See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/301580597

Fabrication of Ti3C2Tx MXene Transparent Thin Films with Tunable

Optoelectronic Properties

Article  in  Advanced Electronic Materials · April 2016

DOI: 10.1002/aelm.201600050

CITATIONS READS
177 2,259

9 authors, including:

Kanit Hantanasirisakul Meng-Qiang Zhao

Drexel University 94 PUBLICATIONS   8,938 CITATIONS   
27 PUBLICATIONS   635 CITATIONS   
SEE PROFILE
SEE PROFILE

Patrick Urbankowski Joseph Halim

Drexel University Linköping University
16 PUBLICATIONS   1,105 CITATIONS    63 PUBLICATIONS   3,987 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Research on MAB phases View project

Hydrogen Storage View project

All content following this page was uploaded by Kanit Hantanasirisakul on 16 June 2016.

The user has requested enhancement of the downloaded file.

www.MaterialsViews.com www.advelectronicmat.de

Fabrication of Ti3C2Tx MXene Transparent Thin Films with

Full paper
Tunable Optoelectronic Properties

Kanit Hantanasirisakul, Meng-Qiang Zhao, Patrick Urbankowski, Joseph Halim,

Babak Anasori, Sankalp Kota, Chang E. Ren, Michel W. Barsoum, and Yury Gogotsi*

properties of novel transparent electrode

MXenes, a new class of 2D transition metal carbides and carbonitrides, show materials include high transmittances
(>85%) in the UV and visible regions and
great promise in supercapacitors, Li-ion batteries, fuel cells, and sensor
low sheet resistances (Rs), in the range
applications. A unique combination of their metallic conductivity, hydrophilic of 0.01–1 kΩ sq−1. In addition, the new
surface, and excellent mechanical properties renders them attractive for materials should be mechanically robust
transparent conductive electrode application. Here, a simple, scalable method for flexible touch screen and organic light-
is proposed to fabricate transparent conductive thin films using delaminated emitting diode applications. On top of
Ti3C2 MXene flakes by spray coating. Homogenous films, 5–70 nm thick, excellent optoelectronic and mechanical
properties, low cost of production per
are produced at ambient conditions over a large area as shown by scanning
unit area and feasibility of large-scale fab-
electron microscopy and atomic force microscopy. The sheet resistances rication are key factors determining their
(Rs) range from 0.5 to 8 kΩ sq−1 at 40% to 90% transmittance, respectively, industrial success.[1a,2]
which corresponds to figures of merit (the ratio of electronic to optical Among numerous materials being con-
conductivities, σDC/σopt) around 0.5–0.7. Flexible, transparent, and conductive sidered for transparent electrode appli-
cations, 2D graphene is arguably the
films are also produced and exhibit stable Rs values at up to 5 mm bend radii.
most studied in the past few years.[1e,3]
Furthermore, the films’ optoelectronic properties are tuned by chemical or Transparent conductive graphene films
electrochemical intercalation of cations. The films show reversible changes of are mainly produced by two methods:
transmittance in the UV–visible region during electrochemical intercalation/ direct chemical vapor deposition (CVD) or
deintercalation of tetramethylammonium hydroxide. This work shows the solution-processing of reduced graphene
potential of MXenes to be used as transparent conductors in electronic, oxide (rGO).[4] Although the CVD method
results in high-performance films, their
electrochromic, and sensor applications.
high fabrication cost and size limitations
have hindered their commercialization.
Several solution-processing methods,
such as spray coating, spin coating, and dip coating, have also
1. Introduction been employed to fabricate thin films from rGO solutions.[5]
However, the transparent films produced by such methods
Transparent conductive electrodes are essential components in exhibit high Rs (1–1000 kΩ sq−1), mainly due to defects (func-
many electronic devices, including touch screens, liquid-crystal tional groups) and inter-flake resistance.[6] The development of
displays, dye-sensitized solar cells, electrochromic devices, novel materials for transparent conductive films and suitable
and sensors among others. To date, the transparent conduc- methods for their large-scale and low-cost production remains
tive electrode of choice is indium tin oxide due to its excellent a challenge.
optoelectronic properties. However, there are ongoing efforts to Recently, a new class of 2D transition metal carbides and/or
replace it with alternative materials, such as conducting poly- nitrides, so-called MXenes, was discovered.[7] Both theoretical
mers, metal and carbon-based nanostructures.[1] The required and experimental results indicate that most MXenes exhibit
metallic conductivity, hydrophilicity, high mechanical strength,
and can act as intercalation hosts.[8] They have shown great
K. Hantanasirisakul, Dr. M.-Q. Zhao, P. Urbankowski, promise as electrodes in supercapacitors, Li-ion and other types
J. Halim, Dr. B. Anasori, S. Kota, C. E. Ren,
Prof. M. W. Barsoum, Prof. Y. Gogotsi of batteries, fuel cells, reinforcement for polymers, adsorbents,
Department of Materials Science and Engineering and sensors.[9] Upon delamination, colloidal MXene solutions
and A. J. Drexel Nanomaterials Institute contain large quantities of ≈1 nm-thick 2D flakes with lateral
Drexel University sizes up to several micrometers, which are perfect for solu-
3141 Chestnut Street, Philadelphia, PA 19104, USA
E-mail: gogotsi@drexel.edu
tion processing.[10] The Ti3C2 MXene flakes possess surface
functional groups similar to graphene oxides (Ti3C2Tx, where
DOI: 10.1002/aelm.201600050 T stands for O, OH, F, and other surface terminations and x

Adv. Electron. Mater. 2016, 1600050 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (1 of 7)  1600050
 www.advelectronicmat.de
Full paper
Figure 1.  Schematic of Ti3C2Tx film preparation by spray coating. Shown in the box is the Ti3C2Tx structure, where Ti, C, O, and H atoms are shown in
gray, black, red, and white, respectively.
is a number of the terminating groups), but offer a much
higher electrical conductivity. Thus, no post-synthesis reduc-
tion process is needed to generate highly conductive films.[8a]
Free-standing MXene films, with thicknesses ranging from
hundreds of nanometers to tens of micrometers, have been pre-
pared by vacuum-assisted filtration. Some of these films show
high conductivity values of ≈2400 S cm−1, and have been widely
studied for use in energy storage and separation applications.[11]
The properties of MXenes, however, afford great potential for
use as transparent conductive electrodes. For instance, it was
found that MXene films with thicknesses of tens of nanometers
prepared by chemical etching of magnetron-sputtered Ti3AlC2
epitaxial thin films were quite transparent while retaining high
electrical conductivity, i.e., Rs value of 2.3 kΩ sq−1 at 68% trans-
mittance for a 17 nm-thick film.[12] However, MXene films fab-
ricated by such method suffer from the same drawbacks as the
CVD graphene films, viz., they are not practical for large-scale
applications, high cost of fabrication, etc. More recent work has
shown that high quality transparent conductive MXene films
with conductivity exceeding 6500 S cm−1 can be prepared by
spin casting of delaminated Ti3C2Tx solution.[13] It is still impor-
tant to further explore the optical and electrical properties of
solution-processed films, towards the production of MXene-
based transparent and conductive films, at low cost.
Herein, we report a simple process of spray coating of col-
loidal delaminated Ti3C2Tx solution to fabricate transparent
conductive films (Figure 1). Homogeneous transparent conduc-
tive films were produced on various substrates over large areas.
These films exhibit optoelectronic properties exceeding those
of solution-processed transparent graphene films. We further
demonstrated that optoelectronic properties of the films can be
readily altered by the chemical and electrochemical intercalation
of organic and inorganic compounds between the Ti3C2 layers.
2. Results and Discussion
2.1. Ti3C2Tx Thin Films by Spray Coating
The synthesis and delamination of Ti3C2Tx has been described
in detail elsewhere.[11a] A typical transmission electron micro-
scope (TEM) image of a single-layered Ti3C2Tx flake obtained
from a colloidal solution is presented in Figure 2a. The lateral
1600050  (2 of 7) wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
dimension of the flakes is generally in the range of hundreds of
nanometers up to several micrometers. Selective area electron
diffraction (SAED) pattern (see inset of Figure 2a) confirms
the hexagonal symmetry of the flakes and their single-crystal
nature.
The Ti3C2Tx thin films were produced by spray coating of
delaminated Ti3C2Tx (d-Ti3C2Tx) colloidal solutions – with a
concentration of ca. 3.0 mg mL−1 – onto a substrate at room
temperature. X-ray diffraction (XRD) patterns (Figure S1, Sup-
porting Information) show that the film consists of only Ti3C2Tx
MXene flakes without any other phases. The c-lattice parameter
of the films, calculated from the (0002) peak, is 29.5 Å.
Scanning electron microscopy (SEM) images show that the
spray-coated Ti3C2Tx film on a glass slide is homogeneous,
without obvious pin-holes or other types of defect over a con-
siderably large area (Figure 2b, left). Folded edges of Ti3C2Tx
flakes can be seen in the high magnification image (Figure 2b,
right). In the same image, a flake with a lateral size of ≈0.5 μm
is marked with a dotted line. Cross-sectional SEM image of the
film (Figure 2c) indicates that the Ti3C2Tx flakes are aligned
parallel to the glass surface, resulting in a compact thin film.
These Ti3C2Tx films showed good transparency (Figure 2d). In
addition to glass slides, other kinds of substrates, such as flex-
ible polyester sheets, can also be used for the spray-coating of
transparent Ti3C2Tx thin films (Figure 2e). Moreover, no visible
damage was observed on the flexible film even after bending to
a small radius of curvature (inset of Figure 2e). This suggests
that Ti3C2Tx thin films can be used in flexible devices. Figure
2f shows an atomic force microscopy (AFM) image of a typical,
70-nm-thick Ti3C2Tx film on a glass substrate. The surface
roughness was measured as ≈10 nm, which is a typical value
for solution-processed thin films.[14]
2.2. Optoelectronic Properties of the Transparent
Ti3C2Tx Thin Films
The optical properties of the Ti3C2Tx films were evaluated by ultra-
violet–visible (UV–vis) spectrophotometry, and their electrical
conductivities were measured by a four-point probe technique.
The UV–vis spectra of these films with different thicknesses
are presented in Figure 3a. The films obviously absorb light in
the UV region, viz. from 300 to 500 nm. Note that the strong
Adv. Electron. Mater. 2016, 1600050
www.MaterialsViews.com www.advelectronicmat.de

Full paper
Figure 2.  a) TEM image of a single layer Ti3C2Tx flake. SAED pattern is shown in the inset. b) SEM images of Ti3C2Tx films with low (left) and high
(right) magnification. Marked with dotted-line is a Ti3C2Tx flake. c) Cross-sectional SEM image of the film. d,e) Optical images of the films on glass
and a flexible polyester substrate, respectively. Inset in panel (e) shows Ti3C2Tx films on the flexible substrate at high degree of bending. Scale bars in
panels (d) and (e) are equal to 1 cm. f) AFM trace and 3D image of the surface of the film.

absorption peak, centered at 270 nm, corresponds to the glass
substrate. Additionally, a broad absorption band at around 700–
800 nm results in the pale greenish color of the films. Because
of the relatively flat absorption in the visible region, these films
hold promise for display applications. A transmittance of 91.2%
was measured for a 5 nm thick Ti3C2Tx film. Not surprisingly,
with increasing thickness, the transmittance gradually decreases,
but a transmittance of 43.8% is retained when the film thickness
reaches ≈70 nm. Transmittances in 40% to 90% are of interest
for transparent conductive thin film applications.[6]
As shown in Figure 3b, the relationship between absorbance,
A, and thickness, t, (A = 0.005t, R2 ≥ 0.99) is linear. When the
spray coated films (black lines in Fig. 3b) are compared with
Ti3C2Tx thin films prepared by etching DC-magnetron sputtered
MAX phases (green line) and solution-processed rGO films
(blue and pink lines), it is obvious that the former have a much
better transparency at the same thickness (Figure 3b).[12,14b,15]
Computational studies have shown that the surface chem-
istry of MXenes and the presence of intercalated species can
play affect on their electronic properties.[16] Thus, it was antici-
pated that changes in MXene surface chemistries would sig-
nificantly affect their optoelectronic properties. For a simple
comparison, we prepared Ti3C2Tx thin films by spray coating
of water-based and ethanol-based d-Ti3C2Tx solutions and com-
pared their optoelectronic properties. Based on Figure 3c, it is
obvious that films made starting with the water-based solutions
are always less resistive than their ethanol-based counterparts
at similar transmittance values. This might be due to the
exchange of the surface groups, e.g., O, OH, F with alkoxide
groups from the solvent resulting in the change in the elec-
tronic band structure of the MXene flakes.[16a] It is also known
that MXene oxidation occurs in wet air leading to formation of
TiO2 and a substantial decrease in conductivity.[10b]
A convenient way to compare the performance of thin film
electrodes is by comparing their figure of merit (FoM), defined
as the ratio of their electronic (σDC) and optical (σopt) conduc-
tivities.[6] FoM can be calculated directly from transmittance (T)
Z 0s opt -2
and sheet resistance (Rs) values according to T = (1 + ) ,
2 Rss DC
where Z0 is the free space impedance (377 Ω). The high value
of FoM, i.e., high σDC and low σopt, implies desirable film
characteristics. FoM obtained from the fitting of the T and
Rs curve for water and ethanol-based films are 0.51 and 0.27,
respectively (Figure S2a, Supporting Information). The water-
based films, with the best FoM value of 0.74, are comparable
to liquid-exfoliated graphene networks films.[6] The optoelec-
tronic properties of the Ti3C2Tx films were also compared with
graphene-based thin films prepared by a similar method and
demonstrated their superiority (Figure S2b, Supporting Infor-
mation).[12,13,15,17] All these results indicate that Ti3C2Tx is a
promising candidate for applications where transparent con-
ductive films are needed.

Adv. Electron. Mater. 2016, 1600050 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (3 of 7)  1600050
 www.advelectronicmat.de
Full paper
Figure 3.  a) UV–vis spectra of Ti3C2Tx films with different thicknesses. b) Effect of thickness on absorbance of Ti3C2Tx films compared with other mate-
rials. c) Sheet resistance versus transmittance at 550 nm of Ti3C2Tx sprayed from ethanol and water solutions. The inset shows the low sheet resistance
region. d) Bending test of a film on a flexible polyester substrate.
In addition to the good optical and electrical properties, the
Ti3C2Tx films exhibited good mechanical properties when coated
on flexible substrates. For example, we evaluated the foldability
of the Ti3C2Tx films coated on flexible polyester substrates by
measuring their sheet resistance (Rs) as a function of bending
radii (r) that ranged from 13.5 to 3.8 mm and compared the
values to their sheet resistance when flat, R0. The films were
bent to selected radii directly and hold for 5 min during which
the conductivity was measured. After that, the films were recov-
ered flat immediately after removing the mechanical stress. As
shown in Figure 3d, the film showed excellent electromechan-
ical stability up to r = 8 mm, after which Rs increased about
15% at smaller bending radius (r = 3.8 mm) during the first
bend cycle. Upon removing the mechanical stress, and R0 was
recovered. To further investigate the film’s resilience, it was sub-
jected to 10 bending cycles to r = 3.8 mm (inset in Figure 3d).
The Rs value increased 14% of the starting value during the
first cycle and fluctuated around 25% during subsequent cycles.
In addition, we noticed that the film remained intact after the
bending tests, with no obvious defects or delaminations. These
good electromechanical properties are promising and suggest
our films can be used in flexible optoelectronic devices.
2.3. Tuning Optical Properties by Intercalation
The optical properties of the Ti3C2Tx thin films can be altered
by intercalation of cations between the negatively charged
Ti3C2Tx layers. This could, partly, be due to the increase/
1600050  (4 of 7) wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
decrease of the c-lattice parameter (c-LP) and/or charge transfer
between intercalants and the conducting Ti3C2Tx layers.[12,18]
Shown in Figure 4a are XRD patterns of the films chemically
intercalated with different monovalent cations in aqueous
basic solutions. Interestingly, Li+ intercalation results in the
largest increase in the c-LP, despite its smallest hydrated radius
among all the cations reported here.[19] This might be due to
high mobility of Li+ in the solution. Note that the c-LP of the
film intercalated with deionized water slightly increased com-
pared to the pristine film, indicating that water molecules can
also intercalate between the Ti3C2Tx layers.[11c] In addition to
inorganic bases, positively charged and neutral polar organic
molecules also intercalated the films resulting in the increases
in the c-LPs in Table S2 (Supporting Information). Shown
in Figure 4b is the percentage change in transmittance (%T)
of intercalated Ti3C2Tx thin films. Tetramethylammonium
hydroxide (NMe4OH) showed the largest increase of %T from
74.9 to 92.0% despite only 3 Å expansion in the c-LP. On the
other hand, LiOH, which exhibited the largest expansion of
the layers, only caused a 7% increase in the %T. As impor-
tantly, not only the increases but also small decreases in %T
were observed when the films were intercalated with hydrazine,
urea, and dimethyl sulfoxide (DMSO). Although the reasons for
the changes in %T upon intercalation are not yet fully under-
stood, this material clearly shows promise for thin film sensors
and electrochromic applications.
To further explore the potential of Ti3C2Tx thin films for sen-
sors and electrochromic devices, they were electrochemically
intercalated/deintercalated with NMe4OH. For this purpose,
Adv. Electron. Mater. 2016, 1600050
www.MaterialsViews.com www.advelectronicmat.de

b)

Full paper
a)

Change in Transmittance (%)

20
NMe4OH

15

e
Intensity (a.u.)

aO

in
H 2O

m
N
10

ia
ed

e
H

n
NMe4OH

in
O

KO

le

m
Li

hy

la
et

py
KOH 5

ro
i -p

O
H
2
NaOH
LiOH 0

hy

ur
pristine

D
dr
-5

ea e
M
az

SO
in
4 6 8 10 12 14 16 18 Intercalant
2θ (°)
Figure 4.  a) XRD patterns of Ti3C2Tx films intercalated with inorganic bases. b) Change in %T of the films due to chemical intercalation (positive change
means increase in %T compared to pristine films).

Ti3C2Tx thin films on glass substrates were employed as the
working electrodes in a typical three-electrode cell configura-
tion with Ag/AgCl, platinum plate, and NMe4OH function as a
reference electrode (RE), a counter electrode (CE), and electro-
lyte, respectively (Figure S4a, Supporting Information). Typi­cal
cyclic voltammogram of the film is presented in Figure 5a
showing only capacitive charging in the narrow voltage window
of 0.15 V from −0.2 to −0.35 V versus Ag/AgCl. Operation of
films in such a small voltage window is an advantage for smart
window applications.[20] The correlation between %T and the
film’s voltage is shown in Figure 5b. An increase of 3.5% from
53.0 to 56.5% was observed after the first negative scan from −0.2
to −0.35 V, possibly due to the expansion of the c-LP from
30.17 to 30.48 Å as indicated by XRD patterns (Figure S3, Sup-
porting Information). The %T of the film decreased to 55.0%
and increased again to 56.0% when the voltage was scanned
to −0.2 and −0.35 V, respectively. In situ UV–vis spectroscopy
was also used to confirm the changes in %T during electro-
chemical intercalation/deintercalation (Figure S5, Supporting
Information). Although the changes in %T observed here are
not sufficient for practical applications, what we show here is a
proof of concept for reversible changes of transmittance during
electrochemical intercalation/deintercalation of Ti3C2Tx films.
3. Conclusions
Thin films of delaminated Ti3C2Tx were prepared on large areas,
up to a letter-size paper sheet, by spray coating on glass and
flexible substrates. Films with sheet resistances (Rs) between
0.5–8 kΩ sq−1 at 40%–90% transmittances, respectively, were
readily fabricated. The FoM given by σDC/σopt was in the range
of 0.5–0.7. The films on flexible substrates exhibited good
electromechanical stability. The optical properties of the as-
prepared Ti3C2Tx films can, in principle, be tuned by simple
chemical intercalation. Reversible changes in transmittance
were also achieved by electrochemical intercalation/deintercala-
tion of tetramethylammonium hydroxide in aqueous solution.

a) b)
0.006
Transmittance at 550 nm (%)

1,3 56.5
0.004 56.0 -0.35 V
0.002 55.5 -0.35 V
i (mA)

55.0
0.000 -0.2 V
54.5
-0.002 54.0
-0.004 OVC = -0.25 V
53.5
ν = 2 mV/s 53.0
-0.006 2,4 -0.2 V
52.5
-0.35 -0.30 -0.25 -0.20 1 2 3 4
Voltage (V vs. Ag/AgCl) Point
Figure 5.  a) Cyclic voltammogram of a Ti3C2Tx film in 10 × 10−3 m NMe4OH recorded with a scan rate (ν) of 2 mV s−1. Transmittance was measured
at −0.20 and −0.35 V. Points 1 and 2 correspond to the first cycle and 3 and 4 to the second cycle. b) %T of the film at each voltage point marked in
panel (a).

Adv. Electron. Mater. 2016, 1600050 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com (5 of 7)  1600050
 www.advelectronicmat.de
The spray-coated Ti3C2Tx thin films reported herein show
Full paper
promise as a transparent conductive electrodes in electronic,
electrochromic, and sensor applications. Sheet resistances
of the films can be increased by increasing lateral flake sizes,
and minimizing oxidation during film deposition. In addition,
thicker films with lower Rs can be deposited with a tradeoff for
their transparency. It is worth noting that post-synthesis treat-
ments and chemical doping might also significantly improve
the film’s conductivity as reported for graphitic thin films.[2a,4,21]
Given the versatility and scalability of spray coating, the method
of thin film preparation developed herein opens a new door for
using, not only Ti3C2Tx, but also other MXenes (about 20 have
been reported to date) in transparent conductive electrodes,
sensors, and other applications.
4. Experimental Section
Synthesis of Ti3C2Tx MXene: Ti3C2Tx MXene was synthesized by
chemical exfoliation of Ti3AlC2. The Ti3AlC2 MAX phase was prepared
by mixing commercial Ti2AlC powders (Kanthal, Sweden) with TiC in a
1:1 molar ratio by ball milling for 18 h. The mixture was then heated to
1350 oC at 5 oC min–1 in a tube furnace under flowing Ar. The resulting,
lightly sintered, brick was ground with a TiN-coated milling bit and
sieved through a 400 mesh sieve to produce powder in which the particle
size was <38 μm. These finely ground Ti3AlC2 powder (2 g) was added to
a premixed solution of LiF (2 g, 0.08 mmol) and 9 m HCl (20 mL) over
the course of 5 min to avoid overheating due to exothermic nature of
the reaction. Then the mixture was stirred at 1000 rpm for 24 h at 35 °C.
The resulting suspension was washed twice by 9 m HCl (total volume
of 100 mL), stirred thoroughly, and centrifuged at 3500 rpm for 3 min.
The acidic supernatant after centrifuging was decanted, and deionized
(DI) water was added to wash the MXene powder several times until its
pH was higher than 4. The Ti3C2Tx aqueous solution was filtered on a
polypropylene membrane (3501 Coated PP, Celgard, USA).
Delamination and Redispersion of MXene: 200 mg of finely ground
multilayer Ti3C2Tx powder was added to 20 mL of DI water. The
suspension was sonicated for 1 h with positive argon pressure in an ice
bath, and centrifuged at 3500 rpm for 1 h to separate the Ti3C2Tx layers.
The delaminated Ti3C2Tx flakes (d-Ti3C2Tx) in the supernatant part were
then dispersed in either an aqueous solution or in ethanol. To redisperse
d-Ti3C2Tx in ethanol, 20 mL of aqueous d-Ti3C2Tx solution was filtered
using a Celgard membrane until almost all of the water was removed,
and 20 mL of ethanol was added on top of the suspension before it was
completely dry. The colloidal suspension was sonicated for 15 min or
until MXene flakes were homogeneously redispersed.
Thin Film Preparation: A glass substrate was sonicated in 3:1
concentrated H2SO4/H2O2 mixture for 1 h, and thoroughly washed with
DI water. The d-Ti3C2Tx solution was sprayed onto the substrate by an
airbrush (Master Airbrush Model G-233, USA) with 0.5 mm nozzle size
and 80 psi operating pressure. The airbrush/substrate distance was kept
at ≈30 cm perpendicularly from one another. The airbrush was moved
steadily at roughly 15 cm s−1 in all directions to obtain a homogeneous
thin film. An air gun (Master heat gun Model HG-201A, USA) was used
to dry the film after each layer of deposition.
Physical Characterization: UV–visible spectra were recorded with a
Thermo Scientific Evolution 600 UV–vis spectrometer (Madison, WI,
USA). Clean glass slides were used for 100% transmittance background
correction. The transmittance was recorded from 250 to 850 nm with
1 nm resolution using deuterium and tungsten lamps.
Sheet resistance of the films was measured using a four-point
probe instrument (ResTest v1, Jandel Engineering, UK). Each film was
measured at five positions: at the four corners and in the middle of the
film. Averaged values were reported.
1600050  (6 of 7) wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
XRD patterns of the films were obtained with a powder diffractometer
(Rigaku SmartLab, Tokyo, Japan) using CuKα radiation (λ = 1.54 Å)
with θ–2θ continuous scan with 0.02° 2θ step size, 1 s step time, and
10 × 10 mm2 window slit.
SEM (Zeiss Supra 50VP, Germany) was employed to study films’
morphology. A conductive silver paint was used to draw a conductive
path between the film and the sample holder.
TEM (JEOL JEM-2100, Japan) with an accelerating voltage of 200 kV
was used to study exfoliated Ti3C2Tx layer. TEM samples were prepared
by dropping d-Ti3C2Tx solution onto a copper grid and dried in air.
AFM (NX-10, Park Systems, Suwon, Korea) performed in contact
mode was used to measure film thickness. The films were carefully
scratched by plastic tweezers without damaging the glass substrate to
mark the 0 nm thickness. The scan size and rate were 45 × 45 μm2 and
0.5 Hz, respectively. The thickness measurements were done on four
different lines across the scanned area.
Electrochemical Measurements: Electrochemical measurements were
performed using a VMP 3 potentiostat (Biologic, France). Ti3C2Tx thin
film with ≈4 cm2 active area on glass substrate, platinum plate with
≈8 cm2 surface area, and Ag/AgCl in 3 m KCl were used as a working,
counter, and RE, respectively. Ti3C2Tx thin film and a platinum wire
CE were used in a two-electrode cell configuration for in situ UV–vis
measurements. Conductive silver paint was applied on the Ti3C2Tx film
to improve electrical contact. The upper voltage window was chosen to
be less than 100 mV above the open circuit voltage to avoid oxidation of
MXene, and the lower voltage window was chosen to avoid irreversible
peak arising from electrolyte decomposition. Cyclic voltammetry was
performed using scan rates from 2 to 10 mV s−1. The voltage was held
constant for at least 10 min before each UV–vis spectrum acquisition.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the US National Science Foundation under
grant number DMR-1310245. K.H. was supported by the Erasmus
Mundus joint master program, Materials for Energy Storage and
Conversion (M.E.S.C.).
Received: February 5, 2016
Revised: March 8, 2016
Published online:
[1] a) T. Gao, Z. Li, P.-S. Huang, G. J. Shenoy, D. Parobek, S. Tan,
J.-K. Lee, H. Liu, P. W. Leu, ACS Nano 2015, 9, 5440; b) D. S. Hecht,
L. Hu, G. Irvin, Adv. Mater. 2011, 23, 1482; c) S. Kirchmeyer,
K. Reuter, J. Mater. Chem. 2005, 15, 2077; d) J.-Y. Lee, S. T. Connor,
Y. Cui, P. Peumans, Nano Lett. 2008, 8, 689; e) Z. Yang, J. Ren,
Z. Zhang, X. Chen, G. Guan, L. Qiu, Y. Zhang, H. Peng, Chem. Rev.
2015, 115, 5159.
[2] a) I. Khrapach, F. Withers, T. H. Bointon, D. K. Polyushkin,
W. L. Barnes, S. Russo, M. F. Craciun, Adv. Mater. 2012, 24, 2844;
b) J. Saghaei, A. Fallahzadeh, T. Saghaei, Org. Electron. 2015, 24, 188.
[3] a) J. D. Roy-Mayhew, I. A. Aksay, Chem. Rev. 2014, 114, 6323;
b) Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts, R. S. Ruoff,
Adv. Mater. 2010, 22, 3906.
[4] J. K. Wassei, R. B. Kaner, Mater. Today 2010, 13, 52.
Adv. Electron. Mater. 2016, 1600050
www.MaterialsViews.com
[5] a) M. Jung de Andrade, M. Dias Lima, V. Skákalová,
C. Pérez Bergmann, S. Roth, Phys. Status Solidi RRL 2007, 1, 178; b) Y.
I. Song, C.-M. Yang, D. Y. Kim, H. Kanoh, K. Kaneko, J. Colloid Inter-
face Sci. 2008, 318, 365; c) V. C. Tung, M. J. Allen, Y. Yang, R. B. Kaner,
Nat. Nanotechnol. 2009, 4, 25.
[6] S. De, J. N. Coleman, ACS Nano 2010, 4, 2713.
[7] M. Naguib, M. Kurtoglu, V. Presser, J. Lu, J. Niu, M. Heon,
L. Hultman, Y. Gogotsi, M. W. Barsoum, Adv. Mater. 2011, 23, 4248.
[8] a) M. Naguib, O. Mashtalir, J. Carle, V. Presser, J. Lu, L. Hultman,
Y. Gogotsi, M. W. Barsoum, ACS Nano 2012, 6, 1322; b) M. Naguib,
V. N. Mochalin, M. W. Barsoum, Y. Gogotsi, Adv. Mater. 2014, 26,
992; c) X. Zhang, X. Zhao, D. Wu, Y. Jing, Z. Zhou, Nanoscale 2015,
7, 16020.
[9] a) M. R. Lukatskaya, O. Mashtalir, C. E. Ren, Y. Dall’Agnese,
P. Rozier, P. L. Taberna, M. Naguib, P. Simon, M. W. Barsoum,
Y. Gogotsi, Science 2013, 341, 1502; b) M. Naguib, J. Come,
B. Dyatkin, V. Presser, P.-L. Taberna, P. Simon, M. W. Barsoum,
Y. Gogotsi, Electrochem. Commun. 2012, 16, 61; c) X. Xie, S. Chen,
W. Ding, Y. Nie, Z. Wei, Chem. Commun. 2013, 49, 10112;
d) X.-F. Yu, Y.-C. Li, J.-B. Cheng, Z.-B. Liu, Q.-Z. Li, W.-Z. Li, X. Yang,
B. Xiao, ACS Appl. Mater. Interfaces 2015, 7, 13707; e) J.-C. Lei,
X. Zhang, Z. Zhou, Front. Phys. 2015, 10, 276.
[10] a) O. Mashtalir, M. R. Lukatskaya, M.-Q. Zhao, M. W. Barsoum,
Y. Gogotsi, Adv. Mater. 2015, 27, 3501; b) O. Mashtalir, M. Naguib,
B. Dyatkin, Y. Gogotsi, M. W. Barsoum, Mater. Chem. Phys. 2013,
139, 147; c) M. Naguib, R. R. Unocic, B. L. Armstrong, J. Nanda,
Dalton Trans. 2015, 44, 9353; d) O. Mashtalir, M. Naguib,
V. N. Mochalin, Y. Dall’Agnese, M. Heon, M. W. Barsoum,
Y. Gogotsi, Nat. Commun. 2013, 4, 1716.
[11] a) M. Ghidiu, M. R. Lukatskaya, M.-Q. Zhao, Y. Gogotsi,
M. W. Barsoum, Nature 2014, 516, 78; b) Z. Ling, C. E. Ren,
M.-Q. Zhao, J. Yang, J. M. Giammarco, J. Qiu, M. W. Barsoum,
Y. Gogotsi, Proc. Natl. Acad. Sci. USA 2014, 111, 16676; c) C. E. Ren,
K. B. Hatzell, M. Alhabeb, Z. Ling, K. A. Mahmoud, Y. Gogotsi,
Adv. Electron. Mater. 2016, 1600050 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
View publication stats
www.advelectronicmat.de
J. Phys. Chem. Lett. 2015, 6, 4026; d) M.-Q. Zhao, C. E. Ren, Z. Ling,
Full paper
M. R. Lukatskaya, C. Zhang, K. L. Van Aken, M. W. Barsoum,
Y. Gogotsi, Adv. Mater. 2015, 27, 339.
[12] J. Halim, M. R. Lukatskaya, K. M. Cook, J. Lu, C. R. Smith,
L.-Å. Näslund, S. J. May, L. Hultman, Y. Gogotsi, P. Eklund,
M. W. Barsoum, Chem. Mater. 2014, 26, 2374.
[13] A. D. Dillon, M. J. Ghidiu, A. L. Krick, J. Griggs, S. J. May, Y. Gogotsi,
M. W. Barsoum, A. T. Fafarman, Adv. Funct. Mater. 2016, in press.
[14] a) N. Behabtu, J. R. Lomeda, M. J. Green, A. L. Higginbotham,
A. Sinitskii, D. V. Kosynkin, D. Tsentalovich, A. N. G. Parra-Vasquez,
J. Schmidt, E. Kesselman, Y. Cohen, Y. Talmon, J. M. Tour,
M. Pasquali, Nat. Nanotechnol. 2010, 5, 406; b) J. Wan, F. Gu,
W. Bao, J. Dai, F. Shen, W. Luo, X. Han, D. Urban, L. Hu, Nano Lett.
2015, 15, 3763.
[15] H. A. Becerril, J. Mao, Z. Liu, R. M. Stoltenberg, Z. Bao, Y. Chen,
ACS Nano 2008, 2, 463.
[16] a) A. N. Enyashin, A. L. Ivanovskii, J. Phys. Chem. C 2013, 117,
13637; b) A. N. Enyashin, A. L. Ivanovskii, J. Solid State Chem.
2013, 207, 42; c) M. Khazaei, M. Arai, T. Sasaki, C.-Y. Chung,
N. S. Venkataramanan, M. Estili, Y. Sakka, Y. Kawazoe, Adv. Funct.
Mater. 2013, 23, 2185; d) Q. Tang, Z. Zhou, P. Shen, J. Am. Chem.
Soc. 2012, 134, 16909; e) X. Zhang, Z. Ma, X. Zhao, Q. Tang,
Z. Zhou, J. Mater. Chem. A 2015, 3, 4960.
[17] a) X. Li, G. Zhang, X. Bai, X. Sun, X. Wang, E. Wang, H. Dai, Nat.
Nanotechnol. 2008, 3, 538; b) M. Myekhlai, S. Lee, T. Lee, H. Chung,
H. Jeong, Ceram. Int. 2015, 41, 983.
[18] W. Bao, J. Wan, X. Han, X. Cai, H. Zhu, D. Kim, D. Ma, Y. Xu,
J. N. Munday, H. D. Drew, M. S. Fuhrer, L. Hu, Nat. Commun. 2014, 5.
[19] J. Mähler, I. Persson, Inorg. Chem. 2012, 51, 425.
[20] C. Bechinger, J. N. Bullock, J. G. Zhang, C. E. Tracy, D. K. Benson,
S. K. Deb, H. M. Branz, J. Appl. Phys. 1996, 80, 1226.
[21] D. Sepideh Khandan, B. Rainer, B. Andreas, S.-E. Heiko, L. Jiantong,
K. Torsten, Ö. Mikael, B. Peter Haring, C. L. Max, 2D Mater. 2015,
2, 011003.
wileyonlinelibrary.com (7 of 7)  1600050