections for weak
Vander Waals interactions between MXene and VS2
have been applied using a dispersion scheme, DFT-
D2. 58 The plane wave basis was established with
an energy cutoff of 520 eV. The conjugate gradient
approach was used for the structural optimizations,
with a convergence threshold of 10−5 eV and 0.01
eV/Å for the forces and energy, respectively. The
Monkhorst–Pack 59 K point grid size of 5×5×1 and
7×7×1 in the Brillouin zone were applied for struc-
tural optimization and electronic or optical properties
calculations, respectively. To avoid the periodic inter-
actions among the planes, we have introduced a suf-

10
ficient vacuum of 20Å along the z-axis perpendicular
to the planar direction.
ASSOCIATED CONTENT
Supporting Information. Sample fabrication, Ma-
terial characterizations, Conventional Z-scan mea-
surement and theory, Open aperture fluence depen-
dent data, Closed aperture fluence dependent data,
four-level rate equation, Fitting parameters for pho-
toluminescence decays
AUTHOR INFORMATION
Corresponding authors:
K. V. Adarsh - Department of Physics, Indian In-
stitute of Science Education and Research, Bhopal
462066 India.
Phone:+91-755-2691207
E-mail: adarsh@iiserb.ac.in
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
The authors extend their sincere gratitude to the
Science and Engineering Research Board (project
no. EMR/2016/002520 and CRG/2019/002808),
DAE BRNS (sanction no. 37(3)/14/26/2016-
BRNS/37245), and the FIST Project for the Depart-
ment of Physics for their invaluable support. BC ac-
knowledges the BARC computer center supercomput-
ing facility and thanks its staff for continuous help
and support. CSR acknowledges the financial support
provided by the SERB Core Research Grant (Grant
No. CRG/2022/000897) and the Department of Sci-
ence and Technology (DST/NM/NT/2019/205(G)),
as well as the Minor Research Project Grant from
Jain University (JU/MRP/CNMS/29/2023).
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