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Ultralarge Flakes of Ti3C2Tx MXene via Soft

Delamination
Mikhail Shekhirev, Jeffrey Busa, Christopher E. Shuck, Angel Torres, Saman Bagheri, Alexander Sinitskii,
and Yury Gogotsi*
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ABSTRACT: Two-dimensional (2D) titanium carbide MXene (Ti3C2Tx) has

attracted significant attention due to its combination of properties and great
promise for various applications. The size of the 2D sheets is a critical parameter
affecting multiple properties of assembled films, fibers and 3D structures. The
increased lateral size of MXene flakes can benefit not only their assemblies by
improving the interflake contacts and alignment but also fundamental studies at
the individual flake level, allowing for facile patterning and investigation of
intrinsic physical properties of MXenes. Increasing the average size of the parent
MAX phase is one of the strategies previously used to increase the flake size of the resultant MXene. Here, we show that the
protocol used for the next step of the synthesis procedure, delamination of multilayer MXene into individual nanosheets,
significantly affects the lateral size of the resultant flakes. We developed a soft delamination approach, which prevents fracture
of flakes and preserves their size. Combining this approach with the large-grain Ti3AlC2 MAX phase precursor, we achieved
individual flakes of up to 40 μm in lateral size. These flakes can be used for patterning multiple contacts and fabrication of
field-effect transistors for multiprobe electrical characterization and other measurements. These findings indicate the
importance of controlling the delamination process in order to achieve large MXene flakes and improve properties of MXene-
based materials and devices.
KEYWORDS: MXene, delamination, large flakes, Ti3C2, 2D materials

INTRODUCTION flake size of oxides and chalcogenides at the micrometer

level.17
Starting with the first exfoliation of graphene crystals,1 different
Titanium carbide (Ti3C2Tx) was the first discovered18 and
two-dimensional (2D) materials, including hexagonal boron
remains the most studied MXene14 with many potential
nitride and transition metal chalcogenides, have been isolated
applications facilitated by a combination of its physical and
and investigated.2 Fabrication techniques, such as micro- chemical properties.14,19 High electrical conductivity,20 easy
mechanical exfoliation and chemical vapor deposition (CVD),3 dispersion in water,21 and rich surface chemistry22 are among
enabled fabrication of large 2D crystals, providing a facile the advantages of MXenes compared to other 2D materials,
platform to study fundamental properties of 2D materials and which brings MXenes to the forefront of research and
heterostructures. In comparison, synthesis of 2D transition development in the materials field. In case of Ti3C2Tx
metal carbides and/or nitrides (MXenes) via chemical etching MXene, its original synthesis heavily relied on sonication of
has not provided such large individual crystals, limiting the the chemically etched Ti3AlC2 MAX phase, and the reported
studies at the single-flake level to just a few examples.4−12 flake size was typically in the sub-micrometer range.18 Further
Large flakes are also extremely important for bulk applications synthetic improvements resulted in the minimally intensive
of MXenes in printed electronics, energy storage, and layer delamination (MILD) method, which avoided the
composite materials,13,14 all of which are rapidly advancing extensive sonication of etched product, and the size of
due to the scalability of the solution synthesis of MXenes and Ti3C2Tx MXene flakes increased up to several micrometers.5
their facile processing. Average flake size is widely recognized This work reports on an improvement in the Ti3C2Tx flake size
as one of the critical parameters for any solution-synthesized by another order of magnitude, which will benefit a broad
2D material. For example, preparation of ultralarge flakes of range of MXene applications.
another popular solution-processable 2D material, graphene
oxide (GO), had been an important target of many dedicated Received: May 8, 2022
studies.15,16 Besides GO, fabrication of large flakes of other 2D Accepted: July 20, 2022
materials in solution had been challenging, keeping the typical

© XXXX American Chemical Society https://doi.org/10.1021/acsnano.2c04506

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Figure 1. Comparison of single-layer MXene flakes prepared by regular delamination and soft delamination. Optical micrographs of the
flakes on a Si/SiO2 wafer prepared by (a) traditional delamination approach and (b) soft delamination. (c) Schematic illustration of the two
approaches.

The lateral size of the nanosheets plays a crucial role in the the size by breaking the flakes. We developed a soft
resultant properties. Since MXenes are typically used as delamination approach that preserves the flakes while allowing
assembled films or fibers, the flake size significantly affects the them to separate from the multilayer particles when deposited
interflake contacts, which are important for conductivity, on substrates. Using this approach, we demonstrate the
mechanical, and thermal properties. Several publications23,24 synthesis of ultralarge MXene flakes with a lateral size of up
have demonstrated increased conductivity of vacuum-filtered to 40 μm. The large size of individual flakes is expected to
films and assembled fibers with increasing flake size of Ti3C2Tx translate into improved electrical, mechanical, and barrier
due to improved interflake contacts and flake alignment. Zhang properties of MXene films and composites. It also provides an
et al.25 also demonstrated that the parent MAX phase used for opportunity for patterning multiple electrical contacts on a
the etching process affects the size of the resultant MXene single flake, as shown with a field-effect transistor, which is
flakes. By eliminating the small MAX particles before the beneficial for electrical measurements of MXenes. Our findings
etching step, the authors prepared MXene with increased flake indicate parameters necessary to control to fabricate large
size, which translated into enhanced mechanical properties and MXene flakes, which will enable the production of MXene
electrical conductivity of the assembled films. Larger Ti3C2Tx films and assemblies with improved properties.
MXene flakes should also translate into improved barrier
properties in membranes as well as more efficient percolation RESULTS AND DISCUSSION
of the flakes in a polymer or ceramic matrix. Still, translating In general, Ti3C2Tx MXene is prepared by acid etching of
progress in the fabrication of large MAX phase particles26,27 aluminum from the Ti3AlC2 MAX phase.14 After the etching is
into large MXene flakes had been challenging. finished and the multilayer MXene is washed to neutral pH,
While MXenes are typically used as multiflake assemblies, the delamination process is typically carried out by stirring the
single-flake characterization and property measurements are powder in a LiCl solution, followed by repeated cycles of
crucially important and require a large flake size, ideally over shaking and centrifugation.26 While some flakes can exceed 10
10−20 μm. Recent studies have suggested that single-layer μm in size, on average, the flakes are smaller (1−10 μm as
MXene flakes can be used as electrodes for various electronic measured by DLS) than the parent MAX phase particles and
devices28 or high-voltage interconnects,11 due to the high multilayer MXene, showing a wide distribution of sizes.
electrical conductivity and breakdown current density of Furthermore, these flakes often demonstrate rough edges and
Ti3C2Tx. In comparison to graphene or transition metal irregular shapes that are different from the shape of the
dichalcogenides, where large-area monolayers can be prepared precursor MAX particles.26 We assumed that the delamination
via CVD or micromechanical exfoliation,3 MXene flakes used step was causing the individual MXene flakes to break, thus
in single-flake studies are limited in size due to the nature of resulting in a decreased flake size and irregular shape. Figure 1a
the synthetic process. shows a typical optical microscopy image of Ti3C2Tx flakes
Here we demonstrate that delamination is the size-limiting prepared by the traditional delamination protocol.
step for MXene synthesis. Particularly, shaking, which is In this report, we demonstrate that by utilizing a soft
typically employed for “mild” delamination, negatively affects delamination approach it is possible to preserve the flakes and
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Figure 2. Soft delamination of MXene. (a) Schematic of the soft delamination process. (b) Photograph of the bottles with MXene solutions
collected during delamination. (c) Optical micrograph of the flakes deposited on the Si/SiO2 substrate via drop-casting. (d) AFM image of
delaminated flakes. The inset shows the height profile along the dashed line. (e) Photograph of vials before and after hand shaking. (f)
Optical micrograph of the flakes from the shaken solution deposited on a Si/SiO2 substrate. (g, h) Optical micrographs of flakes deposited
from an unshaken solution and the solution shaken with vortex. (i, j) Optical micrographs of flakes delaminated from the multilayer
particles.

translate the size of the parent MAX phase particles into (SEM) imaging on Si/SiO2 does not provide enough contrast
individual delaminated flakes. An example of the flakes to properly visualize the flakes (SE2 detector, Figure S1d) or
prepared by this protocol is shown in Figure 1b. These flakes distinguish single- and few-layer flakes (InLens detector, Figure
demonstrate crystallographic edges with the overall shapes S1c). Anodic aluminum oxide (AAO) membranes, which are
resembling the parent MAX particles (Figure S1a,b). All the typically used for SEM imaging of MXene flakes,30 can provide
light-colored flakes are of the same thickness and represent the necessary contrast to identify the single-layer flakes;
single-layer MXene. There are a few double- and multilayer however, we found that the porous nature of the membranes
flakes in the view field in Figure 1b, which are darker in color. may damage the large flakes upon drying/deposition due to
The protocol for the soft delamination is schematically capillary forces in the membrane channels (Figure S1e,f).
shown in Figure 2a. After stirring the multilayer particles in Transmission electron microscopy (TEM) imaging is relatively
LiCl solution, the solution was allowed to settle for time- and cost-consuming and has a limitation of the small
approximately 30 min. During this time, most of the particles field of view (Figure S1g,h), making this technique
precipitate to the bottom of the container. After that, the inconvenient for evaluating large flakes. Distinguishing the
supernatant was carefully pipetted out of the container and number of layers is difficult in both electron microscopy
collected. The bottle was then refilled with water, and MXene techniques. Thus, we primarily used optical microscopy as an
was gently redispersed by inverting the bottle several times. imaging tool to assess delamination.
After allowing the solution to settle for about 30 min, the The deposited MXene flakes (Figure 2c) show a mixture of
procedure was repeated multiple times until the supernatant few- and multilayer MXene particles alongside the single-layer
became transparent, indicating a low concentration of MXene. flakes. These flakes are larger than those prepared via the
Figure 2b shows the bottles containing the solution collected conventional delamination protocol (Figure 1a), with an
during this process. At the beginning (bottles 1−4), the average size of approximately 14 μm. The size distribution for
collected particles settled quickly due to the presence of the single-layer MXene flakes is shown in Figure S2.
concentrated LiCl in solution. As the concentration of LiCl Furthermore, the shape of the monolayer flakes resembles
decreases, MXene flakes start to delaminate spontaneously, the shape of the multilayer particles and the precursor MAX
forming a stable colloidal solution, which visually appears particles (Figure S1a,b),26 indicating that the soft delamination
much darker. The most concentrated solution was found to technique preserves the flake size and shape. Atomic force
contain approximately 2.5 mg of MXene per milliliter, with the microscopy (AFM) imaging of these flakes (Figure 2d) further
total yield of approximately 47%. confirms that the flakes are single-layer. The height profile was
Figure 2c shows optical microscopy image of the flakes from measured at approximately 3.1 nm, which exceeds the
bottle #5 deposited on a Si/SiO2 substrate. Optical microscopy theoretical monolayer MXene thickness due to trapped water
is the best tool to evaluate the delamination process, as it is and other molecules in between the flake and the substrate, but
quick and convenient and provides excellent contrast to image is in agreement with the previous measurements of monolayer
even single-layer MXene flakes.29 Furthermore, optical Ti3C2Tx MXene on Si/SiO2.5,6
microscopy can easily distinguish the single-, double-, and To illustrate the necessity for soft delamination, we hand
few-layer flakes. In comparison, scanning electron microscopy shook a vial of MXene with the large flakes. After shaking the
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solution, MXene immediately formed a stable colloidal

solution (Figure 2e), which is typically observed during
MXene synthesis.30 The shaking, however, breaks the flakes
into smaller particles, as evident from the optical microscopy
images of the resultant MXene (Figure 2f). This experiment
clearly illustrates that the large flakes, having an aspect ratio of
over 10 000, are fragile, and the soft delamination is necessary
to preserve the flake size. We speculated that applying low-
intensity and well-controlled shear force via swirling the
solution (using vortex or orbital shaking) or spin-coating at
low speeds can aid the delamination process. Indeed, vortex
shaking for 21 h significantly reduced the number of multilayer
particles (compare Figure 2g and h). Spin-coating of the
solution on Si/SiO2 substrates at low speeds (500 rpm) yields
similar results, reducing the number of multilayer particles
observed (Figure S3). However, few-layer particles and broken
single-layer flakes were still observed, and further optimization
of the shaking and deposition parameters is necessary to
produce uniformly single-layer MXene.
Interestingly, single-layer flakes usually concentrate close Figure 3. Time-lapse sequence of optical micrographs of multilayer
together in several areas on the substrate, while other sites MXene flakes suspended in a water droplet deposited on a Si/SiO2
typically consist of only multilayer particles. On multiple substrate. Upon drying, the flakes separate from the parent
occasions, we also observed areas where single-layer MXene multilayer MXene (indicated by arrows) and deposit on the
flakes were in close proximity to the parent multilayer particles. substrate (indicated by circles). The last image (230 s) shows a
Figure 2i,j demonstrates examples of MXene flakes delami- completely dried sample. The full video is available as
nated from the parent multilayer particle in the same area, as Supplementary Video 1.
the specific shape of the multilayer particle is inherited by the
single-layer flakes. This fact suggests that the single-layer flakes were randomly distributed across the substrate (Figure
MXene flakes are not present in solution by themselves but S4) when deposited via drop-casting. These experiments
most probably are delaminated from the multilayer particles indicate that the soft delamination process is not instanta-
during processing as the capillary or created shear forces neous, as the freshly deposited flakes are still in the process of
separate the flakes. delamination, and aging or agitation is required to separate
To confirm this mechanism, we performed optical individual flakes from the multilayer particles. Importantly,
microscopy analysis of MXene in solution while allowing these experiments demonstrate another advantage of the large
water to evaporate. Video recording of the process is available flakes fabricated in this work: the ability to perform imaging
as Supplementary Video 1; the time-lapse sequence of images using optical microscopy and visualize the delamination
is shown in Figure 3. In this case, a sample of large MXene process in situ.
particles, the synthesis of which will be discussed later, was The size of the resultant MXene flakes is limited by the size
delaminated using the soft delamination protocol, and a of the parent MAX particles. In order to increase the size of
droplet of the solution was placed on a Si/SiO2 substrate. In MXene flakes, we prepared larger MAX particles by annealing
solution, swelled multilayer MXene particles are elongated the precursor powder containing TiC, Ti, and Al for 24 h at
along the direction perpendicular to the basal plane of the 1400 °C, compared to the usual 2 h (see the Experimental
nanosheets, indicating significant separation of MXene layers. Section for details). Figure 4a shows the powder X-ray
Similar swelling of etched MAX was recently observed as a diffraction (XRD) pattern of the MAX powder, which is in
result of osmotic swelling.31 Flakes in these structures, perfect agreement with the XRD of Ti3AlC2 obtained after
however, still have several points of connection. Upon drying, annealing for 2 h. The resultant powder was sieved into three
the multilayer MXene particles move and MXene sheets fractions with the particle sizes of <20, 20−38, and 38−75 μm,
separate from the parent multilayer particles at the points which accounted for 30, 55, and 15 wt %, respectively. In
where two larger stacks break apart (indicated by arrows in comparison, 80 wt % of the MAX powder prepared by
Figure 3). Eventually, these flakes deposit in the nearby area annealing for 2 h was particles below 20 μm in size.
(indicated by circles in Figure 3) when the water is completely We selected two of the largest fractions, namely, 20−38 and
evaporated. This process is not uniform, as some multilayer 38−75 μm, and etched them for different periods of time (see
particles do not separate into individual flakes, yielding the Experimental Section for details). In both cases, etching for
multilayer MXene deposits on the substrate (stack 1 in Figure 72 h provided complete etching with no MAX phase detected
3). In some cases, the flakes continue to have some points of via XRD; only the (00l) series of MXene peaks was observed,
contact throughout the drying process, resulting in elongated starting with (002) peak at 2θ = 8.5°. In contrast, 48 and 24 h
ribbons of overlapping flakes (parts of the stack 2 in Figure 3). etching procedures showed the peaks of residual Ti3AlC2,
This mechanism was only observed for freshly deposited which decreased in intensity as the etching time increased
samples. For the samples that were stored in solution for an (Figure 4b,c).
extended period of time (approximately one month), the Figure 4d shows optical microscopy images of the MAX
single-layer sheets were already separated, and the multilayer particles prepared by annealing for 2 h, compared to the
particles that were left in solution did not delaminate during particles from the 20−38 and 38−75 μm fractions (Figure
the drying process. As a result, single- and few-layer MXene 4e,f). The longer-annealed particles are noticeably larger,
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Figure 4. Synthesis of large MXene flakes from large MAX particles. (a) XRD of Ti3AlC2 MAX phase prepared by annealing at 1400 °C for 2
or 24 h. (b, c) XRD of MXene etched for different time periods. (d, e, f) Optical micrographs of MAX phase. (g, h, i) Optical micrographs of
MXene etched from the 20−38 μm MAX fraction for different time periods, delaminated using the soft delamination protocol and deposited
on Si/SiO2 substrates. Insets schematically demonstrate the etching process that starts from outer layers, which leads to different sizes of the
flakes.

which increases the limit for the possible MXene flake size. μm, the largest flakes we observed were approximately 40 μm
The size distribution for the MAX particles is shown in Figure in size, as shown in Figure S5.
S2a−d. Unfortunately, our attempts to delaminate the largest The large average size of MXene flakes achieved in this study
38−75 μm fraction etched for 72 h were unsuccessful; MXene expands the horizons of their electronic applications.33 Many
flakes did not spontaneously delaminate, and we observed only recent studies on electronic,34,35 photovoltaic,36 and sens-
multilayer MXene particles as a result. The reasons are not ing37,38 applications of MXenes employed thin films consisting
clear at the moment, but may include strong bonding between of multiple overlapping flakes. Noteworthy, the electrical
large MXene sheets, for instance, due to incompletely removed properties of such films are affected by interflake contacts,
etching byproducts. which strongly depend on the surface chemistry of MXenes
However, delamination of the 20−38 μm particles using the and the presence of intercalated molecules.39 These factors
soft delamination protocol was successful. Figure 4g,h,i shows greatly increase the number of variables affecting the device
optical microscopy of the flakes obtained after soft performance. However, with flake dimensions well exceeding
delamination of the 20−38 μm fraction etched for different 10 μm, as demonstrated in this work, it is feasible to consider
individual MXene flakes as electrical contacts28 or active
times. Interestingly, even incomplete etching for 24 and 48 h
channels5,10,12 of various electronic devices. Importantly, such
yielded single-layer flakes, though the flake size was smaller.
large flakes provide sufficient space for facile patterning of
The size distribution for the MXene flakes is shown in Figure
multiple electrical contacts, as we demonstrate for the MXene
S2f−h. This fact can be rationalized by examining the
device shown in Figure 5a. The SEM image in this figure shows
mechanism of the etching process described in ref 32. The a monolayer Ti3C2Tx flake with six Cr/Au electrodes patterned
etching front is not moving uniformly from the edge of the by standard electron beam lithography (EBL). In general, such
MAX particles but predominantly starts from the surface electrode geometry enables several kinds of electrical
layers. As a result, in the case of incomplete etching, where the characterization ranging from four-probe testing to Hall effect
MAX phase is still present in the sample, the top layers of the measurements. With the size of this flake of >10 μm, additional
MAX particles can be completely etched and provide single- metal probes could have been placed on this MXene
layer flakes upon delamination. As the etching process monolayer, if necessary.
continues, deeper layers of the MAX phase are transformed Figure 5b shows an AFM image of a portion of the Ti3C2Tx
into MXene and become available for delamination, providing device channel. Even after the device fabrication, the flake has a
larger MXene flakes. This mechanism is schematically clean and uniform surface without visible EBL resist residues.
illustrated in the insets of Figure 4g,h,i. Naturally, as the The height profile of this flake reveals its thickness of about 2.6
MAX phase used in these experiments was sieved below 38 nm, which is consistent with the values previously measured by
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Figure 5. Electrical measurements of monolayer Ti3C2Tx flakes. (a) False-color SEM image of a multiterminal device based on a large
monolayer Ti3C2Tx MXene flake. The Cr/Au electrodes are colored in yellow for clarity. (b) Top panel: AFM image of a portion of the
Ti3C2Tx MXene device channel that is marked by a rectangle in panel (a). Bottom panel: AFM height profile measured across the Ti3C2Tx
MXene flake along the gray dashed line in the top panel. (c) IDS−VDS dependence measured between the inner probes of the Ti3C2Tx device
shown in (a). (d) IDS−VG dependence measured between the inner probes of the Ti3C2Tx device shown in (a) at VDS = 0.1 V.

AFM for monolayer Ti3C2Tx flakes on Si/SiO2 substrates.5,6,11 Ti3C2Tx MXene; see details in our previous works.5,11 The
It should be noted that while the theoretical thickness of a calculated field-effect electron mobility of about 4.2 cm2 V−1
Ti3C2Tx monolayer is about 0.98 nm,6 in the experimental s−1 for the device shown in Figure 5a is consistent with the
AFM images, the monolayer Ti3C2Tx flakes on Si/SiO2 appear values previously reported for monolayer Ti3C2Tx MXene11
much thicker, with thicknesses typically in the range of 2.5−3 prepared by the same synthetic method.26
nm, which is likely due to the effect of adsorbed molecules,
such as water. CONCLUSIONS
The Ti3C2Tx MXene flakes prepared in this study were The size of the delaminated Ti3C2Tx MXene depends on the
highly electrically conductive, as illustrated by Figure 5c. The Ti3AlC2 precursor particles, synthesis approach, and delami-
figure shows the current (IDS)−voltage (VDS) dependence that nation protocol. We show that sonication and shaking decrease
was measured between the inner probes of the device shown in the average size of MXene flakes, causing the flakes to break
Figure 5a. The IDS−VDS dependencies exhibit an ohmic into smaller particles. By eliminating shaking and employing
behavior, suggesting good electrical contacts between the the soft delamination approach described in this report, it is
Ti3C2Tx MXene and the Cr/Au electrodes. From the IDS−VDS possible to translate the size of the parent MAX particles into
data, the geometrical parameters of the device, and the individual MXene flakes. By using large MAX particles as
theoretical thickness of the Ti3C2Tx monolayer of 0.98 nm,6 precursors, we demonstrate MXene flakes of up to 40 μm in
we calculated the electrical conductivity of about 6500 S cm−1, size. These flakes can be used for fabrication of various
which is consistent with the recently reported measurements11 electronic devices with enough space for patterning multiple
of MXenes prepared by the same synthetic method.26 Because contacts on a single flake. We anticipate the results of this work
the device was prepared on a p-doped Si substrate covered will further facilitate investigation of fundamental properties of
with a 300-nm-thick layer of SiO2, we could use the electrically MXenes at the individual flake level and will initiate fabrication
of MXene-based materials with improved properties due to the
conductive silicon layer as a global gate electrode in field-effect
increased flake size.
measurements. The resulting dependence of the current
between the inner probes in the same device (Figure 5a) on EXPERIMENTAL SECTION
the gate voltage (VG) is shown in Figure 5d. The positive slope
Synthesis of the Ti3AlC2 MAX Phase. Synthesis of the Ti3AlC2
of the IDS−VG dependence suggests the n-type conductivity of MAX phase was adapted from ref 26. In short, TiC, Ti, and Al
Ti3C2Tx MXene, which is consistent with the previous powders (2:1:1 mass ratio) were ball-milled for 18 h using zirconia
measurements.5,11 From the IDS−VG dependence, we also balls. The mixture was annealed at 1400 °C for 2 h under an Ar
calculated the field-effect electron mobility for monolayer atmosphere. The sintered compact was powdered and washed with 9

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M HCl for 18 h to remove the intermetallic impurities. The resulting ASSOCIATED CONTENT
MAX powder was washed with water and dried under vacuum at 80 *
sı Supporting Information
°C for 6 h and sieved using 400 mesh sieves to obtain MAX particles
The Supporting Information is available free of charge at
with a particle size below 38 μm.
https://pubs.acs.org/doi/10.1021/acsnano.2c04506.
To fabricate large MAX particles, the ball-milled precursor powders
(TiC, Al, Ti) were annealed at 1400 °C for 24 h. The sintered block Figures of electron microscopy characterization of the
(without grinding or powdering) was immersed in 9 M HCl for 3 Ti3AlC2 MAX phase and the large MXene flakes, size
days to remove the intermetallic impurities, then washed with water distribution for the MAX phase particles used in this
until neutral pH and dried in a vacuum at 80 °C for 6 h. The resulting study and the single-layer MXene flakes fabricated via
powders were separated into three samples with particles of <20, 20− soft delamination, optical microscopy of the large
38, and 38−75 μm. MXene flakes deposited via spin-coating at different
Etching Ti3C2Tx MXene. Synthesis of Ti3C2Tx MXene was speeds, in situ optical microscopy of an aged sample
adapted from ref 26. One gram of Ti3AlC2 MAX powder was slowly upon drying, optical microscopy of the large flakes
added to 20 mL of the mixture of concentrated HF (49 wt %), fabricated from the 20−38 μm fraction of the MAX
concentrated HCl (36 wt %), and DI H2O with a volumetric ratio of phase etched for 72 h and delaminated using the soft
1:6:3. The MAX phase was etched at 35 °C for a specific amount of delamination approach (PDF)
time, which was varied between 24 and 72 h. After the reaction was Supplementary Video 1: Delamination of MXene flakes
complete, MXene was washed with DI water via multiple cycles of in solution upon water evaporation tracked via optical
centrifugation until neutral pH. microscopy (MP4)
Delamination of Ti3C2Tx MXene. To intercalate Li+ ions
between the layers of MXene, the multilayer MXene was stirred at
300 rpm in a solution of 1 g of LiCl in 50 mL of water at 35 °C for 18
AUTHOR INFORMATION
h. For the regular delamination, LiCl was removed from the solution Corresponding Author
by centrifuging it for 5 min at 3500 rpm and discarding the clear Yury Gogotsi − A. J. Drexel Nanomaterials Institute and
supernatant. After that, the MXene powder was completely Department of Materials Science and Engineering, Drexel
redispersed in water via shaking and centrifuged for 15 min at 3500 University, Philadelphia, Pennsylvania 19104, United States;
rpm (to precipitate the multilayer MXene and unreacted MAX orcid.org/0000-0001-9423-4032; Email: gogotsi@
particles), and the dark supernatant containing single-layer MXene drexel.edu
was collected.
For the soft delamination, after the LiCl intercalation, the solution Authors
was left undisturbed for approximately 30 min to precipitate the Mikhail Shekhirev − A. J. Drexel Nanomaterials Institute and
multilayer MXene particles, and the clear supernatant was removed Department of Materials Science and Engineering, Drexel
via pipetting. Then the vial was refilled with water, MXene was gently University, Philadelphia, Pennsylvania 19104, United States;
redispersed by inverting the vial several times, and the vial was again orcid.org/0000-0002-8381-1276
left undisturbed for another 30 min, after which the supernatant was Jeffrey Busa − A. J. Drexel Nanomaterials Institute and
collected. After several cycles, the MXene started to delaminate Department of Materials Science and Engineering, Drexel
spontaneously, and the solution became dark. We continued University, Philadelphia, Pennsylvania 19104, United States
collecting the supernatant following these steps until all the dark Christopher E. Shuck − A. J. Drexel Nanomaterials Institute
solution was collected. and Department of Materials Science and Engineering, Drexel
Characterization of MXene. MXene solutions were drop-casted University, Philadelphia, Pennsylvania 19104, United States;
on Si/SiO2 substrates with a 300 nm oxide layer and imaged via a orcid.org/0000-0002-1274-8484
KEYENCE VK-X1000 optical microscope. AFM analysis was Angel Torres − Department of Chemistry and Nebraska
performed using a Bruker Multimode 8 instrument in tapping Center for Materials and Nanoscience, University of
mode. SEM analysis was performed using a Zeiss Supra 50VP electron Nebraska−Lincoln, Lincoln, Nebraska 68588, United States
microscope. TEM imaging was performed using a JEOL 2100 Saman Bagheri − Department of Chemistry and Nebraska
instrument. A Rigaku Miniflex diffractometer was used for XRD Center for Materials and Nanoscience, University of
studies with Cu Kα radiation and the following conditions: (i) for the Nebraska−Lincoln, Lincoln, Nebraska 68588, United States;
MAX powder, step scan of 0.02°, 2θ = 5−90°, step time of 1 s; (ii) for orcid.org/0000-0002-4206-3021
the MXene films, step scan of 0.03°, 2θ = 3−70°, step time of 0.5 s. Alexander Sinitskii − Department of Chemistry and Nebraska
Electrical Characterization of Individual MXene Flakes. Center for Materials and Nanoscience, University of
Ti3C2Tx flakes fabricated from the regular MAX powder (annealed Nebraska−Lincoln, Lincoln, Nebraska 68588, United States;
for 2 h) via soft delamination protocol were deposited on Si/SiO2 orcid.org/0000-0002-8688-3451
substrates and then used for device fabrication, as described in our
previous work.11 In brief, the contacts on Ti3C2Tx flakes were Complete contact information is available at:
patterned by electron beam lithography using a Zeiss Supra 40 field- https://pubs.acs.org/10.1021/acsnano.2c04506
emission scanning electron microscope and a Raith pattern generator,
and then the metallization of contacts was performed using an AJA Notes
electron beam evaporation system. The metallization involved a The authors declare no competing financial interest.
deposition of 3 nm of Cr and 15 nm of Au. The Ti3C2Tx devices were
imaged by SEM using a Zeiss Supra 40 field-emission scanning ACKNOWLEDGMENTS
electron microscope, as well as by AFM using a Bruker Dimension The development of MXene synthesis was supported by
Icon atomic force microscope. The electrical measurements were Murata Manufacturing, Japan, and research on electronic
performed using a Lake Shore TTPX cryogenic probe station, which properties of MXenes was supported by the Army Research
was operated at a base pressure of about 2 × 10−6 Torr, and an Laboratory under Cooperative Agreement number W911NF-
Agilent 4155C semiconductor parameter analyzer. 19-2-0119. We thank Dr. Robert Lord for help with TEM
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imaging of MXene flakes. XRD, SEM, and TEM analyses were Chemical Expansion of Graphite. Chem. Mater. 2017, 29 (2), 564−
performed using instruments in the Materials Characterization 572.
Core at Drexel University. The work at UNL was supported by (17) Nicolosi, V.; Chhowalla, M.; Kanatzidis Mercouri, G.; Strano
the Nebraska Public Power District through the Nebraska Michael, S.; Coleman Jonathan, N. Liquid Exfoliation of Layered
Materials. Science 2013, 340 (6139), 1226419.
Center for Energy Sciences Research (NCESR). The device
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National Nanotechnology Coordinated Infrastructure, which is nanocrystals produced by exfoliation of Ti3AlC2. Adv. Mater. 2011,
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2025298) and the Nebraska Research Initiative. (19) Gogotsi, Y.; Anasori, B. The rise of MXenes. ACS Nano 2019,
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