Articles

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Hydroxypropyl cellulose photonic architectures by

soft nanoimprinting lithography
André Espinha 1, Camilla Dore1, Cristiano Matricardi1, Maria Isabel Alonso 1
, Alejandro R. Goñi1,2
and Agustín Mihi 1*

As contamination and environmental degradation increase, there is a huge demand for new eco-friendly materials. Despite
its use for thousands of years, cellulose and its derivatives have gained renewed interest as favourable alternatives to con-
ventional plastics, due to their abundance and lower environmental impact. Here, we report the fabrication of photonic and
plasmonic structures by moulding hydroxypropyl cellulose into submicrometric periodic lattices, using soft lithography. This
is an alternative way to achieve structural colour in this material, which is usually obtained by exploiting its chiral nematic
phase. Cellulose-based photonic crystals are biocompatible and can be dissolved in water or not depending on the derivative
employed. Patterned cellulose membranes exhibit tunable colours and may be used to boost the photoluminescence of a host
organic dye. Furthermore, we show how metal coating these cellulose photonic architectures leads to plasmonic crystals with
excellent optical properties acting as disposable surface-enhanced Raman spectroscopy substrates.

S
ustainability is one of the fundamental challenges of modern colourful optically active ones5, depending on the amorphous or
society and in this regard, materials science has been evolving crystalline arrangement of the particles. In suspension, it is known
towards the preferential substitution of highly contaminating that cellulose and some of its derivatives may present liquid crystal-
materials by others with lower environmental impact. Polymeric line phases with bright colours13. In particular, the observation of a
materials are not an exception. It is estimated that the production of mesophase in hydroxypropyl cellulose (HPC) was first reported by
plastics worldwide is around 320 million tons each year and increas- Werbowyj and co-workers14. HPC has a structure similar to cellu-
ing1, and only about 10% of that amount is recycled, implying an lose but some of the hydroxyl groups of the glucose building blocks
enormous generation of waste with its dramatic effects on ecosys- are hydroxypropylated (Supplementary Fig. 1). Concentrated solu-
tems at the global scale. In this context, biopolymers offer an excellent tions of HPC present iridescent colours and chiral behaviour due
alternative to common plastics due to characteristics such as large to the molecular arrangement of the linear chains in a helicoidal
availability, low cost and biodegradability. They entail advantages structure. This mesophase in HPC may be very attractive for the
in three parts of product life cycle: material harvesting, processing development of responsive systems, such as recently reported strain
and fabrication, and disposal. An added value of these materials is sensors15. Here, we propose an alternative route to easily provide
their possible biocompatibility, which enables their use in new appli- cellulose derivatives with an optical functionality. We fabricate
cations within areas such as medical or food processing. Cellulose cellulose-based two-dimensional photonic structures with submi-
is probably the most interesting of these biopolymers because it is crometre features and demonstrate their potential in a variety of
the most abundant on Earth and for centuries has had a wide tech- photonic applications.
nological impact in areas such as textiles, packaging and knowledge
storage. Cellulose is a polysaccharide that results from the repetition Results and discussion
of glucose units (Supplementary Fig. 1). It is typically extracted from Nanoimprinting HPC. In the search for more versatile methods
vegetal sources and consists of fibres with dimensions of 2 to 4 mm in for achieving structural colour in cellulose derivatives, current soft
length and diameters in the range of 2 to 200 µ​m (ref. 2). Importantly, lithography techniques16 are especially suited, as they have already
these fibres are organized in a hierarchical structure. By further pro- been demonstrated to be useful for the fabrication of nanostruc-
cessing them by appropriate means such as mechanical, chemical or tures in biopolymers17. Compared with traditional optical lithogra-
enzymatic treatments, it is possible to obtain cellulose nanoparticles phy, soft lithography techniques present advantages such as a low
(nanofibrils or nanocrystals). This nanocellulose is being actively cost, large patterned areas, good quality and reproducibility, non-
investigated for many electronics, energy and biological applica- diffraction-limited and compatible with roll-to-roll processing.
tions3,4. Cellulose and particularly nanocellulose have also enabled Furthermore, while the achievement of structural colour in HPC by
new avenues in the fabrication of photonic components used, for self-assembly is time consuming due to the requirement of molec-
example, in chiral reflectors5,6, photonic electrodes7, anti-reflection ular ordering, which may last for days or weeks, soft lithography
coatings in solar cells8, multifunctional thermal-9 or humidity-10 allows for a much faster processing. For example, it has been shown
responsive optical materials, flexible substrates for plasmonic sens- that it is possible to hot emboss liquid wood18 or to use imprint-
ing11 and surface-enhanced Raman scattering spectroscopy12. ing methods compatible with roll-to-roll19,20 to structure cellulose-
The typical arrangement of cellulose microfibres scatters based polymers in a rapid way.
light diffusively, providing the well-known white colour of paper. Concentrated HPC dilutions (above 35 wt%) may form aniso-
Nanocellulose instead can form compact and transparent films2 or tropic phases21; however, in this work, we used diluted solutions

Institut de Ciència de Materials de Barcelona, Consejo Superior de Investigaciones Científicas, Barcelona, Spain. 2Institució Catalana de Recerca i Estudis
1

Avançats, Barcelona, Spain. *e-mail: amihi@[Link]

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(<​20 wt%) which, additionally, were quickly dehydrated so that the Although fast solubility in water is an attractive feature for envi-
self-assembly was hindered. Therefore, unpatterned regions of the ronmental purposes, some strategies may be adopted for obtaining
samples are homogeneous, isotropic and transparent. For nanoim- cellulose-based insoluble photonic films. Figure 1d–f compares the
printing of the HPC membranes with submicrometric features, the behaviour of three different cellulose-based membranes in water.
two soft lithography protocols illustrated in Fig. 1a were used. The Bare HPC-based films completely dissolved after being immersed
first approach consisted of a hot embossing technique where a com- in water for approximately 30 s (Fig. 1d). A step towards enhanced
posite22 hard polydimethylsiloxane (h-PDMS) stamp was slightly stability was the use of crosslinked HPC membranes (Fig. 1e). The
pressed against a heated HPC membrane. In the second case—replica crosslinking was achieved by adding divinyl sulfone to the HPC
moulding procedure—the HPC solution was poured directly on top solution in water and increasing its pH with sodium hydroxide,
of the h-PDMS stamp, then dried and finally peeled off. Both meth- before carrying out the soft lithographic step. The result is a pat-
odologies produced equivalent structures on the cellulose deriva- terned hydrogel23 that becomes white on water immersion due to
tive, only differing in the higher feature depth of the hot embossing the increased light scattering coming from the nanopores swell-
approach (Supplementary Figs. 2 and 3). The replica moulding is ing in the film. Incidentally, this system is a fast and visual humid-
more adequate for producing thick, flexible membranes while the ity sensor as it undergoes a dramatic transition from colourful to
hot embossing is preferred when highest optical quality is intended white aspect. Finally, full mechanical stability under water could be
throughout the entire area of the crystal. Different kinds of lattices, achieved by imprinting a non-soluble cellulose derivative—acetyl
such as square, hexagonal or simple grooves, with different lattice cellulose (Supplementary Fig. 1). In this case, it is possible to obtain
parameters (L) in the submicrometre region may be obtained in this a non-degradable photonic film that retains its iridescence after
way, depending only on the mould used (Supplementary Figs. 4–7). immersion in water for 60 s (Fig. 1f).
Nanoimprinting is a versatile strategy that allows the fabrica-
HPC photonic crystals. Free-standing patterned membranes were tion of HPC photonic crystal films operating at spectral ranges
achieved after peeling-off the samples fabricated with replica mould- determined by their geometry. The different colours exhibited by
ing (Fig. 1b). Patterns with areas of 1 ×​ 1 cm2, with good reproduc- the films depend on the structure, topology or lattice parameter
ibility through the entire sample, were easily produced. Moreover, imprinted. To exemplify the structural colour functionality and
the patterned films performed as photonic crystals, presenting the characterize the optical properties of the HPC photonic crystal
characteristic iridescent colour. Another attractive feature is their membranes, a set of samples with square lattice and varying L was
flexibility (Fig. 1c) and therefore the potential transfer to other tested. Photographs of the samples under normal incidence to the
surfaces in a conformal way. The possibility of retaining a rigid or films (Fig. 2a) clearly showed the change from blue to green to red,
flexible substrate underneath, accomplished with hot embossing, is as L was increased from 400 to 500 to 600 nm, in agreement with the
also useful for enhancing mechanical stability and ease of inspection colour observed with an optical microscope (Fig. 2b). The scanning
of the optical properties on a flat surface. One major advantage of electron microscopy (SEM) analysis confirmed the good replica-
these photonic crystals is their biodegradability inherited from the tion of the square array of holes, 300 nm in diameter and 220 nm in
HPC material. In fact, they can be washed away just by immersing depth, for the three lattice parameters studied (Fig. 2c)—larger-area
them in water (Fig. 1d). images may be found in Supplementary Fig. 4. Characterization

a b c
Hot embossing Replica moulding

Degradation tests in H2O

d
HPC

e
Acetyl cellulose Crosslinked HPC

Fig. 1 | Fabrication procedures and water solubility tests of cellulose photonic crystal films. a, Scheme illustrating the hot embossing and replica
moulding procedures used for the fabrication of cellulose-based photonic thin films and membranes. Glass substrate, blue; HPC, green; PDMS mould,
brown. See main text for detailed fabrication details. b, Example image of a free-standing HPC photonic crystal. Lateral size of the imprinted area is 1 cm.
c, Example image of the flexibility exhibited by a self-standing HPC photonic film. d, Sequence of photos illustrating the facile solubility of HPC photonic
membranes in water. e, Sequence of photos showing the pattern loss of crosslinked HPC in water. f, Sequence of photos exemplifying the stability of
patterned acetyl cellulose films in water.

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NATuRe PHoToniCs Articles
L = 400 nm L = 500 nm L = 600 nm crystals than in their dielectric counterparts (Fig. 3a). Moreover,
a
the samples keep the original flexibility (Fig. 3b). Optical charac-
terization of plasmonic crystals consisting of a hexagonal lattice of
imprinted nanoholes (Fig. 3c), revealed extinction peaks with up to
80% derived from the presence of the nanopatterns. These peaks
correspond to the excitation of Bragg SPPs and as L is increased, the
b
resonances redshift accordingly. Both the position and the intensity
of the Bragg SPPs agreed significantly well with theoretical simula-
tions performed by FDTD calculations (dashed curves in Fig. 3c).
As pointed out before, a major advantage of the fabrication
methods used in this study is the possibility of imprinting HPC on
top of different substrates. For providing additional functionality to
c the photonic and plasmonic crystals, we tested the fabrication of our
plasmonic architectures using regular paper as substrate. HPC was
coated on top of a piece of paper and then nanoimprinted, followed
by metal evaporation. As illustrated by the SEM images (Fig. 3d,e),
the patterns were transferred with extremely good quality also in
this case. This particular example demonstrates the potential of the
d 0.30
proposed system for functioning as a colourful photonic ink28 in
L = 400 nm
L = 500 nm
applications such as anti-counterfeiting technology, packaging or
0.25
L = 600 nm decorative paper. In fact, intense colours were easily achieved with-
out the use of any expensive or toxic chemical pigment and in all
Reflectance

0.20
cases, the photonic crystal presented a good adhesion to the paper
0.15
substrate as the HPC infiltrated the porous cellulose fibres of the
paper sheet (Supplementary Fig. 8). This method could be adapted
0.10 to other kinds of paper or cardboard with notable industrial impact.

0.05 HPC plasmonic crystals for photoluminescence enhancement.

400 500 600 700 800 Plasmonic architectures have been sought as a way to modify and
Wavelength (nm) enhance the emission of light sources26. The performance of HPC-
based plasmonic crystals was further tested by doping HPC with
Fig. 2 | HPC photonic crystals. a, Photographs of the HPC photonic films an organic dye—rhodamine B (RhB). This dye is attractive due to
(square lattice of imprinted cylindrical holes), for lattice parameters of its high quantum yield and has already been used for doping bio-
400, 500 and 600 nm. Square lateral size is 1 cm. b, Images of the HPC polymers such as silk29 or polydiolcitrates30. The samples as viewed
photonic films acquired with an optical microscope (4×​objective, NA 0.1). from the HPC side exhibited the characteristic magenta colour of
c, SEM micrographs of the HPC photonic films (top view). Scale bar, RhB, whereas inside the patterned areas, strong iridescence was
5 µ​m. d, Specular reflectance characterization of the samples (solid curves), observed, as in bare plasmonic crystals (Fig. 3f). Photoluminescence
along with theoretical modelling of the structures by FDTD calculations measurements were done on these crystals (see Supplementary
(dashed curves). Section 5), according to scheme in Fig. 3g, comparing the emission
from nanopatterned regions and flat regions. An example is pre-
sented for a hexagonal plasmonic crystal of L =​ 800 nm (Fig. 3h).
of the reflectance by Fourier-transform infrared spectroscopy The detected photoluminescence for regions inside the patterned
(Fig. 2d) revealed a peak centred at 430, 550 or 680 nm for each area was approximately tenfold the signal detected in the reference
sample, respectively, in good agreement with simulations performed flat area. RhB has a high quantum yield (close to 70%) and in the
by finite-difference time-domain (FDTD) calculations, also shown proposed system, the plasmonic structure provided a more efficient
Fig. 2d. It is important to highlight that the colours observed in way to extract light from the membrane.
these solid crystals arise from the two-dimensional patterned sur-
face, in contrast to the colour achieved by the presence of anisotro- HPC plasmonic crystals for SERS sensing. Once the optical prop-
pic phases in concentrated HPC dispersions in water. erties of the HPC plasmonic crystal membranes had been charac-
terized, we investigated the use of these architectures as disposable
HPC plasmonic crystals. Enhanced optical properties and further substrates for the detection of surface-enhanced Raman scattering
functionality can be achieved by metal coating the cellulose-based (SERS). Raman sensing is one of the fields where plasmonics has
photonic membranes. Such plasmonic crystals were produced by had the greatest impact. The use of plasmonic resonances greatly
thermal evaporation of 50 nm of silver on top of HPC gratings. In amplifies the Raman scattering from the analyte, leading to its iden-
doing so, the optical properties of these samples result from the tification, even in scarce amounts. Patterned HPC membranes with
combination of photonic and plasmonic modes. In plasmonic crys- hexagonal lattice and pillar morphology (L =​ 700 nm) were fabri-
tals, light fulfilling the condition of Bragg diffraction imposed by cated using the replica moulding technique previously explained.
the lattice launches surface plasmon polaritons (SPPs), where strong Afterwards, they were silver coated by thermal evaporation
electric fields at the surface of the metal can be used to enhance any (100 nm). A representative extinction spectrum of the samples is
light–matter interaction. Previous studies have reported that plas- shown in Fig. 4a. The optical characterization of these architectures
monic crystals have been used to enhance light emission,24 amplify revealed an extinction peak attributed to the excitation of a plas-
light absorption in photodetectors25 and produce structural colour monic resonance sustained by the architecture. To assess the SERS
in metallic surfaces26,27. performance of these substrates, the samples were functionalized
Owing to the negative dielectric permittivity of the metal, the with thiophenol via the vapour phase and analysed (Supplementary
overall refractive index contrast of the system is enhanced, giving Fig. 10). Thiophenol (Fig. 4b, inset) is a well-known Raman probe
origin to much more vivid colours in the cellulose-based plasmonic that easily binds to metal surfaces. Its characteristic vibrational

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a c f
1.0
L = 600 nm
L = 700 nm
L = 800 nm
0.8

0.6

Extinction
HPC side Ag side HPC side
b g
0.4

0.2

0.0
Flexibility assay 500 600 700 800 900

Wavelength (nm)
d e h
Pattern 800 nm

Photoluminescence (×106 counts)

16 Outside pattern

12

Excitation
8

0
500 600 700
Wavelength (nm)

Fig. 3 | HPC plasmonic crystals. a, Picture of both sides of a plasmonic crystal made of silver (50 nm) deposited on a HPC patterned membrane.
b, Example of the flexibility of plasmonic crystals. c, Experimental (solid curves) and simulated (dashed curves) optical extinction spectra of HPC-based
plasmonic crystals (hexagonal array of holes, L =​600, 700 and 800 nm). Inset: measurement scheme (sample studied from the metal side). d, SEM lateral
view of a HPC plasmonic crystal on a paper substrate (square lattice of imprinted holes). Scale bar, 1 µ​m. e, Similar view of a hexagonal lattice of imprinted
pillars. Scale bar, 1 µ​m. f, Image of a plasmonic crystal fabricated with RhB-doped HPC. g, Scheme of photoluminescence measurements showing light
impinging the HPC face. h, Comparison between photoluminescence spectrum of RhB in a patterned area (hexagonal plasmonic crystal; L =​800 nm) and a
planar reference.

modes are positioned at 1,001, 1,026, 1,094 and 1,586 cm−1 (ref. 31). simulations, in which the position of the extinction peak was fitted
These modes could be clearly identified in the spectra taken and the spatial distribution of the electric field intensity at both laser
from the probe adsorbed to the surface of our plasmonic crystals frequencies reproduced (Fig. 4f and Supplementary Fig. 12). Whereas
(Fig. 4b). Interestingly, the geometry employed in our plasmonic at λ =​ 532 nm the electric field distribution revealed the presence of
crystals was suitable for the excitation of plasmonic resonances, an extended mode, λ =​ 633 nm corresponded to a hybrid mode where
which in turn facilitated the use of these membranes as SERS the electric field was concentrated mostly at the top of the pillars.
substrates, active at different excitation wavelengths (λ =​  532 and The good agreement between simulations and Raman measurement
633 nm). When comparing spectra collected from the flat regions maps demonstrated that we were capable of imaging the spatial dis-
of the substrate (grey curves in Fig. 4b) with the spectra collected tribution of hotspots in our plasmonic structures for two different
inside the patterns, a clear enhancement of the signal was observed. resonant optical modes. Moreover, they demonstrate the importance
SERS is a phenomenon characterized by the presence of hotspots of the imprinted nanostructure for enhancing the Raman signal.
at the dielectric/metal interface. These are spatial regions with
extremely intense electric field31. The Raman signal measured Conclusions
originates from the effect of these hotspots on the molecules placed We have shown how to produce photonic and plasmonic crystal thin
therein. There is great interest in the imaging of the above men- films out of HPC. The resulting structures incorporate the biocom-
tioned hotspots, to identify the active sensing regions of the SERS patibility and biodegradability aspects inherited form the cellulose
substrate. Here we demonstrate how the excellent quality of our derivative used. Following the recent tendency to explore materials
HPC plasmonic crystal membranes enables the identification of for transient electronics32,33, our system opens a wide range of poten-
the hotspots for the two laser frequencies employed. First, electron tial applications in transient photonics. Two routes were presented to
microscopy images (Fig. 4c) and optical microscopy images (Fig. 4d) integrate these photonic architectures in applications: to produce free-
were used to illustrate the hexagonal array of Ag-coated pillars form- standing flexible samples that may be transferred to other surfaces;
ing the plasmonic substrate. Second, Raman spectroscopy maps and to directly nanoimprint a HPC coating on the desired substrate.
were performed by scanning the signal throughout the surface and HPC nanoimprinted crystals are a convenient platform for the realiza-
monitoring the Raman peak of thiophenol at 1,578 cm−1 (Fig. 4e), tion of plasmonic systems by simply metal coating the HPC photonic
for both laser frequencies. The Raman signal map for the 532 nm membranes. Different morphologies and topologies were produced
laser excitation revealed that the majority of the signal came from with this method, both free-standing and on top of functional sub-
the regions located between the metallic pillars. In contrast, when strates. These samples offer a convenient opportunity for the produc-
the sample was illuminated with the 633 nm laser, coinciding with tion of colour in packaging systems and in photonic papers30 and they
the extinction peak, the Raman signal originated at the pillars them- could accomplish the function of washable and edible34 detectors or
selves. This observation was further corroborated with n ­ umerical labels in food industry. In fact, HPC is an excellent candidate for such

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a 1.0 b
Simulation SH λ = 532 nm
Experimental
Flat reference
0.8 Patterned area

a.u.
Extinction 0.6

1,000 1,578 2,000 3,000

0.4 λ = 633 nm

Flat reference
Patterned area

a.u.
0.2

0.0
500 600 700 1,000 1,578 2,000 3,000
Wavelength (nm) ∆υ (cm–1)

c e
λ = 532 nm λ = 633 nm
Experimental

CCD CCD
3,700 counts 4,400 counts

3,000 counts 2,200 counts

d f
λ = 532 nm λ = 633 nm

|E|2 |E|2
Simulations

–1
5Vm 5 V m–1

0 V m–1 0 V m–1

Fig. 4 | HPC plasmonic crystal membranes as SERS substrates. a, Representative extinction spectrum of a silver-coated HPC hexagonal lattice of pillars
(L =​700 nm)—experimental results (solid curve) and FDTD simulation (dashed curve). b, Raman spectra of thiophenol (inset) collected in reference flat
areas (grey curves) and in HPC/Ag patterned substrates, for excitation wavelengths of 532 and 633 nm; curves are vertically displaced for clarity.
c, Representative SEM image of the sample. Scale bar, 600 nm. d, Representative optical microscopy image of the sample observed with a
100×​magnification objective used to measure Raman maps. Scale bar, 600 nm. e, Raman maps of the surface, monitoring the intensity of the peak at
1,578 cm−1, for excitation wavelengths of 532 nm (left) and 633 nm (right). Scale bars, 600 nm. f, FDTD theoretical simulations of the electric field (E) spatial
distributions for the corresponding wavelengths.

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novel dye-doped white paints with shape memory. Adv. Opt. Mater. 3, Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in
1080–1087 (2015). published maps and institutional affiliations.

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NATuRe PHoToniCs Articles
Methods backscattering geometry. The microscope was coupled to a high-throughput and
Chemicals. A h-PDMS kit was acquired from Gelest and a soft poly-PDMS high-resolution LabRam HR800 spectrometer using a grating of 600 lines mm−1
Sylgard 184 kit was acquired from Dow Corning. 1H,1H,2H,2H-perfluoro- and equipped with a liquid nitrogen cooled charge-coupled device (CCD) detector.
octyltrichlorosilane, 97% was purchased from Alfa Aesar. Acetone, divinyl sulfone, A scheme of the experimental setup is provided in Supplementary Fig. 9. All
acetyl cellulose with average molecular weight Mw =​ 30 kDa and HPC with measurements were performed at room temperature.
average Mw =​ 100 kDa were acquired from Sigma-Aldrich. All chemicals
were used as received. Raman spectroscopy measurements. The initially free-standing membranes were
transferred to a flat PDMS block so that their surface was free from wrinkles or
curving. Raman images were obtained at ambient conditions and in backscattering
Stamps preparation. Composite bilayer stamps comprising a thin h-PDMS layer
geometry using the WITec Alpha300 R confocal setup. For excitation, either a
to ensure good pattern replica and mechanical stability, and a thick soft PDMS
frequency-doubled neodymium-doped yttrium aluminium garnet (Nd:YAG)
(s-PDMS) layer to allow their manipulation were prepared according to previously
laser emitting at 532 nm or a He–Ne gas laser (633 nm) was coupled into a Zeiss
reported methods22.
microscope through a wavelength-specific single-mode fibre and collimated by
an achromatic lens. The beam was focused onto the sample, with power 0.25 mW,
Nanoimprinting of cellulose derivatives. A HPC solution in water was prepared using a Zeiss EC Epiplan-Neofluar (100×​, 0.9 NA) objective, giving an estimated
by adding 23 ml of deionized water to 5 g of HPC powder. The solution was spot size of 0.35 μ​m (green) or 0.43 μ​m (red). The pixel size for the images was
intensively stirred and reserved for use in a sealed vial. Regarding the replica 0.1 ×​  0.1 μ​m2, given by the scanning movement of a piezo-motor-driven sample
moulding procedure, the HPC solution was poured on top of a h-PDMS mould stage. The collected light was focused into a multimode optical fibre, which
and spin coated at 500 r.p.m. with an initial acceleration of 100 r.p.m. min s−1. served as the entrance slit for the spectrometer. The 3.5-μ​m-diameter single-mode
Once finished, the membranes were peeled off to obtain free-standing samples. input fibre and the 50-μ​m-diameter multimode output fibre provided the optical
For hot embossed samples, a dilution of the original HPC at a new concentration apertures for the confocal arrangement. A Si back-illuminated 1,024 ×​  127 pixel
of 41 mg ml−1 was initially prepared. Then thin films were prepared by spin CCD cooled at −​60 °C was used for detection. Using gratings of 600 grooves mm−1
coating (parameters: acceleration ramp of 1,000 r.p.m. s−1, duration of 60 s at with blaze at 500 nm (green) and of 300 grooves mm−1 with blaze at 750 nm (red),
3,500 r.p.m.) on top of glass slides or silicon wafers as substrate. The samples complete Raman spectra in the interesting spectral range (from about 200 to
were heated at 140 °C and imprinted with the h-PDMS mould by applying a light 3,500 cm−1) were acquired at each image pixel using integration times of 0.1 s with
pressure for approximately 30 s. Finally, the h-PDMS was demoulded. In the case submicrometre spatial resolution (Supplementary Fig. 10). Images were analysed
of samples produced with the crosslinker, a solution of NaOH in water was first using WITec Project FOUR software.
prepared at a concentration of 1 mg ml−1. A HPC mass of 0.16 g was added to a
volume of 1.808 ml of the NaOH solution and magnetically stirred overnight. A Theoretical modelling. A commercial-grade simulator based on the FDTD
divinyl sulfone mass of 0.032 g were added to the mixture and stirred for a few method was used to perform the calculations (Lumerical Solutions, [Link]
more minutes. The replica moulding process was repeated. Insoluble photonic [Link]/tcad-products/fdtd). For simulating the thick free-standing HPC
membranes were prepared by mixing 0.16 g of acetyl cellulose in 1.832 ml of membranes, 120 reflectance spectra for different thicknesses were calculated
acetone, magnetically stirring overnight and repeating the replica moulding and averaged so that oscillations due to Fabry–Perot interference were averaged.
procedure. Silver films were deposited on top of HPC membranes using a A mesh refinement of 5 nm was used in all structures. Transmittance (T) and
MBRAUN thermal evaporator. The chamber pressure was 4 ×​  10−7 bar and an reflectance (R) were calculated and extinction as 1 −​  R −​  T. The simulations were
evaporation rate of 10 nm min−1 was used. performed for both polarizations and averaged to reproduce unpolarized light
(Supplementary Fig. 12).
Photoluminescence measurements. The photoluminescence was excited using
either the 405 nm line of a continuous-wave laser diode or the 514 nm line of Data availability. The data that support the plots within this paper and
an Ar+-ion gas laser. The photoluminescence signal was collected using an other findings of this study are available from the corresponding author upon
Olympus microscope with a 20×​ objective (numerical aperture (NA) =​  0.35) in reasonable request

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