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Ultrafast Large Third‐Order Optical Nonlinearity in Titanium

Carbide MXene‐VS2 Hybrids

Vinod Kumar1 Naresh Aggrwal1 Aditya Sharma2 Pratap Mane3 Brahmananda

Chakraborty4,5 Chandra S. Rout2 K. V. Adarsh*1

1
Department of Physics, Indian Institute of Abstract
Science Education and Research, Bhopal
462066 India Ultrafast nonlinear optical responses of materials play a significant role in developing modern pho‐
2
Centre for Nano and Material Sciences, Jain tonic and optoelectronic devices including optic time crystals. However, conventional materials
(Deemed‐to‐be University), Jain Global often display either weak optical nonlinearities or slow response times when subjected to intense
Campus, Kanakapura Road, Bangalore – ultrafast optical fields. This limitation can be overcome by leveraging the charge transfer mechanism
562112, Karnataka, India of a donor‐acceptor material pair. However, the low charge transfer rates limit their effectiveness
3
Seismology Division, Bhabha Atomic Research in high‐speed applications. Here, we synthesized titanium carbide MXene‐VS₂ hybrids character‐
Centre, Trombay, Mumbai‐400085, India
ized by strong electronic coupling, resulting in a remarkable enhancement in third‐order nonlinear
4
High Pressure and Synchrotron Radiation optical responsee. For instance, we obtained a third‐order nonlinear optical absorption coefficient
Physics Division, Bhabha Atomic Research
(150 ± 16) × 10–3 cm/GW and self‐focusing (positive) nonlinear refractive index ∼ (94 ± 9) × 10–6
Centre, Trombay, Mumbai 400085, India
5
cm2 /GW at 800 nm in the femtosecond domain, both exceeding control samples by more than
Homi Bhabha National Institute, Mumbai
an order of magnitude. These enhancements are attributed to efficient charge transfer within the
400085, India
hybrid structure, supported by first‐principles calculations and Bader charge analysis. Our findings
Correspondence resulted in the development of an ultrafast optical limiter, featuring an onset threshold as low as
Corresponding author K. V. Adarsh*, 0.6 mJ/cm2 with a differential limiting transmittance of 0.46,these parameters are better or com‐
Email: [email protected] parable with the known benchmarks for high‐speed nonlinear optical applications.

material can be markedly enhanced through charge transfer by creating

1 INTRODUCTION
hybrids of charge‐donating and charge‐accepting materials[13]. Such

Recent advancements in nonlinear optics have increasingly focused on hybrid systems offer a promising approach to overcome these limita‐

third‐order nonlinear optical phenomena, where significant changes in tions. For example, enhanced nonlinear optical responses have been re‐

nonlinear absorption and refractive index are crucial for applications ported in VSe2 ‐rGO[21] and single‐walled CNT‐VSe2 nanohybrids[22],

such as all‐optical switching[1,2]. quantum information processing[3,4], where the nonlinearity is ∼ 10 times larger than that of their individ‐

soliton generation[5], time reflection and refraction[6,7], and time crys‐ ual components. Other hybrid materials, such as MoSe2 /GO[23], hy‐

tals[8]. All these applications require a very large and fast nonlinear brids of gold nanoparticles with CdSe/WS2 [24,25] and Ge24 Se76 [19],

optical response. With that demand, a variety of material systems graphene/MoS2 [26], and inorganic‐organic halide perovskites[17], have

are explored by exploiting the natural nonlinear response and typical also shown improved nonlinear optical responses. However, responses

examples are quantum wells[9], plasmonic metals[10], epsilon‐near‐ of most of these hybrids are limited to picosecond or nanosecond

zero materials[11,12], graphene oxide (GO)[13], black phosphorous[14], timescales due to slow charge transfer rates[13,17]. Consequently, the

fullerenes[15], carbon nanotubes (CNT)[16], inorganic‐organic halide identification of donor‐acceptor hybrid materials capable of operating in

perovskites[17], transition metal dichalcogenides[18], and amorphous femtosecond pulse regimes with ultrafast charge transfer rates remains

chalcogenide films[19], etc. However, the intrinsic nonlinear optical in‐ a critical challenge. This challenge has pushed the exploration of novel

teractions in most materials are typically weak due to their perturbative or previously overlooked material systems, including quantum wells[9].

nature[20]. It has been demonstrated that the intrinsic nonlinearity of a One plausible way to tackle this issue could be by creating donor‐
acceptor hybrid structures of Ti3 C2 Tx (MXene) and VS2 . Our motivation

Abbreviations: ANA, anti‐nuclear antibodies; APC, antigen‐presenting cells; IRF,

behind selecting this hybrid is due to (a) MXene, a new family of layered
interferon regulatory factor.

Journal 2023;00:1–6 wileyonlinelibrary.com/journal/ © 2023 Copyright Holder Name 1

2 TAYLOR et al.

material with high light transmission and tuneable electronic struc‐ is attributed to the ultrafast charge transfer between MXene and VS2 .
ture[27,28] (b) Among the TMDs, VS2 stands out due to, its excellent First‐principles calculations and Bader charge analysis reveal strong
potential as a nonlinear optical material leveraging its large chemically electronic coupling in the hybrid, with electron transfer from MXene to
active surface area and extreme mechanical strength inherent in its VS2 . Exploiting the strong ESA of our hybrid system, we have success‐
2D structure[29,30]. Individually, MXenes and VS2 exhibit beneficial fully fabricated a high‐performance ultrafast optical limiter, exhibiting
nonlinear optical properties with lower magnitudes[31,32]. Thus, incor‐ key device parameters such as an onset threshold of 0.6 mJ/cm2 and
porating VS2 with MXene presents an effective strategy to enhance a limiting differential transmittance of 0.46. These results surpass the
third‐order optical nonlinearity and device performance through charge performance of several benchmark optical limiters operating in the
transfer mechanisms. Recent research has indicated effective charge femtosecond regime.
transfer in MXene‐VS2 hybrids, suggesting their promise for energy
storage and gas sensing applications[30,33]. Despite these advances,
active control of optical third‐order optical nonlinearity mediated by 2 RESULTS AND DISCUSSION
charge transfer remains largely unexplored. Here, we report a manifold
enhancement in the magnitude of the imaginary part of the optical sus‐ We have synthesized high‐quality VS2 nanosheets and strongly coupled
ceptibility β (excited state absorption coefficient) and the real part of MXene (Ti3 C2 Tx )‐VS2 hybrid by using the hydrothermal method and
the optical susceptibility n2 (nonlinear refractive index) of the MXene‐ MXene by the minimally intensive layer delamination (MILD) method.
VS2 hybrid at 800 nm excitation compared to individual materials which The synthesis process is schematically outlined in Figure S1 (Supporting
show only saturable absorption and negative n2 within the femtosecond Information), with additional experimental details in the Experimen‐
regime. For instance, we demonstrate β of (150 ± 16) × 10–3 cm/GW tal section. The successful formation of strongly coupled MXene‐VS2
and a n2 of ∼ (94 ± 9) × 10–6 cm2 /GW, which exceeds control sam‐ hybrids is confirmed through the powder X‐ray diffraction (PXRD) pat‐
ples by at least an order of magnitude. This significant enhancement tern shown in Figure S2 (Supporting Information). Notably, a shift in
of the real and imaginary part of the third‐order optical susceptibility the Bragg peak from ∼8.7◦ to 6.9◦ , along with the emergence of a

F I G U R E 1 High‐magnification FE‐SEM images of (a) MXene, (b) VS2 nanosheets, and (c) MXene‐VS2 hybrid, showing the distinct morphologies
of each sample. (d) FTIR spectra of VS2 , MXene, and the MXene‐VS2 hybrid, highlighting the shifts in vibrational modes indicative of strong
interactions between MXene and VS2 . (e) UV‐vis absorption spectra of MXene (violet line), VS2 (green line), and the MXene‐VS2 hybrid (pink line)
highlight the distinct absorption features of each component and the redshift observed in the MXene‐VS2 hybrid due to electronic coupling.
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broad peak at ∼27.9◦ , absent in the isolated samples, confirms the Figure 1e presents the UV‐Vis absorption spectra of MXene (violet
formation of hybrid structures (detailed in Section S2.1; Supporting line), VS2 nanosheets (green line), and the MXene‐VS2 hybrid (pink line).
Information). The morphologies of the synthesized samples were char‐ MXene shows a relatively flat absorption across the visible region, con‐
acterized by field emission scanning electron microscopy (FE‐SEM), as sistent with its metallic nature as previously reported[32,35]. In contrast,
depicted in Figure 1. Figures 1a,b show the FE‐SEM image of VS2 and VS2 exhibits an absorption onset of around 530 nm. In the MXene‐VS2 ,
MXene, which exhibit uniform layered sheet‐like morphology and uni‐ the absorption spectrum integrates characteristics of both MXene and
formly etched layers, respectively. Figure 1c shows the FE‐SEM image VS2 , with the absorption features of VS2 with a pronounced redshift.
of the MXene‐VS2 hybrid, where VS2 sheets disintegrate into smaller This behaviour indicates strong electronic coupling and efficient charge
fragments that assemble on or between the MXene flakes, effectively transfer between MXene and VS2 in the hybrid structure.[21,22]
preventing restacking —an effect not observed in the isolated VS2 To investigate the third‐order nonlinear optical response of MXene‐
samples. VS2 , MXene, and VS2 samples, we employed the open‐aperture Z‐scan,
The strong interaction between VS2 nanosheets and MXene lay‐ which quantifies the total transmittance as a function of incident laser in‐
ers in the hybrid structures is confirmed by Fourier transform infrared tensity. Details about the experiments are provided in Section S3 within
(FTIR) spectroscopy (Figure 1d). The observed shift in the bending vibra‐ Supporting Information. Figure 2a displays the Z‐scan traces for the
tions of the S‐V‐S and V=S bands in the MXene‐VS2 hybrid indicates MXene‐VS2 hybrid at 800 nm, using an on‐axis peak intensity of 90
the strong interaction between the MXene functional groups and the GW/cm2 at the focal point. Notably, the Z‐scan traces of the sample ex‐
doubly bridged S2– species[34]. Further, the Raman spectrum of the hibit a distinct reduction in transmission as the sample approaches the
MXene‐VS2 hybrid (Figure S3, Supporting Information) shows a combi‐ focal point, a behavior indicative of nonlinear absorption processes. The
nation of signals from the control samples, with a prominent blue shift experimental data were analyzed using nonlinear absorption models
of the characteristic peak from 510 cm–1 in MXene to 525 cm–1 in the (detailed section S3.1; Supporting Information), providing a nonlinear
hybrid. This shift provides further evidence of strong electronic coupling absorption coefficient, (β ) of (150 ± 16) × 10–3 cm/GW, along with the
between VS2 and MXene in the hybrid.

F I G U R E 2 Open‐aperture Z‐scan traces measured at 800 nm for (a) MXene‐VS2 hybrid, (b) MXene, and (c) VS2 nanosheets at varying on‐axis
peak intensities, illustrating the distinct nonlinear optical responses: ESA in the MXene‐VS2 hybrid, and SA in MXene and VS2 . (d) Variation of β
with input intensity for MXene‐VS2 hybrid, MXene and VS2 .
4 TAYLOR et al.

F I G U R E 3 Closed‐aperture Z‐scan traces measured at 800 nm for (a) MXene‐VS2 hybrid, (b) MXene, and (c) VS2 nanosheets at varying on‐
axis peak intensities, illustrating the distinct nonlinear optical responses: self‐focusing (positive nonlinearity) in the MXene‐VS2 hybrid, and self‐
defocusing (negative nonlinearity) in MXene and VS2 . (d) Variation of n2 with input intensity for MXene‐VS2 hybrid, MXene and VS2 .

saturation intensity (I0 ) (6.1 ± 0.5) × 10–2 GW/cm2 . To further under‐ T A B L E 1 The calculated σGS and σES for MXene, VS2 , and MXene‐
stand the mechanism behind the nonlinear absorption, we performed VS2 hybrid under 800 nm excitation.
additional Z‐scan measurements across a range of intensities. Table 2
Sample Intensity σGS σES
demonstrates that the β values increase systematically with increasing GW cm–2 (10–20 cm2 ) (10–20 cm2 )
laser intensity, indicating that the nonlinear optical response originates MXene 30 1.5 ± 0.2 0.7 ± 0.1
from excited state absorption (ESA), as opposed to the two‐photon ab‐ 90 2.2 ± 0.4 1.1 ± 0.2
150 3.5 ± 0.5 1.6 ± 0.4
sorption, where a constant β would be expected. In further support of
VS2 30 1.0 ± 0.2 0.5 ± 0.1
the ESA mechanism, we calculated the excited state (σES ) and ground 90 1.6 ± 0.4 0.9 ± 0.3
state (σGS ) absorption cross‐sections. The analysis revealed that the val‐ 150 2.4 ± 0.6 1.5 ± 0.4
MXene‐VS2 30 2.5 ± 0.6 6.0 ± 0.9
ues of σES exceed σGS , as presented in Table 1. This result validates the
90 3.8 ± 1.0 8.6 ± 1.5
occurrence of ESA in the MXene‐VS2 hybrid[22]. 150 5.4 ± 1.2 15.0 ± 2.0
In stark contrast to the MXene‐VS2 hybrid, the Z‐scan traces of MX‐
ene show an increase in transmittance as the sample moves toward the
focal point, reaching a maximum at the focus, which is characteristic of density and show SA when excited at 800 nm. Our calculations further

SA[36] (Figure 2b). This behavior can be understood by considering the support this explanation, showing that for VS2 , σES < σGS , (see Table

fact that, at this intensity, ground‐state carriers are depleted, leading to 1) confirms the SA behavior through sub‐bandgap absorption mediated

a condition where the σES < σGS , a key criterion for observing SA[13,22]. by defect states[38]. Our results demonstrate that the integration of

The Z‐scan traces for VS₂ exhibit a similar SA response (Figure 2c). This electron‐donating MXene with VS2 can induce ESA in the hybrid, a sig‐

behavior in VS2 can be explained by band structure modulation due to nificant departure from the SA observed in the individual materials. This

defect states, such as vanadium or sulphur vacancies, or the coexistence unprecedented nonlinear optical response in the MXene‐VS2 hybrid is

of both semiconducting and metallic phases[37,38]. These defects in‐ driven by efficient ultrafast charge transfer between the two compo‐

troduce sub‐bandgap states, which can easily saturate due to their low nents, marking a novel approach to tune the nonlinear optical properties.
PLEASE INSERT YOUR ARTICLE TITLE HERE 5

Additionally, the intensity‐dependent variation of β has a monotonic in‐ which plays a crucial role in the distinct nonlinear optical response ob‐
crease with peak intensity, as shown in Figure 2d, further confirming served in the MXene‐VS2 system. Moreover, the n2 variation with input
the ESA of MXene‐VS2 hybrid. intensity are shown in Figure 3d, which is also monotonically increasing
After observing the enhanced imaginary part of the third‐order non‐ with the intensity.
linear optical response in the MXene‐VS2 hybrid, we investigated the Moreover, we calculated the third‐order nonlinear optical suscepti‐
effect of charge transfer on the real part of the nonlinear refractive bility (χ(3) ) for these materials using the following equation[40]:
index (n2 ). The sign and magnitude of n2 were determined using the
(3) (3)
closed‐aperture Z‐scan technique, with an aperture positioned before χ(3) = χR + ιχI (1)

the detector to reduce transmission to one‐third of the input laser in‐ (3) (3)
where χR and χI are the real and imaginary parts of the nonlinear op‐
tensity. Figures 4a,b,c presents the closed‐aperture Z‐scan results for
tical susceptibility. The calculated values of the real and imaginary parts
the MXene‐VS2 and individual components (MXene and VS2 ) at vari‐
of the third‐order nonlinear susceptibility at various on‐axis peak inten‐
ous on‐axis peak intensities. Notably, the MXene‐VS2 hybrid displays
sities are plotted in Figure S5a,b in Supporting Information, showing a
a valley‐to‐peak pattern, indicative of a self‐focusing nonlinearity that
monotonic increase with increasing peak intensity. This behavior further
corresponds to positive nonlinearity (Reχ(3) > 0). In contrast, the
supports the hypothesis of effective charge transfer in the MXene‐VS2 ,
individual MXene and VS₂ samples exhibit the typical peak‐to‐valley pat‐
which contributes to the enhanced nonlinear optical properties.
tern, which is characteristic of a self‐defocusing effect associated with
To theoretically investigate the charge‐transfer mechanism, we per‐
negative nonlinearity (Reχ(3) < 0).
formed first‐principles density functional theory (DFT) simulations us‐
To quantify these observations, we modeled the closed‐aperture Z‐
ing VASP[41–43]. Details of the calculations are provided in the Experi‐
scan traces using the equations[39] S4 (Supporting Information), and
mental section. For the MXene‐VS2 hybrid, we modeled the system with
the extracted n2 values are summarized in Table 2. The n2 value for the
a monolayer corresponding to the (002) plane of MXene from the MAX
MXene‐VS2 at the onset peak intensity of 90 GW/cm2 was determined
phase. The optimized structures of the VS2 monolayer and the MXene‐
to be (94 ± 9) × 10–6 cm2 /GW, which is an order of magnitude larger
VS2 hybrid (001) plane are presented in Figures 4a,b, respectively. The
than the values for the individual components: (8 ± 0.7) × 10–6 cm2 /GW
MXene‐VS2 hybrid comprises two layers: a 3×3 supercell of VS₂ under
for MXene and (5 ± 0.4) × 10–6 cm2 /GW for VS2 . The significant en‐
periodic boundary conditions, positioned 3.5 A◦ above a 3×3 MXene
hancement in the nonlinear refractive index of the MXene‐VS2 can be
layer.
attributed to the charge transfer mechanism between MXene and VS2 ,

F I G U R E 4 Optimized structure of (001) plane (a) VS2 (b) MXene‐VS22 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.
6 TAYLOR et al.

FIGURE 5 (a) Normalized transmittance versus input intensity. (b) Output fluence versus input fluence.

To understand the hybridization effect between MXene and VS2 , we

computed the total density of states (TDOS) for the VS2 (001) mono‐
layer and the MXene‐VS2 hybrid (Figure 4c). The TDOS reveals an
enhancement in the states across the entire valence band due to MXene
addition to VS2 . For a more detailed analysis of orbital interaction and
charge contribution after hybridization, we plotted the partial density of
states (PDOS) for the S 3p orbital of VS2 and the Ti 3d orbital of MXene
(Figure 4d,e). After hybridization, the S 3p orbital shows a sharp increase
in states below the Fermi level, while the Ti 3d orbital exhibits an over‐
all decrease in states in the hybrid system. To quantitatively confirm
the charge transfer, we conducted Bader charge partitioning[44]. The
Bader analysis indicates that VS₂ gains 0.07e from MXene in the MXene‐
VS2 hybrid, consistent with the PDOS analysis. To further visualize the
charge transfer, Figure 4f presents the charge density difference be‐
tween the MXene‐VS2 hybrid and pristine MXene. The yellow regions
represent VS₂ gaining charge, while the blue regions show MXene losing
charge. This visualization clearly demonstrates electron transfer from
MXene to VS2 in the hybrid, validating the charge‐transfer mechanism.
The MXene‐VS2 hybrid exhibits a notable enhancement in both the
β and n2 , emphasizing its potential as a high‐performance ultrafast
optical limiter capable of delivering ultrafast and efficient protection
against intense light pulses. Two key metrics define its optical limiting
performance: (a) Onset threshold fluence (FON )‐the fluence at which
normalized transmittance begins to deviate from linearity, marking the
initiation of optical limiting and (b) Limiting differential transmittance
′
Tdiff (dIout /dIin )‐which quantifies the material’s ability to attenuate trans‐
mitted light as fluence increases[22]. A superior optical limiter requires
′
both low FON and Tdiff values. The MXene‐VS2 hybrid achieves an
′
exceptionally low Fₒ� of 0.6 mJ/cm² and a Tdiff of ∼0.6, (see Figure
5a,b), outperforming many established benchmarks in optical limiting.
′
This low FON and Tdiff highlights the MXene‐VS₂ hybrid’s promise for
next‐generation optical limiting applications, offering a powerful com‐
bination of speed, efficiency, and material versatility.