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Thermoresponsive Shape-Memory Photonic

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Nanostructures
André Espinha, María Concepción Serrano,* Álvaro Blanco, and Cefe López

Technological applications increasingly demand materials with preparation of compression sensitive inverse opals which allow
sophisticated features and improved functionalities. In this the mechanical tuning of the photonic stopgap position.[18]
context, multifunctional materials (MFMs) are especially attrac- Elastomers have also played a fundamental role for studying
tive as they are often capable of responding to different phys- color tunable photonic crystals (PCs),[19,20] whose lattice param-
ical, chemical and/or biological stimuli. A particularly useful eter might be controlled by deformation (mechanochromic
property that has been incorporated into MFMs is the shape- effect) or elastomer swelling.[21] An equivalent approach was
memory effect (SME), which was first identified in a gold- proposed for the development of tunable phononic crystals.[22]
cadmium alloy[1] and posteriorly discovered in polymers (the Another active area of research concerns flexible systems imple-
so-called shape-memory polymers, SMPs).[2,3] SMPs are able mented, for instance, as UV-filters[23] and light emitting diodes
to switch from a temporary to a permanent shape in response or displays.[24] The present work addresses the fabrication of
to an external stimulus.[4] They represent a more efficient periodic nanofeatures with SME by using a replica molding
alternative, less expensive and easier to implement with high approach for imprinting a 2D photonic nanostructure on the
throughput, than conventional shape-memory alloys. Although surface of a shape-memory elastomer. Structural and optical
heat is typically responsible for directly triggering SME,[5] recent characterization of the as-produced system allowed to demon-
advances have identified indirect mechanisms such as electrical strate its shape-memory functionality for configuring the lattice
stimulation[6] or alternating magnetic field excitation.[7] Interest- parameter or erasing the nanopattern. This property might be
ingly, there are also reports describing heat-independent light- very attractive, for example, for the development of reusable or
activated SME.[8,9] In terms of chemical composition, SMPs self-healing photonic elements with adaptive properties.
made of acrylamides,[10] caprolactones,[11] and polyurethanes[12] Polydiolcitrates (PDCs), first described by Ameer and col-
have been explored as stimuli-sensitive polymers with advanced leagues in 2004,[25] have been recently identified as thermore-
functionalities.[13] They are suitable for applications as diverse sponsive elastomers presenting SME.[26] However, as far as we
as self-deployable sun-sails or microfoldable vehicles.[14,15] know, their applicability in the accomplishment of photonic
Despite SMPs having been extensively explored in bulk nanostructured systems has not been reported in the literature
form,[12] the investigation of the SME at the micro/nano scales yet. The synthesized polyester networks were obtained upon:
is a very recent topic.[16] Furthermore, the use of SMPs for pro- (1) increase of the mol ratio of hydroxyl to carboxyl groups in
ducing nanostructures with photonic functionality is still in its the reaction mixture (4:3 in hydroxyl-dominant PDCs versus 1:1
infancy. In general terms, photonic structures refer to patterned in the original ones) and (2) the use of a more hydrophobic diol
media with features in a typical size of the order of, or below, (e.g., 1,12-dodecanediol, DD). These polymers include covalent
visible or near-infrared radiation wavelengths. These features netpoints responsible for the permanent shape and hydrophobic
translate into a modulation of the refractive index that causes micro-domains (either pre-polymer or DD-rich domains) physi-
a strong radiation/matter interaction and significantly affects cally cross-linked by intermolecular hydrophobic interactions as
the electromagnetic density of states. In this context, strategies switch structures to fix the temporary shape. To investigate the
for achieving periodic structures exhibiting SME are highly SME of these polymers for potential photonic applications, we
desirable, in order to develop novel MFMs and optical devices. followed the general procedure depicted in Figure 1. The first
Contrary to SMPs, elastomers have been more employed in step consisted of the synthesis of the pre-polymer solution com-
photonics although almost exclusively to take advantage of posed of DD and citric acid. 1H nuclear magnetic resonance (1H-
their elastic properties. For instance, some reports have dem- NMR) confirmed the mol ratio expected for both components
onstrated their use in the fabrication of elastic transmission (1.5) and the beginning of the condensation reaction (e.g., mul-
gratings or lenses with real time control of the periodicity or tiplicity of peaks at 2.6–2.9 ppm) (see Supporting Information
the focal length, respectively.[17] They have been applied to the (SI), Figure S7). Nanopatterning of the elastomer surface was
achieved by using an approach inspired in soft-lithography[27]
and, more specifically, in replica molding (Figure 1a).[28,29]
Briefly, the pre-polymer solution was spread over the template,
A. Espinha, Dr. M. C. Serrano, Dr. A. Blanco,
Prof. C. López
in our case a colloidal monolayer composed of polystyrene (PS)
Instituto de Ciencia de Materiales spheres of 870 nm in diameter (d). After curing at 90 °C for
de Madrid (ICMM-CSIC) 12 h, the resulting cross-linked polymer (PDDC-HD) was peeled
Calle Sor Juana Inés de la Cruz, 3 off from the monolayer. When evaluating the cross-linking
Cantoblanco 28049, Madrid, Spain degree of the so-produced elastomer, a Mc value of 736 g mol−1
E-mail: [email protected]
was obtained, in range with those previously reported for this
DOI: 10.1002/adom.201300532 type of polyesters.[26] During cross-linking, the surface of the

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Figure 1. Scheme of the protocol followed for the grating imprint on the PDDC-HD elastomer surface (a) and study of its programmable shape-memory
properties either varying the lattice parameter (b) or erasing the surface nanotopography (c).

PDDC-HD polymer acquired the permanent shape determined existence of these two transitions at a similar range of tem-
by the colloidal crystal structure, as confirmed by atomic force peratures. Young modulus values of ca. 100 MPa were meas-
microscopy (AFM) studies (Figure 2). As can be observed, the ured at 10 °C (T < Ttrans) and 2 MPa above Ttrans (e.g., 35 °C)
elastomer surface consisted of a homogeneous hexagonal array (Figure S9). Interestingly, this transition could be monitored
of nanobowls of an average depth of 140 ± 30 nm. This surface additionally via the optical properties of the polymer. The
nanopattern was created as a replica of the PS spheres mon- opaqueness characteristic of its glassy state at low tempera-
olayer, which remained in the mold after peeling off the cured ture, caused by the scattering of light from the solid non-
polymer (Figure S1). This protocol was further confirmed suit- cross-linked micro-domains of pre-polymer and DD, gradu-
able for templates composed of spheres with other diameters, ally disappears as the material transits to the rubbery state. In
as exemplified in Figure S2 for d = 200 nm. To avoid polymer this state, the micro-domains melt giving rise to a significant
cross-linking with the mold that could impair its removal, PS increase in transparency. This effect is exhibited in Figure 3,
spheres were intentionally selected. By doing so, it was possible which presents the visual aspect of the sample at both room
to peel off the cured elastomer from the template while still temperature (Figure 3a) and above Ttrans (Figure 3b). We fur-
warm, to take advantage of its elastic properties. Additionally, ther explored this thermally-induced phenomenon by total
the hydrophobic nature of the PS spheres contributed to repeal optical transmittance spectroscopy measurements (Figure S3).
the elastomer from embedding deeply into the monolayer, thus A small disk of PDDC-HD (2.5 mm-thick) was heated at 90 °C
explaining why the groove's depth obtained was on the order of for 10 min and then allowed to cool down at its natural pace
140 nm instead of the expected 435 nm, should the elastomer while monitoring simultaneously the temperature and the
have reached at least the equator of the spheres. total transmittance. Results for the wavelengths λ = 532 and
Similarly to original PDDC-HD elastomers,[26] surface- 633 nm are presented in Figure 3c. From 70 °C to 26 °C, a
nanopatterned PDDC-HD displayed both a glass transition constant plateau in which the transmittance was on the order
at ca. –4 °C and a melting thermal transition responsible of 95% was observed. As the temperature decreased below
for the SME at ca. 30 °C, as revealed in the thermograms 26 °C, the transition was confirmed by a decrease in trans-
obtained by modulated differential scanning calorimetry mittance of ca. 70% (final sample transmittance 25–31%).
(mDSC) (Figure S8). Above Ttrans the polymer becomes an This property is of considerable interest since it supports the
elastomer (rubber state) in which the degree of cross-linking applicability of PDDC-HD as a thermo-optical trigger (i.e., a
and hydrogen bonding controls the elasticity of the network. device that transmits light only above a particular temperature
Dynamic mechanical analysis (DMA) further confirmed the threshold).

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been investigated for thermochromic effects, e.g., the fabrica-

tion of inverse opals with demonstrated stopgap dependence on
temperature.[30] A more recent work described novel elastomeric
crystalline films with triple stimuli response to strain, light and
temperature.[31] On the other side, the full advantages of SME are
starting to be explored in the design of photonic devices. Davies
et al. reported on a chiral-nematic polymer network presenting
SME applied into manufacturing an optical temperature sensor,
which changed color as the original form of the material was
restored above a certain temperature threshold.[32] The SME was
also the driving mechanism that enabled Xie and co-workers
to develop metallic wrinkle membranes exhibiting structural
color.[33,34] They demonstrated a correlation between the pitch of
the wrinkles and the strain applied to the polymeric substrate.
Besides these findings, Rogers et al. reported on the exploration
of SMPs towards the fabrication of micro-optical devices or PCs
with reversible but programmable characteristics.[35] By using
interference lithography, Yang and colleagues developed mem-
branes with programmable color switching.[36] In comparison
to this previous work, our strategy for the fabrication of SME
photonic nanostructures presents important advantages due to
the use of colloidal crystals as templates. Since these are fabri-
cated with monodisperse particles which are available in a wide
range of diameters, an increased control over the final structure
and lattice parameter could be achieved. Further, our method
is straightforward and does not require complex or expensive
equipment.
Light diffraction was used for systematically studying the
possibility of programing the sample towards the development
of a thermoresponsive optical grating with shape-memory.
This was achieved by observing the diffraction figure projected
Figure 2. AFM 3D surface reconstructions of the nanopatterned elas- on a screen positioned in the far-field. First, the angle of dif-
tomer at two different magnifications. These images demonstrate the fraction (θd) was measured for the sample at its initial state.
successful imprinting of the nanobowls in the PDDC-HD surface. The obtained results and their comparison with the theoretical
model (SI) are presented in Table S1. As can be appreciated,
Tailoring of materials towards the development of thermo- the agreement is excellent. We next explored how elongation
optical systems has attracted considerable interest from the pho- affected the PC imprinted in the elastomer. A single iteration
tonics community. On one side, materials without SME have of the protocol followed is presented in Figure 1b. Diffraction

Figure 3. Visual aspect of the surface-nanopatterned PDDC-HD elastomer at room temperature (a) and above Ttrans (b). Temperature dependence of
the total optical transmittance of the sample, for λ = 532 and 633 nm, exhibiting the change in transparency characteristic of the transition (c).

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discussed in detail in the SI. Strain was
increased up to 100% (with greater preci-
sion for small strains) while monitoring the
angles at λ = 532 nm or λ = 633 nm. Good
agreement was found between experimental
data and theoretical predictions up to strains
of 100%, thus confirming that it was pos-
sible to fix the lattice parameter of the 2D
PC in the predefined way. Nevertheless, the
concordance was slightly worse above 60%
of strain possibly due to two contributing
factors. On the one hand, the deformation
got increasingly inhomogeneous along the
sample, being more intense near the sus-
taining clamps. On the other hand, the dif-
fraction spots projected on the screen gradu-
ally deformed into line segments implying a
worse defined θd. In any case, as exhibited in
the right plot of Figure 4c, the original dif-
fraction angles were entirely restored after
heating the sample at the end of the pro-
cess, which demonstrates the SME affecting
the 2D grating. It is worth noting that the
data plotted correspond to a single piece of
polymer and that each data point entails a
heat-stretch-cool-relax cycle followed by a
heat-relax cycle, setting a cyclability indica-
tion. In this particular study, up to 35 cycles
were achieved with a representative sample.
However, a modest cyclability is expected for
this type of polymers as higher temperatures
impact on polymer cross-linking and gradu-
ally eliminate the shape-memory properties
of the material while increasing its stiffness.
The second test to ascertain program-
Figure 4. Representative polar plots exhibiting the experimental points coordinates of a dif-
mable features of the photonic nanostruc-
fraction figure from nanopatterned PDDC-HD in the initial state (a) and after fixing a strain of
15% (b) for two wavelengths: λ = 532 (green) and 633 nm (red). Experimental (triangles) and ture imprinted in the PDDC-HD polymer
theoretical (solid
 lines)
 behaviors of the diffraction angles along the two principal symmetry was to study if it could be erased and later
directions (b1 and b2) as a function of the strain imposed to the sample (c). The inset exhibits recovered by using its SME. This hypoth-
the complete range up to 100% of strain. Plot on the right (iii) corresponds to the angles esis was supported by previous work on
measured after re-heating the polymer and recovering its initial shape. SME at the nanoscale.[16] The procedure
was implemented as depicted in Figure 1c.
images were collected in the cycle steps labelled as i, ii and iii – Accordingly, the sample was compressed between two hydro-
some key examples are provided in Figure S4. The process was phobic surfaces of polypropylene. The thickness reduction of
continued by successively increasing the applied strain while the elastomeric piece, after fixing the temporary shape and
monitoring the diffraction
 angles along the two symmetry releasing the applied stress, was on the order of 50%. The
directions (b1 and b2) of the reciprocal space (Figure 4). When morphology of the PDDC-HD elastomer in the three states
the sample was stretched and cooled below Ttrans, the tempo- labelled as i, ii and iii was characterized by AFM, scanning
rary shape was fixed   and thus the lattice parameter increased electron microscopy (SEM) and optical diffraction measure-
(decreased) along b1 (b2 by Poisson effect). These changes in the ments (Figure 5). As expected, the obtained pattern profile
periodicity of the grating directly affected the diffraction angles was very similar for states i and iii, contrarily to that obtained
and, therefore, the diffraction figure gradually deformed from for state ii (Figure 5a). The surface roughness in state ii
a circumference to an ellipse as clearly exhibited in Figure decreased in comparison to i and iii (Table 1), in agreement
4a and b, respectively. This effect can be compared with the with its much smoother aspect observed by SEM (Figure 5b).
control of plasmonic resonances in stretched hexagonal lat- In ii, the pattern might still be intuited, although with a sig-
tices used for fabricating elliptical gold rings.[37] The behavior nificant decrease of contrast. Finally, diffraction images were
of the diffraction angles as a function of the applied strain collected in order to study how the described behavior
is presented in Figure 4c, along with the theoretical model affected the optical properties of the PDDC-HD-based PC. As

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Figure 5. Horizontal profiles as measured by AFM of the initial sample (i), after compression and nanopattern erasing (ii) and after shape recovery
(iii) (a). Similar characterization using SEM (b). Diffraction images of the PDDC-HD sample in the referred states for two wavelengths: λ = 532 and
633 nm (c and d, respectively).

observed in Figure 5c, hexagonal patterns were obtained and with thermoresponsive shape-memory characteristics. Two
reproduced along the entire sample area in states i and iii. On proofs of concept were reported herein, representing advances
the contrary, for state ii, it was impossible to observe any dif- in both SMPs and photonics fields. Firstly, we showed that
fraction image while scanning through the whole surface. We the lattice parameter of the 2D grating was programmable
hypothesize that, although the nanopattern was not entirely and dependent of the strain imposed to the polymer. Sec-
erased by compression (see results from SEM analysis), the ondly, it was feasible to transitorily erase the surface nanopat-
periodic part of the modulation became comparable to, or tern from the optical point of view. In both cases, the char-
smaller than, the random part so that light scattering was acteristics of the original structure were entirely recovered
essentially insensitive to it. by simply heating the sample above Ttrans, thus proving the
The multifunctional nature of PDDC-HD is confirmed by SME affecting the optical properties of the PC and also its
several interesting features. It is elastomeric, biocompatible, read/write capabilities with potential application in emergent
biodegradable and also presents SME and drug releasing technologies. Alternatively, the use of light-induced SME,
capabilities. In the present work, we further expanded this independent from temperature, might be a valuable asset for
spectrum of functionalities. It was shown that, by using a future developments in this area. We also envision the pre-
simple procedure based in replica molding, it was possible sent system to have a wide impact, not exclusively in the field
to engrave a hexagonal nanostructured pattern from a col- of photonics, due to the feasibility of incorporating additional
loidal crystal template in the surface of the PDDC-HD elas- components such as bioactive molecules or nanoparticles
tomer. By doing so, we demonstrated the applicability of the into the polymeric network. This fact opens a wide range of
reported system in the achievement of active optical elements opportunities for the combination of different functionalities
in these nanostructured PDDC-HD elastomers, thus creating
systems with application in biomaterials, nanoelectromechan-
Table 1. Comparison among the average (Ra), root mean squared (Rrms)
and maximum (Rmax) surface roughness of the PDDC-HD sample in
ical devices, self-healing optical elements, or devices with pro-
states i, ii and iii, as measured by AFM. grammable hydrophobicity. To guarantee a long-term usage,
for this particular choice of materials, storage in dry condi-
State Ra Rrms Rmax tions at temperatures below 4 °C is recommended in order
[nm] [nm] [nm] to preserve polymer cross-linking and avoid its degradation.
i 52.8 68.4 774.8 At the same time, their biodegradability could be especially
attractive for the fabrication of disposable devices with appli-
ii 7.1 9.6 71.1
cation in areas such as biomedicine and biophotonics, when
iii 54.4 68.0 631.3 only the temporal presence of the material is pursued.

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thermocamera. A.E. was supported by the FPI Ph.D. program from the
MICINN. M.C.S. acknowledges MINECO for a Juan de la Cierva fellowship.
Detailed information about the experimental procedures is included in
the Supporting Information. Received: December 22, 2013
Chemicals: All chemicals were purchased from Sigma-Aldrich and Revised: February 20, 2014
used as received unless otherwise indicated. Colloidal spherical particles Published online: March 19, 2014
of PS with polydispersity of 3% were purchased from Thermo Scientific.
Fabrication of the Monolayers: The monolayers of PS spheres were
[1] L. C. Chang, T. A. Read, Trans. AIME 1951, 189, 47.
grown according to a previously reported method.[38] A wedge shape
[2] B. K. Kim, S. Y. Lee, M. Xu, Polymer 1996, 37, 5781.
cell was used to confine the colloid and allow solvent evaporation in
controlled conditions. [3] Y. Osada, A. Matsuda, Nature 1995, 376, 219.
Synthesis of the Elastomer: Elastomer synthesis was performed [4] M. Behl, A. Lendlein, Mater. Today 2007, 10, 20.
following the general procedure previously described.[26] To create the [5] I. Bellin, S. Kelch, R. Langer, A. Lendlein, Proc. Natl. Acad. Sci. USA
surface relief grating on the elastomer, the liquid pre-polymer solution 2006, 103, 18043.
was placed on top of a monolayer of PS spheres of different diameters [6] J. W. Cho, J. W. Kim, Y. C. Jung, N. S. Goo, Macromol. Rapid Comm.
(either 200 or 870 nm) and allowed post-polymerizing at 90 °C for 2005, 26, 412.
12 h (for 2 mm-thick samples). After that time, the cross-linked [7] T. Weigel, R. Mohr, A. Lendlein, Smart Mater. Struc. 2009, 18,
elastomer (PDDC-HD polymer) was removed from the sphere monolayer 025011.
by carefully peeling it off when still warm. [8] A. Lendlein, H. Y. Jiang, O. Jünger, R. Langer, Nature 2005, 434, 879.
Chemical, Thermal and Optical Characterization: 1H-NMR spectrum of [9] H. Y. Jiang, S. Kelch, A. Lendlein, Adv. Mater. 2006, 18, 1471.
the pre-polymer solution was recorded at room temperature by using a [10] R. Yoshida, K. Uchida, Y. Kaneko, K. Sakai, A. Kikuchi, Y. Sakurai,
Bruker spectrometer DRX-500 at 500 MHz. The mol ratio of DD to citric T. Okano, Nature 1995, 374, 240.
acid was confirmed as 1.5, according to the theoretical value (mol ratio [11] A. Lendlein, R. Langer, Science 2002, 296, 1673.
3:2, respectively) and corroborating the dominance of hydroxyl versus [12] M. Behl, M. Y. Razzaq, A. Lendlein, Adv. Mater. 2010, 22, 3388.
carboxyl groups in these polymers. Details for the chemical shifts of [13] A. Lendlein, V. P. Shastri, Adv. Mater. 2010, 22, 3344.
the different groups are included in SI (Figure S7). The degree of post- [14] J. Hu, Shape Memory Polymers and Textiles, Woodhead Publishing
polymerization in the resulting cross-linked PDDC-HD was evaluated
Limited, Cambridge, UK 2007.
by calculating the molecular weight between cross-links (Mc) through
[15] W. M. Huang, C. W. Lee, H. P. Teo, J. Intel. Mater. Syst. Str. 2006, 17, 753.
swelling studies in dimethylsulfoxide.[39] mDSC studies were performed
[16] T. Altebaeumer, B. Gotsmann, H. Pozidis, A. Knoll, U. Duerig,
by using a Discovery DSC Calorimeter (TA Instruments). Briefly, samples
were cooled to –60 °C, held for 5 min and then ramped from –60 °C to Nano. Lett. 2008, 8, 4398.
75 °C at a rate of 2 °C min−1 (modulation amplitude ±2 °C and frequency [17] J. L. Wilbur, R. J. Jackman, G. M. Whitesides, E. L. Cheung, L. K. Lee,
60 s−1) (Figure S8). Total transmission of the PDDC-HD sample was M. G. Pretiss, Chem. Mater. 1996, 8, 1380.
collected from 90 °C to 23 °C with an integrating sphere fiber-coupled to [18] A. C. Arsenault, T. J. Clark, G. von Freymann, L. Cademartiri,
an Ocean 2000 compact spectrometer. The temperature was monitored R. Sapienza, J. Bertolotti, E. Vekris, S. Wong, V. Kitaev, I. Manners,
in parallel with a thermocamera Fluke Ti10. R. Z. Wang, S. John, D. Wiersma, G. A. Ozin, Nat. Mater. 2006, 5, 179.
Thermomechanical Characterization: The complex Young modulus [19] C. I. Aguirre, E. Reguera, A. Stein, Adv. Funct. Mat. 2010, 20, 2565.
(viscoelastic behaviour) of the PDDC-HD elastomer was measured from [20] B. Viel, T. Ruhl, G. P. Hellmann, Chem. Mater. 2007, 19, 5673.
−30 to 50 °C at a rate of 2 °C min−1 at 5 Hz in a triple point bending [21] J. M. Jethmalani, W. T. Ford, Chem. Mater. 1996, 8, 2138.
configuration by using a Dynamic Mechanic Analyzer DMA 7e (Perkin [22] J. H. Jang, C. K. Ullal, T. Gorishnyy, V. V. Tsukruk, E. L. Thomas,
Elmer). The first heating run of the DMA spectrum of a representative Nano Lett. 2006, 6, 740.
sample is presented in Figure S9. [23] M. E. Calvo, H. Míguez, Chem. Mater. 2010, 22, 3909.
Surface Grating Characterization: The surface nanotopography of the [24] J. Liang, L. Li, X. Niu, Z. Yu, Q. Pei, Nat. Photonics 2013, 7, 3.
PDDC-HD samples was first characterized at room temperature by using [25] J. Yang, A. R. Webb, G. A. Ameer, Adv. Mater. 2004, 16, 511.
an AFM multimode Nanoscope III A (Bruker) with a FESP tip working in [26] M. C. Serrano, L. Carbajal, G. Ameer, Adv. Mater. 2011, 23, 2211.
tapping mode. Additionally, the nanometric grating was characterized by [27] Y. Xia, G. M. Whitesides, Angew. Chem. Int. Ed. 1998, 37, 550.
SEM. Samples were mounted on stubs with carbon tape and visualized
[28] H. J. Nam, D. Jung, G. R. Yi, H. Choi, Langmuir 2006, 22, 7358.
in a FEI NovaNano SEM 230 microscope. Finally, diffraction patterns
[29] D. Losic, J. G. Mitchell, R. Lal, N. H. Voelcker, Adv. Funct. Mater.
were acquired in a home-built setup extensively described in SI.
2007, 17, 2439.
[30] G. Wu, Y. Jiang, D. Xu, H. Tang, X. Liang, G. Li, Langmuir 2011, 27, 1505.
[31] C. G. Schäfer, M. Gallei, J. Zahn, J. Engelhardt, G. Hellmann,
Supporting Information M. Rehahn, Chem. Mater. 2013, 25, 2309.
Supporting Information is available from the Wiley Online Library or [32] D. Davies, A. R. Vaccaro, S. M. Morris, N. Herzer, A. Schenning,
from the author. C. Bastiaansen, Adv. Funct. Mater. 2013, 23, 2723
[33] T. Xie, X. Xiao, J. Li, R. Wang, Adv. Mater. 2010, 22, 4390.
[34] J. Li, Y. An, R. Huang, H. Jiang, T. Xie, ACS Appl. Mater. Interfaces
Acknowledgements 2012, 4, 598.
[35] H. Xu, C. Yu, S. Wang, V. Malyarchuk, T. Xie, J. Rogers, Adv. Funct.
This work was partially supported by EU FP7 NoE Nanophotonics4Energy
grant No. 248855, the Spanish MICINN project MAT2012–31659 Mater. 2013, 23, 3299.
(SAMAP), and Comunidad de Madrid S2009/MAT-1756 (PHAMA) [36] L. Li, J. Shim, J. Deng, J. Overvelde, X. Zhu, K. Bertoldi, S. Yang, Soft
program. The authors thank Dr. Francisco del Monte (ICMM-CSIC) for Matter 2012, 8, 10322.
scientific support and fruitful discussions, Dr. María José de la Mata [37] Y. Cai, Y. Li, P. Nordlander, P. S. Cremer, Nano Lett. 2012, 12, 4881.
(Servicio Interdepartamental de Investigación, Universidad Autónoma [38] A. Espinha, M. Ibisate, J. Galisteo-López, A. Blanco, C. López, Lang-
de Madrid, UAM) for assistance with mDSC studies, Dr. Ricardo muir 2012, 28, 13172.
Jiménez (ICMM-CSIC) for his technical support in thermomechanical [39] A. R. Webb, J. Yang, G. A. Ameer, J. Polym. Sci., Part A: Polym. Chem.
characterization studies and Dr. Daniel Jaque (UAM) for support with the 2008, 46, 1318.

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