Ceramics International 46 (2020) 17729–17734

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Ceramics International
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Mechanical response of layered titanate nanowires T

∗
L. Rossi , R. Foschia, A. Glushkova, L. Forró, E. Horváth
Laboratory of Physics of Complex Matter, École Polytechnique Fédérale de Lausanne, 1015, Lausanne, Switzerland

A R T I C LE I N FO A B S T R A C T

Keywords: The mechanical response of individual titanate nanowires (H2Ti3O7), synthesized in an upscaled production (kg/
Layered ceramic month) was investigated by means of an Atomic Force Microscope (AFM) in nanomechanical spectroscopic
Young modulus mode. Because of their layered structure, besides the Young's modulus (E) of 66.7 ± 25 GPa, an important
Shear modulus contribution to the mechanical response was identified as coming from the low shear modulus (G) of
Fatigue
1.5 ± 0.8 GPa between the layers. The mechanical energy loss due to shear is at the origin of the material's
fatigue, during which the individual titanate layers crack gradually, until the final failure of the structure. The
high-temperature treatment at 800 °C transforms the material into anatase (TiO2) nanowires, which have a
considerably higher elastic modulus.

1. Introduction shape, replacing isotropic particles with highly anisotropic, fiber-like

particles may open new avenues for the long-sought satisfactory elec-
TiO2 nanoparticles, mostly in the anatase polymorph, are very tronic and mechanical performance metrics of flexible devices.
popular in several applications, ranging from sunscreens to photo- Here, we report a detailed study of the mechanical response of ti-
voltaic (PV) devices [1–4]. Their sister materials, the anatase nanowires tanate nanowires: their elastic and shear modulii, their flexibility, fa-
(NWs) are equally interesting, gaining more and more emphasis in PV tigue behavior and the rupture force. We also characterize the change
because of their higher dimensionality, the charge extraction is much of Young's modulus due to the thermal transformation of titanate into
more efficient. Beyond PV, they are used in photocatalytic water and air anatase NWs.
purification [5–10], in memristors [11], sensors [12,13], super-
capacitors [14,15] and batteries [16]. Their precursor structures, from 2. Experimental methods
which they are obtained by thermal treatment, the titanates (e.g.
H2Ti3O7), are equally important, as in the case when they are the active 2.1. Titanate material and fabrication
components of a very sensitive humidity sensor [17], they serve as
reinforcement fibers in composites [18], super-insulation aerogels [19] Protonated titanate nanowire (H2Ti3O7) were prepared by a two-
or catalyst [20]. All these applications are getting credibility, since the step hydrothermal process; the typical synthesis procedure, which re-
synthesis from mg quantity by hydrothermal synthesis in autoclave, has sults in single-crystalline nanowires, is described elsewhere [29]. A
been scaled up by an original approach to kg/month production rate large assembly of them is shown on an Transmission Electron Micro-
[21]. scope (TEM) image in Fig. 1(a). They have belt-like shape and their
In all these devices it is important to assess the mechanical prop- width ranges from 10 to 100 nm and their length can go up tens of μm
erties of the final system (for example in a water filter weaved from [30]. On the High Resolution-Transmission Electron Microscope (HR-
titanate nanowires) which depend on the properties of the single fibers. TEM) image of Fig. 1(b), one can clearly notice the layered structure of
Also, there is a significant interest to extend the applicability of titania the NWs. This observation of the gallery spacing is feasible when the
thin films to flexible substrates in dye-sensitized solar cell (DSSC) belt-like nanowire is laying in a tilted position, with its thinner sides on
[22–24], supercapacitors [25], perovskite solar cell [26,27], gas sensors the substrate. It is more frequent that the nanowires are attached with
[28]. In these applications, the preparation of porous, uniform and their wider base on a given substrate. It is important to point out, that
crack-free nanoparticle-based films is particularly challenging due to this latter scenario, when the nanobelts layer planes are in parallel with
the intrinsic rigidness of sintered titania, ultimately deteriorating the the surface is chosen for this study. The layered structure has been
performance values of lab-scale prototype devices. The effect of particle confirmed by TEM image and the corresponding electron diffraction

∗
Corresponding author. EPFL SB IPHYS LPMC PH D2 355 (Bâtiment PH) Station 3 CH-1015, Lausanne, Switzerland.
E-mail address: lidia.rossi@epfl.ch (L. Rossi).

https://doi.org/10.1016/j.ceramint.2020.04.077
Received 18 February 2020; Received in revised form 4 April 2020; Accepted 7 April 2020
Available online 08 April 2020
0272-8842/ © 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
L. Rossi, et al. Ceramics International 46 (2020) 17729–17734

Fig. 1. (a) TEM image of a large assembly titanate NW (H2Ti3O7). (b) HR-TEM image showing the layered and single crystalline nature of the NW. (c) The highly
elastic character of the NW is shown by adopting the shape of a hole made in silicon. (d) A membrane made of titanate NW.

pattern showing a crystalline structure with a gallery spacing of 0.7 nm specifically calibrated for our experiments. The results shown in this
(see Fig. 1(b) and Fig. S1). The high crystallinity and concomitant high article were obtained with a 47.038 N/m spring constant and 30.1 nm
flexibility could be seen in Fig. 1(c), where an individual NW, deposited tip end radius cantilever. An SEM image of the tip used for the mea-
from suspension on a membrane, adopts to the curvature of the hole. surements is shown in Fig. S2. The AFM (XE-100 PSIA) used a 2-di-
This high flexibility of the titanate NW allows making highly functional mensional flexure stage to scan the sample in the XY direction, and a
membranes from them (see Fig. 1(d) and Horváth et al. [17]). stacked piezoelectric actuator to scan the probe in the Z direction. In
this way, the accurate position of the probe was ensured while elim-
inating the crosstalk issues commonly faced in such measurements. The
2.2. Titanate characterization
deflection sensitivity is determined from a force versus piezo extension
curve on a stiff substrate in the linear region of both stacked piezo-
Titanate NW were characterized by an Scanning Electron
Microscope (SEM, Zeiss Merlin, Gemini II column) to localize and ob- electric actuator and deflection detector.
serve the morphology of nanowires. SEM images were acquired at an
accelerating voltage of 2 kV and 150 pA electron beam current. TEM
2.4. Mechanical characterization method
image was performed at 200 kV high voltage on a FEI Talos microscope
in bright field.
In order to carry out mechanical characterization of NWs, we ap-
An Atomic Force Microscope (AFM, XE-100 PSIA) operating in air plied the three points bending measurement method using an AFM in
was used to investigate the surface topography and to apply a load to
conjunction with the so-called “Swiss cheese method” as first proposed
the NWs in order to determine directly the resulting. by J. P. Salvetat and colleagues [31,32] for carbon nanotubes. The
configuration is the following: on e-beam lithography defined holes in a
2.3. AFM and cantilever calibration silicon substrate (800 nm diameter and 400 nm depth), individual ti-
tanate NWs are deposited from an ultrasonicated suspension via a
To provide accurate nanomechanical property measurements, both, stamping method. First, the nanowire suspension was filtered on a
the cantilever spring constant and the deflection sensitivity are re- Teflon membrane and subsequently stamped against the micro-
quired. Conventional spring constant calibration techniques rely on fabricated hole-containing silicon substrate. Due to the wettability
multiple cantilever probe tip contacts to the surface with the con- differences of the substrates, the nanowires were preferentially trans-
sequences of damaging the tip. Therefore, we preferred to use com- ferred to the silicon substrate with high yield. After the evaporation of
mercially available cantilevers, laser Doppler vibrometry (LDV) cali- the remaining isopropanol, the NWs’ adhesion to the silicon substrate is
brated, RTESPA-300-30 from Bruker. We have chosen a cantilever type strong, so they can be treated as a double clamped beams of suspended
with high nominal 40 N/m spring constant and 30 nm tip end radius, length L (see Fig. 2(a)) [32]. This strong attachment is caused by

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Fig. 2. Experimental configuration for measuring the

elastic response of titanate NWs. (a) Sketch of the
three-point bending test by AFM, indicating the
major parameters for the evaluation: the inset shows
an SEM image of the suspended NW over the litho-
graphically defined hole in silicon. (b) Applied force
versus displacement for the three-point bending test.
The black line, the reference curve, measured on the
NW supported by the solid substrate; while red line is
recorded in the middle of the hole, The deflection δ,
used for the calculation of the bending modulus in
equation (1), is extracted as the difference between
the red and black curves at a given force, as shown in
the inset. (For interpretation of the references to
colour in this figure legend, the reader is referred to
the Web version of this article.)

adhesion, as well as hydroxyl bond formation between the titanate and calculated from the slope of the linear regression of the F-δ graph ac-
native silicon oxide layer, and is clearly demonstrated during extended cording to equation (1). The suspended length and the cross-section of
AFM imaging, where no displacement of the portion lying of the NW is the NWs varied considerably for each sample.
observed. This is also illustrated in Fig. S3 from the repeatability test by In the case of a uniform beam, with negligible shear, Eb coincides
applying a force-release cycle 300-times, where no movement of the with the Young's modulus E. If there are subunits in the beam, which
suspended NW was observed. can slide on each other under the loading force, then both E and G, the
SEM images show that the NWs possess a typical rectangular cross- shear modulus, influence Eb . In this case the extraction of the moduli
section (of width b, and height h), and lay over the substrate with their requires a more careful data analysis, where the bending is measured
wider surface. More details are explained in the Supplementary for various diameters (D) and suspended lengths (L). In this case, one
Material and Fig. S4. In this model, of a double clamped beam [33] the can extract the two modulii (E and G) using the following relation [33]:
bending modulus (Eb ) is related to the deflection δ via the moment of
1 1 10 1 D 2
inertia I of the NW, to the suspended length and to the loading force F = +
Eb E 3 G L2 (2)
according to the following relationship:
This analysis was successfully applied for single-walled carbon na-
FL3
Eb = , notube bundles in which the individual nanotubes are held together
192δI (1)
with weak Van der Waals forces. The obtained values were E = 1 TPa
where I = bh3/12
for rectangular cross-section beams. and G = 5 GPa [32]. Upon electron irradiation, the nanotubes got
One has to notice that the bending modulus has a strong depen- cross-linked and G tremendously increased [34].
dence on the NW dimensions (L, b, h – the suspended length, width and
height, respectively). Although AFM is a high precision tool, small 3. Results and discussion
uncertainty could add up a high error bar, in the range of 20–30
[31,32]. 3.1. Mechanical properties
The bending data were collected in the following way. After the
deposition of the suspension of titanate NW on the silicon substrate Fig. 3(a) displays the measured Eb for a large assembly of NWs.
with the array of holes and the evaporation of the liquid, the surface Surprisingly, it has a strong cross-section (translated into equivalent
was imaged in a non-contact AFM mode. In cases, where NWs were diameter) dependence. Actually, we have considerable bending due to
bridging a hole, force-displacement measurements were taken in con- the weak interaction between the layers in the structure. In con-
tact AFM mode. For each NW, before measuring the deflection on the sequence, shear contribution plays an important role in the mechanical
hole, we carried out spectroscopy on the part laying on the substrate; response of NWs. In the spirit of equation (2), shear is important when:
this measurement served as a reference (black curve in Fig. 2(b)). Then L/ R ≤ 4 E / G [33]. In our case, L/ R ranges from 7.5 to 20 (evaluated
the same measurement was taken in the middle of the NW suspended by SEM and AFM measurements), so the ratio of E/G should be above
on the hole. Both force-displacement measurements were taken with a 25. Using equation (2), the two modulii are deconvoluated in the fol-
speed of 0.3 μm/s. The difference in position, i.e. of the displacement lowing way.
signal, for the same applied force between the two measurements define The titanate NWs have rectangular cross-section, of aspect ratio
the actual deflection δ, as plotted in the inset of Fig. 2(b). The Eb is width/height between 0.7 and 2, that can be conveniently

Fig. 3. (a) Measured bending modulus Eb for 25

different titanate NWs with different equivalent
diameters between 26 and 95 nm; in the inset the 1/
Eb as a function of (D/L)2 for determination of E and
G, according to equation (2). (b) Sketch of the crystal
structure of titania NW, in order to illustrate the E
and G modulii extracted from the left panel.

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characterized by an equivalent diameter, Deq. The use of Deq permits a

more direct comparison with the results of other authors obtained on
nanowires with circular cross-section. The Eb values shown in Fig. 3(a)
for 25 titanate NWs as a function of the Deq were calculated from the
linear part of the (F-δ) curves, typically restricted to the 50–150 nN
force range (or 25–35 nm displacement range), well below the rupture
point. The reason for not going too high in loading, was to avoid da-
maging the NWs, which were later submitted to thermal treatment, to
transform them into anatase, of single-crystalline structure. Making use
of equation (2), the plot of 1/Eb versus D2/L2 in the inset to Fig. 3(a)
allows to extract E and G. The slope gives G while the intercept gives
directly 1/E. We obtained: G = 1.5 ± 0.8 GPa and
E = 66.7 ± 25 GPa. Despite the considerable error bar the presence of
G (of a non-zero slope) is evident in these measurements.
Other publications on Na2Ti3O7 NWs, report an elastic modulus E Fig. 5. SEM image of a typical titanate NW (a) Before and (b) after the thermal
for the NWs of 33 ± 7 GPa [35] and between 37 and 250 GPa [36]. We treatment at 800 °C which transforms it into the anatase phase. (c) Histogram of
believe that their low value and the large dispersion is due the presence the bending modulus (Eb) measured on 15 NWs in the titanate and anatase
of shear modulus in their measurements. To our knowledge, our result forms.
is amongst the first ones to report G for layered titanate NWs. We il-
lustrate this new notion found for our system in Fig. 3(b), which could unloading cycle (dark green for the loading and light green for un-
be important for other layered or composite nanostructures too. The loading) one can observe a dramatic change in the bending modulus
only other report on the mechanical response of layered titanate na- with a drop of factor 3. We interpret these changes as a gradual rupture
noribbons is that of Humar et al. [37] which values are however sur- of the layers upon mechanical loadings composing the NWs. Pre-
prising: E reaches 400 GPa, but G is in the 0.01 GPa range (hundred sumably, the shear, translated into friction between the layers has a role
times smaller than ours). Actually, the very low value for G is coming in the breaking of the individual layers. In the end, the sample did not
from the shear modulus between nanoribbons in a bundle, and not that oppose any resistance to the AFM tip, the NW was ruptured. The SEM
within a ribbon, measured in this work. image in Fig. 4(b) illustrates the end result.
It has to be mentioned that the E vs diameter trend shown in
Fig. 3(a) is similar to the one reported by Chen et al. [38], for ZnO NWs.
Beyond the fact that they have covered a broader diameter range, the 3.3. Transformation of titanate into anatase
ZnO has no layered structure, so they attribute the decrease of the
modulus to binding energy balance in a core-shell model. However, we After full characterization of the titanate NWs at room temperature,
underline that in our case the mechanism causing the decrease of they were submitted to a thermal treatement up to 800 °C in air in order
flexural modulus is different from that of Chen et al. It is due to the to transform them into anatase polymorph of TiO2. The temperature
intrinsic layered structure of our nanowires and the size-dependent ramp rate was 20 °C/min and the samples were kept at 800 °C for 1 h.
convolution of the shear between layers to the overall response. One has to observe, that at such a high-temperature, usually the bulk
anatase transforms into rutile polymorh. But our structural investiga-
tions show that the anatase nanowires preserve their structure even at
3.2. Fatigue this high-temperature [42]. A representative SEM imaging of this
transformation is shown in (a) (titanate) and Fig. 5(b) (anatase). The
If one is dealing with functional NWs, exposed to repeated me- shrinkage of the NW upon this transformation is clearly visible, since
chanical loadings, it is important to check the fatigue of the material. A the layered texture is lost and the anatase has a uniform structure.
NW was submitted to a fatigue cycle with the result shown in Fig. 4(a). Shrinkage due to recrystallization into the anatase phase introduces
The red curve represents the first 600 force-release cycle up to F = 300 mechanical stresses in the structure, enhanced by the mismatch of NW-
nN. The overlap of different cycles is remarkable: the NW did 600 cycles substrate thermal expension coefficient and despite great care in
and still remained perfectly elastic, with the absence of noticeable handling, only 15 out of 25 samples survived the heat treatment.
hysteresis. The following cycles, in turquoise for the load and blue for These were exposed again to bending measurements, and the values
the unload, show a lower force than previous one (red) for the same of Eb are reported in Fig. 5(c), where for the sake of comparison, the
displacement and a marked hysteresis. In the subsequent #602 loading/ titanate NWs are plotted, as well. One can notice that Eb is much higher

Fig. 4. Fatigue-test of the titanate NW. (a) The force – release cycle has been applied multiple times, showing the gradual decrease of the slope (stronger and stronger
deflection) due to the consecutive ruptures of the titanate layers, until the final rupture of the NW. (b) SEM image showing the rupture in the middle of the NW.

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for the anatase NWs, due to the absence of the shear modulus in the [3] B. O'Regan, M. Grätzel, A low-cost, high-efficiency solar cell based on dye-sensitized
mechanical response, so Eb corresponds to E. It is known from in- colloidal TiO 2 films, Nature 353 (1991) 737–740, https://doi.org/10.1038/
353737a0.
dentation measurement, that for the bulk, anatase single crystal [4] D. Gust, T.A. Moore, A.L. Moore, Mimicking photosynthetic solar energy trans-
E = 167 ± 15 GPa [39]. Recent atomistic simulations of mechanical duction, Acc. Chem. Res. 34 (2001) 40–48, https://doi.org/10.1021/ar9801301.
deformation of anatase sample performed on an assembly of nano- [5] R.L. Pozzo, M.A. Baltanás, A.E. Cassano, Supported titanium oxide as photocatalyst
in water decontamination: state of the art, Catal. Today 39 (1997) 219–231,
crystalline grains of 2–6 nm in size, resulted in Young's modulus in the https://doi.org/10.1016/S0920-5861(97)00103-X.
170–200 GPa range [40]. Our anatase NWs cover this range, although [6] R.W. Matthews, Photooxidation of organic impurities in water using thin films of
the high abundance of lower values testify that during the re- titanium dioxide, J. Phys. Chem. 91 (1987) 3328–3333, https://doi.org/10.1021/
j100296a044.
crystallization a considerable amout of defects were created, which [7] S. Malato, P. Fernández-Ibáñez, M.I. Maldonado, J. Blanco, W. Gernjak,
reduce its mechanical response. Decontamination and disinfection of water by solar photocatalysis: recent overview
and trends, Catal. Today 147 (2009) 1–59, https://doi.org/10.1016/j.cattod.2009.
06.018.
3.4. Superelasticity of titanate NWs
[8] A. Fujishima, T.N. Rao, D.A. Tryk, TiO2 photocatalysts and diamond electrodes,
Electrochim. Acta 45 (2000) 4683–4690, https://doi.org/10.1016/S0013-4686(00)
The surprising observation of the super elastic behavior of the ti- 00620-4.
tanate nanowire shown in Fig. 1(c), inferring a radius of curvature of [9] A. Fujishima, K. Hashimoto, T. Watanabe, TiO2 Photocatalysis: Fundamentals and
Applications, Bkc, Tokyo, 1999.
1.5–2.5 μm merits few words. It has to be mentioned that this behavior [10] K. Nakata, A. Fujishima, TiO2 photocatalysis: design and applications, J.
is not restricted to titanate NWs, but has been observed for other NWs Photochem. Photobiol. C Photochem. Rev. 13 (2012) 169–189, https://doi.org/10.
as well (gold NWs [41], CH3NH3PbI3 NWs [39]). In our view, this ne- 1016/j.jphotochemrev.2012.06.001.
[11] D.B. Strukov, G.S. Snider, D.R. Stewart, R.S. Williams, The missing memristor
cessitates the absence of grain boundaries, of dislocation which would found, Nature 453 (2008) 80–83, https://doi.org/10.1038/nature06932.
cause a departure from the elastic behavior and would result in a higher [12] P.K. Dutta, A. Ginwalla, B. Hogg, B.R. Patton, B. Chwieroth, Z. Liang, P. Gouma,
fragility. It means that a good number of our titanate NWs (without M. Mills, S. Akbar, Interaction of carbon monoxide with anatase surfaces at high
Temperatures: optimization of a carbon monoxide sensor, J. Phys. Chem. B 103
improved statistics) have a high structural quality. (1999) 4412–4422, https://doi.org/10.1021/jp9844718.
[13] M.M. Arafat, B. Dinan, S.A. Akbar, A.S.M.A. Haseeb, Gas sensors based on one di-
4. Conclusion mensional nanostructured metal-oxides: a review, Sensors 12 (2012) 7207–7258,
https://doi.org/10.3390/s120607207.
[14] H. Wu, C. Xu, J. Xu, L. Lu, Z. Fan, X. Chen, Y. Song, D. Li, Enhanced super-
In conclusion, we performed mechanical measurements on titanate capacitance in anodic TiO2nanotube films by hydrogen plasma treatment,
NWs using an AFM-based bending test. In this layered structured ma- Nanotechnology 24 (2013) 455401, , https://doi.org/10.1088/0957-4484/24/45/
455401.
terial, we have given evidence of the presence of a low shear modulus of
[15] M. Salari, K. Konstantinov, H. Kun Liu, Enhancement of the capacitance in TiO 2
G = 1.5 ± 0.8 GPa, which strongly influences the mechanical re- nanotubes through controlled introduction of oxygen vacancies, J. Mater. Chem. 21
sponse of these NWs, despite the high E of 67 ± 25 GPa. The low G (2011) 5128–5133, https://doi.org/10.1039/C0JM04085A.
may play a role in the fatigue of the NWs. The thermal transformation [16] J. Xu, C. Jia, B. Cao, W.F. Zhang, Electrochemical properties of anatase TiO2 na-
notubes as an anode material for lithium-ion batteries, Electrochim. Acta 52 (2007)
and recrystallization of the titanate into anatase NWs, without shear 8044–8047, https://doi.org/10.1016/j.electacta.2007.06.077.
behavior, increases E towards the bulk value. [17] E. Horváth, P.R. Ribič, F. Hashemi, L. Forró, A. Magrez, Dye metachromasy on
Owing to the low radius of curvature coupled with superior me- titanate nanowires: sensing humidity with reversible molecular dimerization, J.
Mater. Chem. 22 (2012) 8778–8784, https://doi.org/10.1039/C2JM16443D.
chanical strength of titanate and anatase nanowires against repetitive [18] M.T. Byrne, J.E. McCarthy, M. Bent, R. Blake, Y.K. Gun’ko, E. Horvath, Z. Konya,
bending stress conditions, these materials may serve as building blocks A. Kukovecz, I. Kiricsi, J.N. Coleman, Chemical functionalisation of titania nano-
of future flexible energy devices, environmental decontamination sys- tubes and their utilisation for the fabrication of reinforced polystyrene composites,
J. Mater. Chem. 17 (2007) 2351–2358, https://doi.org/10.1039/B612886F.
tems, super thermal-insulators, sensors, catalyst supports and fiber-re- [19] X. Mettan, J. Jaćimović, O.S. Barisić, A. Pisoni, I. Batistić, E. Horváth, S. Brown,
inforced plastics, metals and ceramics. L. Rossi, P. Szirmai, B. Farkas, H. Berger, L. Forró, Tailoring thermal conduction in
anatase TiO2, Commun. Phys. 2 (2019), https://doi.org/10.1038/s42005-019-
0224-7.
Declaration of competing interest
[20] P. Hernández-Hipólito, M. García-Castillejos, E. Martínez-Klimova, N. Juárez-
Flores, A. Gómez-Cortés, T.E. Klimova, Biodiesel production with nanotubular so-
dium titanate as a catalyst, Catal. Today 220–222 (2014) 4–11, https://doi.org/10.
The authors declare that they have no known competing financial
1016/j.cattod.2013.09.003.
interests or personal relationships that could have appeared to influ- [21] E. Horváth, L. Forró, A. Magrez, Titanium Oxide Aerogel Composites,
ence the work reported in this paper. EP2964577A1, 2016, https://patents.google.com/patent/EP2964577A1/en ac-
cessed December 17, 2019.
[22] Y. Xiao, J. Wu, G. Yue, G. Xie, J. Lin, M. Huang, The preparation of titania nano-
Acknowledgments tubes and its application in flexible dye-sensitized solar cells, Electrochim. Acta 55
(2010) 4573–4578, https://doi.org/10.1016/j.electacta.2010.03.011.
The discussion of the superelastic behavior of NWs with Dr. D. Mari [23] D. Zhang, J.A. Downing, F.J. Knorr, J.L. McHale, Room-temperature preparation of
nanocrystalline TiO2 films and the influence of surface properties on dye-sensitized
and the support of pre-launched Swoxid SA are greatly acknowledged. solar energy conversion, J. Phys. Chem. B 110 (2006) 21890–21898, https://doi.
We thank the technical help of Dr. N. Jomaa, Dr. L. Ćirić, V. org/10.1021/jp0640880.
Nussbaumer, and Dr. M. Spina as well as the CIME-EPFL for access to [24] X. Li, H. Lin, J. Li, N. Wang, C. Lin, L. Zhang, Chemical sintering of graded TiO2 film
at low-temperature for flexible dye-sensitized solar cells, J. Photochem. Photobiol.
the electron microscopes. Chem. 195 (2008) 247–253, https://doi.org/10.1016/j.jphotochem.2007.10.010.
[25] J. Zhi, C. Yang, T. Lin, H. Cui, Z. Wang, H. Zhang, F. Huang, Flexible all solid state
Appendix A. Supplementary data supercapacitor with high energy density employing black titania nanoparticles as a
conductive agent, Nanoscale 8 (2016) 4054–4062, https://doi.org/10.1039/
C5NR08136J.
Supplementary data to this article can be found online at https:// [26] Y. Dkhissi, F. Huang, S. Rubanov, M. Xiao, U. Bach, L. Spiccia, R.A. Caruso, Y.-
doi.org/10.1016/j.ceramint.2020.04.077. B. Cheng, Low temperature processing of flexible planar perovskite solar cells with
efficiency over 10%, J. Power Sources 278 (2015) 325–331, https://doi.org/10.
1016/j.jpowsour.2014.12.104.
References [27] D. Liu, T.L. Kelly, Perovskite solar cells with a planar heterojunction structure
prepared using room-temperature solution processing techniques, Nat. Photon. 8
[1] U. Diebold, The surface science of titanium dioxide, Surf. Sci. Rep. 48 (2003) (2014) 133–138, https://doi.org/10.1038/nphoton.2013.342.
53–229, https://doi.org/10.1016/S0167-5729(02)00100-0. [28] N.-S. Jang, M.S. Kim, S.-H. Kim, S.-K. Lee, J.-M. Kim, Direct growth of titania na-
[2] L.G. Phillips, D.M. Barbano, The influence of fat substitutes based on protein and notubes on plastic substrates and their application to flexible gas sensors, Sensor.
titanium dioxide on the sensory properties of lowfat milks, J. Dairy Sci. 80 (1997) Actuator. B Chem. 199 (2014) 361–368, https://doi.org/10.1016/j.snb.2014.03.
2726–2731, https://doi.org/10.3168/jds.S0022-0302(97)76234-9. 113.
[29] N. Tétreault, E. Horváth, T. Moehl, J. Brillet, R. Smajda, S. Bungener, N. Cai,

17733
L. Rossi, et al. Ceramics International 46 (2020) 17729–17734

P. Wang, S.M. Zakeeruddin, L. Forró, A. Magrez, M. Grätzel, High-efficiency solid- [35] A. Bo, H. Zhan, J. Bell, H. Zhu, Y. Gu, Mechanical bending properties of sodium
state dye-sensitized solar cells: fast charge extraction through self-assembled 3D titanate (Na2Ti3O7) nanowires, R. Soc. Chem. 4 (2014) 56970–56976, https://doi.
fibrous network of crystalline TiO2 nanowires, ACS Nano 4 (2010) 7644–7650, org/10.1039/c4ra11753k.
https://doi.org/10.1021/nn1024434. [36] A. Bo, K. Chen, E. Pickering, H. Zhan, J. Bell, A. Du, Y. Zhang, X. Wang, H. Zhu,
[30] E. Horváth, I. Szilágyi, L. Forró, A. Magrez, Probing titanate nanowire surface Z. Shan, Y. Gu, Atypical defect motions in brittle layered sodium titanate nanowires,
acidity through methylene blue adsorption in colloidal suspension and on thin J. Phys. Chem. Lett. 9 (2018) 6052–6059, https://doi.org/10.1021/acs.jpclett.
films, J. Colloid Interface Sci. 416 (2014) 190–197, https://doi.org/10.1016/j.jcis. 8b02349.
2013.10.049. [37] M. Humar, D. Arčon, P. Umek, M. Škarabot, I. Muševič, G. Bregar, Mechanical
[31] J.-P. Salvetat, A.J. Kulik, J.-M. Bonard, G.A.D. Briggs, T. Stöckli, K. Méténier, properties of titania-derived nanoribbons, Nanotechnology 17 (2006) 3869–3872,
S. Bonnamy, F. Béguin, N.A. Burnham, L. Forró, Elastic modulus of ordered and https://doi.org/10.1088/0957-4484/17/15/043.
disordered multiwalled carbon nanotubes, Adv. Mater. 11 (1999) 161–165, https:// [38] C.Q. Chen, Y. Shi, Y.S. Zhang, J. Zhu, Y.J. Yan, Size dependence of Young's modulus
doi.org/10.1002/(SICI)1521-4095(199902)11:2<161:AID-ADMA161>3.0. in ZnO nanowires, Phys. Rev. Lett. 96 (2006) 075505, , https://doi.org/10.1103/
CO;2-J. PhysRevLett.96.075505.
[32] J.-P. Salvetat, G.A.D. Briggs, J.-M. Bonard, R.R. Bacsa, A.J. Kulik, T. Stöckli, [39] L. Ciric, Unpublished, n.d., personal communication.
N.A. Burnham, L. Forró, Elastic and shear moduli of single-walled carbon nanotube [40] X. Zhang, H. Gao, X. Li, Atomistic simulations of superplasticity and amorphization
ropes, Phys. Rev. Lett. 82 (1999) 944–947, https://doi.org/10.1103/PhysRevLett. of nanocrystalline anatase TiO2, Extreme Mech. Lett. 22 (2018) 131–137, https://
82.944. doi.org/10.1016/j.eml.2018.05.009.
[33] J.M. Gere, S.P. Timoshenko, Mechanics of Materials, PWS Publishing Company, [41] B. Wu, A. Heidelberg, J.J. Boland, Mechanical properties of ultrahigh-strength gold
Boston, MA, 1990. nanowires, Nat. Mater. 4 (2005) 525–529, https://doi.org/10.1038/nmat1403.
[34] A. Kis, G. Csányi, J.-P. Salvetat, T.-N. Lee, E. Couteau, A.J. Kulik, W. Benoit, [42] L. Rossi, X. Berdat, M. Spina, S. Brown, S. Katrych, L. Forró, E. Horváth, Thermal
J. Brugger, L. Forró, Reinforcement of single-walled carbon nanotube bundles by coarsening of individual titanate nanowires and their assemblies: surface vs. bulk
intertube bridging, Nat. Mater. 3 (2004) 153–157, https://doi.org/10.1038/ diffusion, Ceram. Int. (2020), https://doi.org/10.1016/j.ceramint.2020.03.189.
nmat1076.

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