ORIGINAL PAPER

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Broadband Nonlinear Photonics in Few-Layer MXene

Ti3C2Tx (T = F, O, or OH)
Xiantao Jiang, Shunxiang Liu, Weiyuan Liang, Shaojuan Luo, Zhiliang He, Yanqi Ge,
Huide Wang, Rui Cao, Feng Zhang, Qiao Wen,* Jianqing Li, Qiaoliang Bao,
Dianyuan Fan, and Han Zhang*

1. Introduction
Studies of the nonlinear optical phenomena that describe the light-matter
interactions in 2D crystalline materials have promoted a diverse range of Nonlinear optical (NLO) materials, as
a fundamental building block of laser
photonic applications. MXene, as a recently developed new 2D material, has optics, photonics circuits and optical
attracted considerable attention because of its graphene-like but highly communication, have garnered signif-
tunable and tailorable electronic/optical properties. In this study, we icant interest since the first laser was
systematically characterize the nonlinear optical response of MXene Ti3 C2 Tx demonstrated.[1] Two dimensional (2D)
nanosheets over the spectral range of 800 nm to 1800 nm. A large effective materials, which feature distinctive
electronic, optical and mechanical prop-
nonlinear absorption coefficient (β eff -10−21 m2 /V2 ) due to saturable
erties absent in their bulk counterparts,
absorption is observed for all of the testing wavelengths. The contribution of strongly match with the increasing
saturable absorption is two orders of magnitude higher than other lossy demands of compactness, small foot-
nonlinear absorption processes, and the amplitude of βeff strongly depends print, high efficiency and broadband
on the light bleaching level. A negative nonlinear refractive index (n2 -10−20 in photonic and optoelectronic devices.
m2 /W) with value comparable to that of the intensively studied graphene was Graphene, as a pioneering 2D mate-
rial, has been intensively investigated
demonstrated for the first time. These results demonstrate the efficient as a NLO material for use in diverse
broadband light signal manipulating capabilities of Ti3 C2 Tx , which is only one applications, such as broadband optical
member of the large MXene family. The capability of an efficient broadband modulator,[2] optical frequency mixing,[3]
optical switch is strongly confirmed using Ti3 C2 Tx as saturable absorbers for ultrafast laser generation[4] and surface
mode-locking operation at 1066 nm and 1555 nm, respectively. A highly stable plasmonic;[5] however, the intrinsically
gapless band structure and the weak elec-
femtosecond laser with pulse duration as short as 159 fs in the
tronic on/off ratio limit its use to a certain
telecommunication window is readily obtained. Considering the diversity of degree.[6] Recently, a bunch of novel 2D
the MXene family, this study may open a new avenue to advanced photonic materials in the phase of semiconduc-
devices. tor and metallic, such as topological

X. Jiang, W. Liang, S. Luo, Z. He, Y. Ge, H. Wang, F. Zhang, D. Fan, Prof. X. Jiang, S. Liu, W. Liang, S. Luo, Z. He, Y. Ge, H. Wang, F. Zhang, Prof. Q.
H. Zhang Wen, D. Fan, Prof. H. Zhang
Shenzhen Engineering Laboratory of Phosphorene and Optoelectronics Key Laboratory of Optoelectronic Devices and Systems of Ministry of
Collaborative Innovation Center for Optoelectronic Science and Education and Guangdong Province
Technology College of Optoelectronic Engineering
College of Optoelectronic Engineering Shenzhen University
Shenzhen University Shenzhen 518060, China
Shenzhen 518060, China E-mail: [email protected]
E-mail: [email protected] R. Cao, Prof. J. Li
Faculty of Information Technology
Macau University of Science and Technology
Macao, P. R. China
Prof. Q. Bao
The ORCID identification number(s) for the author(s) of this article
Department of Materials Science and Engineering
can be found under https://doi.org/10.1002/lpor.201700229
Monash University
DOI: 10.1002/lpor.201700229 Clayton, Victoria, Australia

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insulators (TIs, e.g., Bi2 Te3 ), transition metal dichalcogenides 2. Optical Nonlinearity Characteristics
(TMDCs, e.g., MoS2 and WS2 ) and black phosphorus (BP),
have been shown to demonstrate tempting optical nonlinearities. Typically, MXene Ti3 C2 Tx features an ABC stacking order in
However, the lack of fine-controlled material fabrication remains a hexagonal crystal lattices, where carbon atoms fill the octa-
a hurdle to commercialization of 2D materials, and their optical hedral sites between two titanium atom layers, as shown in
properties still require deeper understanding. For example, syn- Figure 1a. The accordion-like structures of delaminated Ti3 C2 Tx
thesizing single atomic layer black phosphorus via conventional can be clearly observed after the acid etching process (see the
chemical vapor deposition (CVD) still remains a challenge. The experimental section) using a scanning electronic microscope
development of promising novel NLO materials, especially in the (SEM), as shown in Figures 1c and 1d. The inter-layer distance is
2D phase, is still a longstanding goal. determined as 9.82 Å, which matches well with the previously de-
In the past several years, MXene,[6] as a new member of the 2D termined theoretical value (9.93 Å).[29] The as-prepared few-layer
material family, has attracted considerable attention from divisive Ti3 C2 Tx -NMP solution can be deposited onto a clean 170 μm
research fields because of its outstanding merits, including good borosilicate glass substrate for optical characterization. Figure 1b
conductivity, high elastic moduli, high electric capacity, tunable shows an impartial linear absorption over the spectral range of
bandgap, high optical transparency, ability to perform ion inter- 400 nm to 3000 nm, corresponding to the zero-gap band struc-
calation, room temperature and ambient fabrication, and com- ture of Ti2 C3 (or Eg < 0.2 eV of Ti3 C2 Tx ),[6,28,30] indicating its po-
patibility of water and organic solvents.[6–16] Nevertheless, the op- tential for use in broadband optical devices.
tical nonlinearities and the related applications of MXene have The optical nonlinearity of MXene Ti3 C2 Tx is characterized
been rarely investigated to date,[17] although the linear optical using the widely employed Z-scan measurement technique (see
properties have been experimentally[14,18] and theoretically[19–22] the supporting information S1).[31,32] The MXene “thin” sample
studied. (220 μm, smaller than the Rayleigh length) is transferred along
The general formula of MXene is Mn+1 Xn Tx , where M is an the optical axis and across the focus of the incident laser beam.
early transition metal, X is C and/or N, T is the surface ter- The sequentially measured transmittance under open and close
minations (hydroxyl, oxygen or fluorine), and n = 1, 2, or 3. aperture conditions as a function of the laser intensity can reveal
MXenes can be fabricated through the following processes: 1) the information of the sample’s nonlinear absorption, scattering
top-down selective aqueous acid etching[6] or high-temperature and refractive index. Nonlinear absorption can be further subdi-
etching[23] of “A” atomic layers from their ternary MAX phase pre- vided into multiphoton absorption (MPA), saturable absorption
cursors, due to weaker M-A metallic bonds compared to the cova- (SA), reverse saturable absorption (RSA), and free-carrier absorp-
lent/metallic/ionic mixed M-X bond,[24] where A represents the tion (FCA) that typically occur on the sub-picosecond time scale.
A-group elements (normally groups 13 and 14) and 2) bottom-up To investigate the broadband optical nonlinearities, four excita-
chemical vapor deposition (CVD).[25] The wet etching approach tion sources with wavelengths centered at 800 nm, 1064 nm, 1550
had been most widely employed in delivering high-quality MX- nm and 1800 nm are applied to perform the characterizations.
ene with the existence of terminations,[26] leading to an intrinsi- Figure 2 shows the open aperture Z-scan measurement results
cally hydrophilic nature. Moreover, the terminations and arrange- of Ti3 C2 Tx sample #2 (see Figure 1b). Obviously, nonlinear ab-
ment of the transition metal layers can be utilized to significantly sorption phenomenon is manifested at all of those wavelengths,
alter the electronic band structure.[26–28] Over 70 types of differ- that is, the transmission increases nonlinearly with increasing
ent MAX ternary carbides and nitrides have been reported to illuminating laser intensity. As mentioned above, several mech-
date,[26] representing the rich variety of the MXene family. The anisms can lead to the nonlinear absorption; an effective non-
wide ranges of chemistries and electronic band structure tunabil- linear absorption coefficient (βeff ) is usually introduced, and the
ity indicate that MXene may process the ability to be tailored for absorption coefficient (α) can be expressed as
different applications, ranging from nuclear waste management
to biosensors.[26] α = α0 + βeff I. (1)
In this contribution, a typical MXene Ti3 C2 Tx was deliber-
ately chosen as the investigation object to highlight broadband Where α0 is the linear absorption coefficient component, and
nonlinear optical response in the near infrared region. Efficient I is the laser intensity. The determined βeff as a function of the
saturable absorption with negligible lossy nonlinear absorption incident pulse energy (Ep ) is presented in Figure 3a. The largest
components is found in the spectral range from 800 nm to 1800 values of βeff obtained at 800 nm, 1064 nm, 1550 nm and 1800
nm. The resulting maximum nonlinear absorption coefficient nm are –0.297 cm/GW, –0.206 cm/GW, –0.358 cm/GW and –
(βeff ) is found to be on the order of 10−21 m2 /V2 (or 10−13 esu), 0.112 cm/GW, respectively. The imaginary part of the third-order
which is comparable or much higher than the values reported in nonlinear optical susceptibility (Imχ (3) ) can be calculated based
other 2D materials. The detected Kerr effect coefficients (n2 ) in on the following formula[33] :
the testing spectral range are negative, with values comparable
2ε0 c2 n0 2
to that of graphene. As with graphene, our study suggests that Im χ (3) = βeff . (2)
MXene may be considered as a new suitable candidate 2D mate- 3ω
rial for use in nonlinear optics, electro-optics and nanophotonics. Where c is the vacuum light speed, ε0 is the vacuum perme-
As an example application in ultrafast photonics, highly stable ability, ω is the angular frequency, and n0 is the linear refractive
femtosecond mode-locked fiber lasers are realized using MXene index (n0 ≈ 2[22] ). The calculated Imχ (3) features a similar vari-
Ti3 C2 Tx as an efficient saturable absorber. ation trend as βeff and is on the order of 10−21 m2 /V2 (or 10−13

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Figure 1. a) Three atomic layers of MXene Ti3 C2 Tx . The right-hand side shows the primitive cell (space group P63 /mmc). The parameters of the crystal
structure are based on REF.[29] b) Linear transmittance of as-prepared few layer MXene Ti3 C2 Tx deposited on a 170 μm borosilicate glass substrate
over the spectral range from 400 to 3000 nm. The Fresnel reflection and glass absorption were baselined by a bare glass substrate. #1-3 indicates three
different Ti3 C2 Tx -glass samples with increasing Ti3 C2 Tx concentrations on the glass substrates. The concessions between 2700 to 2800 nm are due to
the absorption of CO2 and H2 O in the air.[54] c) and d) SEM images of delaminated Ti3 C2 Tx after HF etching under different magnifications. e) High
resolution TEM (HRTEM) image of monolayer Ti3 C2 Tx . f) Atomic lattice of Ti3 C2 Tx under an HRTEM. g) The inter-layer distance is measured to be 9.82
Å, close to the theoretical value of 9.93 Å[29] shown in (a). h) Selected area electron diffraction (SAED) image of Ti3 C2 Tx .

esu), as shown in Figure 3b. The resulting value of βeff (or Imχ (3) ) ing effective coefficient βeff  can be used to represent the con-
in Ti3 C2 Tx is similar to that of graphene oxide[34] and is two or- tributions of the other nonlinear absorption processes. The sat-
ders of magnitude higher than those of transition metal dichalco- urable absorption caused by Pauli blocking can be well-described
genide MoS2 [35] and black phosphorus,[36] indicating a strong op- by a two-level energy system (see the supporting information S2).
tical switch capability. Therefore, the absorption coefficient can be rewritten as
Note that the effective nonlinear absorption coefficient is not
a constant for a given wavelength and shows a decreasing trend α1 
α = α0 + + βeff I. (3)
with respect to different pulse energies, indicating that the one- 1 + I/Is
photon process saturable absorption process dominates the non-
linear absorption at low pulse energy, whereas multiple pho- Where Is is the saturation intensity, α1 is the modulation depth
ton absorption processes occur as the pulse energy increases. If parameter,[37] and βeff  I = βeff I − α1 /(1 + I/Is ). Note the contri-
the Ti3 C2 Tx sample is well-saturated/bleached such that the sat- butions of MPA, RSA and FCA to the absorption coefficient are
urable absorption contribution can be ruled out, then the remain- positive. Figure 4 shows the absorption coefficient changes as a

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Figure 2. Open aperture Z-scan characterizations of MXene Ti3 C2 Tx at wavelengths of a) 800, b) 1064, c) 1550 and d) 1800 nm. Solid lines are the fitting
results with a two-level energy system model.

function of illuminating laser intensity at highly bleached level. decay time. The absorber features the lowest saturation inten-
The estimated βeff  for the four wavelengths of 800, 1064, 1550 sity at 1800 nm, with a value of 31.4 ± 5 GW/cm2 . The mod-
and 1800 nm are 11.7, 3.86, 7.65 and 14.3 × 10−3 cm/GW, re- ulation depth in this study is defined as the normalized trans-
spectively, two orders of magnitude smaller than the contribution mittance difference between high and low illumination intensi-
of saturable absorption, indicating low additional optical losses. ties ( T = 1 − exp(−α1 ) ≈ α1 , if α1 ∼ 0). At the wavelength of
However, when the laser intensity is above the laser thresholds 1064 nm, the absorber features the highest modulation depth
(Ith ) on the scale of a few-hundred to one-thousand GW/cm2 , the of 38.3 ± 2.0%. The modulation depth is related to the density
other nonlinear absorption processes are nontrivial compared to of states (DOS) of the ground and excited states; however, the
saturable absorption and become the dominant processes in MX- modulation depth in this experiment shows an ambiguous de-
ene Ti3 C2 Tx (see Figure 4). pendence on the incident photon energy. The saturation fluence
To characterize the saturable absorption properties of MXene (Fs ) can be estimated based on Fs = Is t, where t is the pulse du-
Ti3 C2 Tx , the optical transmittance as a function of the incident ration of the pump laser pulses, to be 8.4 ± 0.4, 8.2 ± 0.4, 5.7 ±
laser intensity is fitted with a two-level system (see supporting 0.5 and 5.8 ± 0.6 mJ/cm2 for 800, 1064, 1550 and 1800 nm re-
information S3). The resulting saturation intensities are in the spectively, under the assumption of a fast saturable absorber.[38,39]
range of tens of GW/cm2 (the averaged Is for 800, 1064, 1550 The observed saturation intensities/fluences of the Ti3 C2 Tx sat-
and 1800 nm are 88.6 ± 5, 61.2 ± 5, 39.1 ± 5 and 31.4 ± 5 urable absorber are similar to saturable absorbers based on
GW/cm2 , respectively) under the assumption of a diffraction- graphene,[40] carbon nanotubes,[41] dichalcogenides,[35,42] topolog-
limit Gaussian beam (see Figure 5). Therefore, these saturation ical insulators[43,44] and black phosphorus,[45] while featuring a re-
intensities can be regarded as the upper limits of the absorber. markably high modulation depth and low linear losses.
The saturation intensity is inversely proportional to the wave- The nonlinear refractive index of MXene Ti3 C2 Tx can be
length, in agreement with the two-level energy system model characterized using the closed aperture Z-scan approach.[32]
(see supporting information S2), Is = hν/σ τr , where hν is the Figure 6 shows the normalized transmittance of the closed
photon energy, σ is the absorption cross section, and τr is the aperture Z-scan results baselined to the identical open aperture

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Figure 3. a) Effective nonlinear absorption coefficient (βeff ) and b) imaginary part of the third-order nonlinear optical susceptibility (Imχ (3) ) as a function
of pulse energy (Ep ) at different wavelengths.

Figure 4. Absorption coefficient of MXene Ti2 C3 Tx as a function of laser intensity at a highly saturated level: a) 800 nm, b) 1064 nm, c) 1550 nm, and d)
1800 nm.

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Figure 5. a) Saturation intensity (Is ) and b) modulation depth ( T) as a function of incident pulse energy at different wavelengths. Note the Is values in
(a) follow a similar trend with wavelength as the Is values in Figure 4, and the values of Is in (a) are determined while neglecting the two-order smaller
contribution of βeff  .

Figure 6. Closed aperture Z-scan at wavelengths of a) 800 nm, b) 1064 nm, c) 1550 nm and d) 1800 nm performed to reveal the nonlinear refractive
index (n2 ) and the real part of the third-order nonlinear optical susceptibility (Reχ (3) ).

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Figure 7. a) Schematic of the ytterbium-doped fiber laser passively mode locked using a MXene Ti2 C3 Tx saturable absorber. LD: laser diode. WDM:
wavelength division multiplexer. YDF: ytterbium-doped fiber. PI-ISO: polarization independent isolator. PC: polarization controller. SA: saturable absorber.
OC: output coupler. Filter: fiber-pigtailed filter centered at 1064 nm with a bandwidth of 10 nm. b) Typical oscilloscope pulse trains of mode-locking. c)
Mode-locked optical spectrum centered at 1065.89 nm. The bandwidth at 3 dB is 4.4 nm. d) Mode-locked pulse duration characterized via oscilloscope,
τ = 480 ps. e) Radio frequency spectrum of the mode-locked pulses, inset: the broadband RF spectrum.

Z-scan ones. The normalized transmittance can be fitted using waist, λ is the wavelength, and I0 is the on-axis intensity at focus.
the following formula: The peak-valley shapes of the transmittance suggest negative
refractive indices. The resulted nonlinear refractive indices
1 are –4.66, –3.47, –4.89 and –9.85 × 10−20 m2 /W at 800, 1064,
Tnorm (z) = . (4)
1− 4x
2 + 4 2
1550 and 1800 nm, respectively. The real part of the third-order
( 1+x2 ) (1+x2 )3
nonlinear optical susceptibility (Reχ (3) ) can be expressed as[33]
Where x = z/z0 , z is the Z-scan displacement, = 4ε0 cn0 2
2π n2 I0 Leff /λ is the phase change, n2 is the nonlinear refractive Re χ (3) = n2 . (5)
3
index, Leff = (1 − e−α0 L )/α0 is the effective thickness of the The calculated Reχ (3) for the four wavelengths of 800, 1064,
sample, L is the physical thickness of the sample, z0 = πω0 2 /λ 1550 and 1800 nm are –6.61, –4.93, –6.93 and –13.9 × 10−22
is the Rayleigh length of the Gaussian beam, ω0 is the beam m2 /V2 (or 9 × 108 /4π esu), respectively, as shown in Figure

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Figure 8. a) Schematic of the erbium-doped fiber laser passively mode locked using a MXene Ti2 C3 Tx saturable absorber. LD: laser diode. WDM:
wavelength division multiplexer. EDF: erbium-doped fiber. OC: output coupler. PI-ISO: polarization independent isolator. SA: saturable absorber. PC:
polarization controller. b) Typical oscilloscope pulse trains of mode-locking. c) Mode-locked optical spectrum centered at 1555.1 nm under the pump
power of 238 mW. The bandwidth at 3 dB is 22.2 nm. d) Autocorrelation trace with a sech2 fitting, τ = 159 × 1.543 fs. e) Radio frequency spectrum of
the mode-locked pulses, inset: the broadband RF spectrum.

6. The nonlinear refractive index of a 2D material is a key 3. Ultrafast Photonics Applications

parameter for the diverse applications to be studied. However,
the reported values usually show discrepancies and heavily The large optical nonlinearities of MXene Ti3 C2 Tx over a broad
depend on the characterization techniques and material fabri- spectral bandwidth presented above suggest promising appli-
cation methods. For example, the reported nonlinear refractive cations of MXene in ultrafast laser photonics. Femtosecond
indices of graphene range over eight orders of magnitude, from lasers are strongly demanded in such application fields as
10−19 m2 /W to 10−11 m2 /W.[46,47] In this primary study on the micromachining,[49] chemical reaction detecting,[50] and medical
optical nonlinearities of MXene Ti3 C2 Tx , we observed that the surgery.[51] A few layer MXene Ti3 C2 Tx based saturable absorber
resulting n2 (or Reχ (3) ) is close the values of graphene reported (SA) is implemented in a Yb-doped fiber ring cavity for mode-
in Refs. [46,48] locking operation (see Figure 7). Because the laser cavity is at the
state of all-normal dispersion, a spectral filter is essential for a

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stable mode-locking operation. In this experiment, a fiber- mode-locking operation is confirmed by the high signal-to-noise
pigtailed filter centered at 1064 nm with a bandwidth of 10 nm is ratio (SNR>62 dB) of the fundamental peak and the broadband
inserted in the cavity, resulting in a cavity length of 10.9 m. The signals without jitter observed in the RF spectrum.
absorber is formed by depositing Ti3 C2 Tx from its solution onto a
side-polished fiber (D-shaped fiber in Figure 7a). A highly stable
continuous wave mode locked (CWML) laser pulse train is ob-
tained when the pump power is above 84 mW. Figure 7b shows
4. Conclusions
the typical oscilloscope trace of the pulse train of mode-locked We investigated the broadband nonlinear optical response in few
laser operation at the pump power of 482 mW. The correspond- layer MXene Ti3 C2 Tx flakes over the spectral range from 800 nm
ing output power, pulse energy and peak power are 9 mW, 0.47 to 1800 nm. Large saturable absorption response, two orders of
nJ and 482 W, respectively. This performance of the ytterbium- magnitude greater than other lossy nonlinear absorption pro-
doped fiber laser is similar to previously reported values ob- cesses, were observed for all the characterization wavelengths,
tained using saturable absorbers based on graphene, MoS2 , WS2 , indicating the photonic applications of MXene materials for ef-
phosphorene or Bi2 Se3 . The time interval between two pulses is ficient broadband optical signal amplitude switches. Depositing
52.7 ns, which corresponds to a repetition rate of 18.96 MHz. a Ti3 C2 Tx film onto a side-polished fiber as a saturable absorber
The insert of Figure 7b shows uniform intensity pulses of the realizes a compact integrated fiber cavity for femtosecond laser
mode-locked laser over a time scale of 1 ms, which demonstrates generation (τ 159 fs), which will be beneficial to a wide range of
the highly stable operation of the mode-locked laser. A typical industrial applications. The high-intensity illumination induced
bell-shaped mode-locked optical spectrum is observed; the wave- refractive index changes (Kerr effects) in the Ti3 C2 Tx nanosheets
length center is located at 1065.89 nm with 4.4 nm bandwidth were investigated, and the determined nonlinear refractive index
at 3 dB. The mode-locking pulse duration is characterized via a was observed to be comparable to the level of the 2D material
digital oscilloscope to be 480 ps. The mode-locked pulsed is heav- pioneering material of graphene. Considering the lower linear
ily chirped, with a time-bandwidth product of 557.7, because of absorption losses of MXene Ti3 C2 Tx (1 %/nm[14] ) compared to
the bandwidth filter. The radio frequency (RF) spectrum shows a graphene (2.3 % per atomic layer[53] ), it is likely that MXene will
clean fundamental peak at 18.96 MHz, which is consistent with deliver similar or even better optical manipulating performance
the optical path of the fiber cavity. The absence of any parasitic in photonic applications. Considering the multifaceted nature of
side peaks and a signal-noise ratio (SNR) of >56 dB confirm the MXene family and their highly electronic/optical tunability, MX-
highly stable mode-locking operation. ene has the potential to be exploited as a novel 2D nonlinear op-
To demonstrate the broadband optical switches capabilities of tical material. However, the understanding of the light/MXene
MXene Ti3 C2 Tx , we established a similar fiber ring cavity with interaction and the nonlinear optical phenomena in MXene is
an Er-doped fiber gain medium, which is widely used as the still at the early stage, and there exist many unexplored MXene-
basis of light sources in telecommunication applications. The related nonlinear photonic applications that warrant further in-
Ti3 C2 Tx is prepared in a similar manner as that in the previ- vestigation. The work presented in this contribution may open
ous experiment; however, the bandpass filter is removed because a path towards understanding MXene’s unique NLO properties
of the anomalous dispersion state of the cavity. Highly stable and enable an excellent 2D material to be used in nonlinear pho-
self-started CWML is readily obtained when the pump power is tonics, optoelectronics and plasmonics.
above 60 mW. The output power, pulse energy and peak power at
pump power of 238 mW are 3 mW, 410 pJ and 2578.6 W, respec-
tively. The power and energy performances in this work are com-
parable to those of the erbium-doped mode-locked fiber lasers Supporting Information
using saturable absorbers based on other 2D materials, includ- Supporting Information is available from the Wiley Online Library or from
ing graphene, TMDCs, black phosphorus, Bi2 Se3 , and Sb2 Te3 the author.
TIs, and the very recently reported MXene Ti3 CNTx (see Table
S1). A typical pulse train is shown in Figure 8b with an inter-
pulse time difference of 137.4 ns, corresponding to the cavity
length of 27.2 m. The mode-locked wavelength range from 1550 Acknowledgments
to 1620 nm covers the whole conventional telecommunication
Xiantao Jiang and Shunxiang Liu contributed equally. Finan-
band (C-band). The autocorrelation trace of the corresponding
cial support from the National Natural Science Foundation
mode-locked pulse is shown in Figure 8d. According to the fit to of China (Grant Nos. 61435010 and 61575089), the Sci-
a squared hyperbolic secant (sech2 ) pulse shape, the pulse dura- ence and Technology Innovation Commission of Shenzhen
tion is estimated to be 159 fs, corresponding to a time bandwidth (Grant Nos. KQTD2015032416270385, JCYJ20150625103619275,
product (TBP) of 0.45. This finding indicated that the mode- JCYJ20170302153540973 and JCYJ20170412111625378), the Science
locked pulses are slightly chirped. This pulse duration via evanes- and Technology Planning Project of Guangdong Province (Grant No.
2016B050501005), the Educational Commission of Guangdong Province
cent field interaction in the Er-doped fiber laser is remarkably
(Grant No. 2016KCXTD006), the Shenzhen-Hong Kong Innovation
shorter than the previously reported pulse durations (see Table Cooperation Project (Grant No. SGLH20150205162842428), the Science
S1). Such short pulses are comparable to commercial Er-doped and Technology Development Fund (No. 007/2017/A1), Macao SAR,
femtosecond fiber laser sources that are practically applicable China, and the Student Innovation Development Fund of Shenzhen
for materials processing and laser probing.[52] The highly stable University (PIDFP-ZR2017002) are gratefully acknowledged.

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Conflict of Interest [23] P. Urbankowski, B. Anasori, T. Makaryan, D. Er, S. Kota, P. L. Walsh,

M. Zhao, V. B. Shenoy, M. W. Barsoum, and Y. Gogotsi, Nanoscale
The authors have declared no conflict of interest. 2016, 8, 11385.
[24] Z. M. Sun, D. Music, R. Ahuja, S. Li, and J. M. Schneider, Phys. Rev.
B 2004, 70, 3.
[25] Y. Gogotsi, Nat. Mater. 2015, 14, 1079.
Keywords
[26] B. Anasori, M. R. Lukatskaya, and Y. Gogotsi, Nat. Rev. Mater. 2017,
large Kerr coefficient; mode-locked femtosecond lasers; MXene Ti3 C2 Tx ; 2, 16098.
nanomaterials; nonlinear optical properties [27] B. Anasori, C. Shi, E. J. Moon, Y. Xie, C. A. Voigt, P. R. C. Kent, S. J.
May, S. J. L. Billinge, M. W. Barsoum, and Y. Gogotsi, Nanoscale Horiz.
Received: August 22, 2017 2016, 1, 227.
Revised: October 6, 2017 [28] M. Naguib, V. N. Mochalin, M. W. Barsoum, and Y. Gogotsi, Adv.
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