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Fabrication of Ti3C2Tx MXene Transparent Thin Films with Tunable

Optoelectronic Properties

Article in Advanced Electronic Materials · April 2016

DOI: 10.1002/aelm.201600050

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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

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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 dimension of the flakes is generally in the range of hundreds of
higher electrical conductivity. Thus, no post-synthesis reduc- nanometers up to several micrometers. Selective area electron
tion process is needed to generate highly conductive films.[8a] diffraction (SAED) pattern (see inset of Figure 2a) confirms
Free-standing MXene films, with thicknesses ranging from the hexagonal symmetry of the flakes and their single-crystal
hundreds of nanometers to tens of micrometers, have been pre- nature.
pared by vacuum-assisted filtration. Some of these films show The Ti3C2Tx thin films were produced by spray coating of
high conductivity values of ≈2400 S cm−1, and have been widely delaminated Ti3C2Tx (d-Ti3C2Tx) colloidal solutions – with a
studied for use in energy storage and separation applications.[11] concentration of ca. 3.0 mg mL−1 – onto a substrate at room
The properties of MXenes, however, afford great potential for temperature. X-ray diffraction (XRD) patterns (Figure S1, Sup-
use as transparent conductive electrodes. For instance, it was porting Information) show that the film consists of only Ti3C2Tx
found that MXene films with thicknesses of tens of nanometers MXene flakes without any other phases. The c-lattice parameter
prepared by chemical etching of magnetron-sputtered Ti3AlC2 of the films, calculated from the (0002) peak, is 29.5 Å.
epitaxial thin films were quite transparent while retaining high Scanning electron microscopy (SEM) images show that the
electrical conductivity, i.e., Rs value of 2.3 kΩ sq−1 at 68% trans- spray-coated Ti3C2Tx film on a glass slide is homogeneous,
mittance for a 17 nm-thick film.[12] However, MXene films fab- without obvious pin-holes or other types of defect over a con-
ricated by such method suffer from the same drawbacks as the siderably large area (Figure 2b, left). Folded edges of Ti3C2Tx
CVD graphene films, viz., they are not practical for large-scale flakes can be seen in the high magnification image (Figure 2b,
applications, high cost of fabrication, etc. More recent work has right). In the same image, a flake with a lateral size of ≈0.5 μm
shown that high quality transparent conductive MXene films is marked with a dotted line. Cross-sectional SEM image of the
with conductivity exceeding 6500 S cm−1 can be prepared by film (Figure 2c) indicates that the Ti3C2Tx flakes are aligned
spin casting of delaminated Ti3C2Tx solution.[13] It is still impor- parallel to the glass surface, resulting in a compact thin film.
tant to further explore the optical and electrical properties of These Ti3C2Tx films showed good transparency (Figure 2d). In
solution-processed films, towards the production of MXene- addition to glass slides, other kinds of substrates, such as flex-
based transparent and conductive films, at low cost. ible polyester sheets, can also be used for the spray-coating of
Herein, we report a simple process of spray coating of col- transparent Ti3C2Tx thin films (Figure 2e). Moreover, no visible
loidal delaminated Ti3C2Tx solution to fabricate transparent damage was observed on the flexible film even after bending to
conductive films (Figure 1). Homogeneous transparent conduc- a small radius of curvature (inset of Figure 2e). This suggests
tive films were produced on various substrates over large areas. that Ti3C2Tx thin films can be used in flexible devices. Figure
These films exhibit optoelectronic properties exceeding those 2f shows an atomic force microscopy (AFM) image of a typical,
of solution-processed transparent graphene films. We further 70-nm-thick Ti3C2Tx film on a glass substrate. The surface
demonstrated that optoelectronic properties of the films can be roughness was measured as ≈10 nm, which is a typical value
readily altered by the chemical and electrochemical intercalation for solution-processed thin films.[14]
of organic and inorganic compounds between the Ti3C2 layers.

2.2. Optoelectronic Properties of the Transparent

2. Results and Discussion Ti3C2Tx Thin Films

2.1. Ti3C2Tx Thin Films by Spray Coating The optical properties of the Ti3C2Tx films were evaluated by ultra-
violet–visible (UV–vis) spectrophotometry, and their electrical
The synthesis and delamination of Ti3C2Tx has been described conductivities were measured by a four-point probe technique.
in detail elsewhere.[11a] A typical transmission electron micro- The UV–vis spectra of these films with different thicknesses
scope (TEM) image of a single-layered Ti3C2Tx flake obtained are presented in Figure 3a. The films obviously absorb light in
from a colloidal solution is presented in Figure 2a. The lateral the UV region, viz. from 300 to 500 nm. Note that the strong

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

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

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

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The spray-coated Ti3C2Tx thin films reported herein show

Full paper

XRD patterns of the films were obtained with a powder diffractometer

promise as a transparent conductive electrodes in electronic, (Rigaku SmartLab, Tokyo, Japan) using CuKα radiation (λ = 1.54 Å)
electrochromic, and sensor applications. Sheet resistances with θ–2θ continuous scan with 0.02° 2θ step size, 1 s step time, and
10 × 10 mm2 window slit.
of the films can be increased by increasing lateral flake sizes, SEM (Zeiss Supra 50VP, Germany) was employed to study films’
and minimizing oxidation during film deposition. In addition, morphology. A conductive silver paint was used to draw a conductive
thicker films with lower Rs can be deposited with a tradeoff for path between the film and the sample holder.
their transparency. It is worth noting that post-synthesis treat- TEM (JEOL JEM-2100, Japan) with an accelerating voltage of 200 kV
ments and chemical doping might also significantly improve was used to study exfoliated Ti3C2Tx layer. TEM samples were prepared
the film’s conductivity as reported for graphitic thin films.[2a,4,21] by dropping d-Ti3C2Tx solution onto a copper grid and dried in air.
AFM (NX-10, Park Systems, Suwon, Korea) performed in contact
Given the versatility and scalability of spray coating, the method
mode was used to measure film thickness. The films were carefully
of thin film preparation developed herein opens a new door for scratched by plastic tweezers without damaging the glass substrate to
using, not only Ti3C2Tx, but also other MXenes (about 20 have mark the 0 nm thickness. The scan size and rate were 45 × 45 μm2 and
been reported to date) in transparent conductive electrodes, 0.5 Hz, respectively. The thickness measurements were done on four
sensors, and other applications. 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
4. Experimental Section ≈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
Synthesis of Ti3C2Tx MXene: Ti3C2Tx MXene was synthesized by CE were used in a two-electrode cell configuration for in situ UV–vis
chemical exfoliation of Ti3AlC2. The Ti3AlC2 MAX phase was prepared measurements. Conductive silver paint was applied on the Ti3C2Tx film
by mixing commercial Ti2AlC powders (Kanthal, Sweden) with TiC in a to improve electrical contact. The upper voltage window was chosen to
1:1 molar ratio by ball milling for 18 h. The mixture was then heated to be less than 100 mV above the open circuit voltage to avoid oxidation of
1350 oC at 5 oC min–1 in a tube furnace under flowing Ar. The resulting, MXene, and the lower voltage window was chosen to avoid irreversible
lightly sintered, brick was ground with a TiN-coated milling bit and peak arising from electrolyte decomposition. Cyclic voltammetry was
sieved through a 400 mesh sieve to produce powder in which the particle performed using scan rates from 2 to 10 mV s−1. The voltage was held
size was <38 μm. These finely ground Ti3AlC2 powder (2 g) was added to constant for at least 10 min before each UV–vis spectrum acquisition.
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 Supporting Information
of 100 mL), stirred thoroughly, and centrifuged at 3500 rpm for 3 min.
The acidic supernatant after centrifuging was decanted, and deionized Supporting Information is available from the Wiley Online Library or
(DI) water was added to wash the MXene powder several times until its from the author.
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 Acknowledgements
suspension was sonicated for 1 h with positive argon pressure in an ice This work was supported by the US National Science Foundation under
bath, and centrifuged at 3500 rpm for 1 h to separate the Ti3C2Tx layers. grant number DMR-1310245. K.H. was supported by the Erasmus
The delaminated Ti3C2Tx flakes (d-Ti3C2Tx) in the supernatant part were Mundus joint master program, Materials for Energy Storage and
then dispersed in either an aqueous solution or in ethanol. To redisperse Conversion (M.E.S.C.).
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, Received: February 5, 2016
and 20 mL of ethanol was added on top of the suspension before it was
Revised: March 8, 2016
completely dry. The colloidal suspension was sonicated for 15 min or
Published online:
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 [1] a) T. Gao, Z. Li, P.-S. Huang, G. J. Shenoy, D. Parobek, S. Tan,
and 80 psi operating pressure. The airbrush/substrate distance was kept J.-K. Lee, H. Liu, P. W. Leu, ACS Nano 2015, 9, 5440; b) D. S. Hecht,
at ≈30 cm perpendicularly from one another. The airbrush was moved L. Hu, G. Irvin, Adv. Mater. 2011, 23, 1482; c) S. Kirchmeyer,
steadily at roughly 15 cm s−1 in all directions to obtain a homogeneous K. Reuter, J. Mater. Chem. 2005, 15, 2077; d) J.-Y. Lee, S. T. Connor,
thin film. An air gun (Master heat gun Model HG-201A, USA) was used Y. Cui, P. Peumans, Nano Lett. 2008, 8, 689; e) Z. Yang, J. Ren,
to dry the film after each layer of deposition. Z. Zhang, X. Chen, G. Guan, L. Qiu, Y. Zhang, H. Peng, Chem. Rev.
Physical Characterization: UV–visible spectra were recorded with a 2015, 115, 5159.
Thermo Scientific Evolution 600 UV–vis spectrometer (Madison, WI, [2] a) I. Khrapach, F. Withers, T. H. Bointon, D. K. Polyushkin,
USA). Clean glass slides were used for 100% transmittance background W. L. Barnes, S. Russo, M. F. Craciun, Adv. Mater. 2012, 24, 2844;
correction. The transmittance was recorded from 250 to 850 nm with b) J. Saghaei, A. Fallahzadeh, T. Saghaei, Org. Electron. 2015, 24, 188.
1 nm resolution using deuterium and tungsten lamps. [3] a) J. D. Roy-Mayhew, I. A. Aksay, Chem. Rev. 2014, 114, 6323;
Sheet resistance of the films was measured using a four-point b) Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts, R. S. Ruoff,
probe instrument (ResTest v1, Jandel Engineering, UK). Each film was
Adv. Mater. 2010, 22, 3906.
measured at five positions: at the four corners and in the middle of the
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