Progress Report

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Understanding the Self-Assembly of Cellulose

Nanocrystals—Toward Chiral Photonic Materials
Andy Tran, Charlotte E. Boott, and Mark J. MacLachlan*

signals. The color can originate from the

Over millions of years, animals and plants have evolved complex molecules use of dyes, pigments, metals, and biolu-
and structures that endow them with vibrant colors. Among the sources of minescence, which focus on the absorption
natural coloration, structural color is prominent in insects, bird feathers, or emission of light, or from structural
snake skin, plants, and other organisms, where the color arises from the color. Structural color occurs due to the
interaction of the material with light.
interaction of light with nanoscale features rather than absorption from a
Although structural color was reported by
pigment. Cellulose nanocrystals (CNCs) are a biorenewable resource that Hooke in 1665,[2] it took the invention of
spontaneously organize into chiral nematic liquid crystals having a hierar- the electron microscope in the late 1930s
chical structure that resembles the Bouligand structure of arthropod shells. for the microstructures responsible for
The periodic, chiral nematic organization of CNC films leads them to diffract structural color to be revealed. In 1942,
Richards et al. used electron microscopy
light, making them appear iridescent. Over the past two decades, there have
to study the structures involved in the
been many advances to develop the photonic properties of CNCs for applica- color of the Serica sericea beetle and the
tions ranging from cosmetics to sensors. Here, the origin of color in CNCs, Morpho cypris butterfly.[3] In both cases, the
the control of photonic properties of CNC films, the development of new color arises from ordered micro­structures,
composite materials of CNCs that can yield flexible photonic structures, and where the layers are 0.8 and 0.2 µm apart,
the future challenges in this field are discussed. In particular, recent efforts to respectively. Since this discovery, the field
has grown and now encompasses any
make flexible photonic materials using CNCs are highlighted.
color generated due to the interference,
diffraction, refractive dispersion, and dif-
ferential scattering or polarization of light.
Other examples of structural color from nature include chitin
1. Introduction to Structural Color
nanocrystals in the jewel beetle,[4] guanine nanocrystals in
The human eye can see over one million colors and color plays the panther chameleon[5] and tetra fish,[6] reflectin proteins in
a critical role in everyday life. We know red lights mean stop squid,[7] and cellulose in the fruit Pollia condensata (Figure 1).[8]
and green lights mean go, while in battle a white flag means Structural color can also be classified as iridescent if the color
surrender. These are very simple ways to use colors to codify changes with viewing angle or noniridescent if it is inde-
actions. However, as technology has advanced, the ways we use pendent of the viewing angle.
and produce color have evolved. For example, liquid crystal dis- It is worth noting that in nature the ordered structure can
plays in smart phones, computers and TV screens are central to have additional functions to color production, such as self-
the communication and entertainment industries. cleaning.[9,10] For example, the nanostructure in butterfly wings
Nature also heavily relies on color for a range of functions, increases the hydrophobicity of the wing surface, allowing
including camouflage, biological ornaments, and warning water droplets to be dispersed more efficiently, simultane-
ously removing dirt particles and cleaning the wings. This has
been termed the “lotus effect”[11] and is a great example of how
A. Tran, Dr. C. E. Boott, Prof. M. J. MacLachlan sophisticated nature is at self-assembly; it can produce the per-
Department of Chemistry fect structure with high complexity and multiple functions.
University of British Columbia This level of precision is unparalleled in the synthetic world
2036 Mail Mall, Vancouver, BC V6T 1Z1, Canada
E-mail: mmaclach@chem.ubc.ca but provides a great source of inspiration to scientists. Specifi-
Prof. M. J. MacLachlan cally, for the subject of this progress report, structural color is
Stewart Blusson Quantum Matter Institute extremely attractive in materials fabrication as it can be tuned,
2355 East Mall, Vancouver, BC V6T 1Z4, Canada will not fade (photobleaching) and does not require the use of
Prof. M. J. MacLachlan toxic dyes.[12,13]
WPI Nano Life Science Institute In an attempt to mimic nature and prepare materials with
Kanazawa University
structural color, researchers have employed two main fabrica-
Kanazawa 920-1192, Japan
tion methods: top-down and bottom-up assembly. The first
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201905876. methodology to be explored was a top-down approach using
lithographic methods that are complex, precise, and able to pro-
DOI: 10.1002/adma.201905876 duce photonic crystals of high quality. However, this method

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is often not amenable to high throughput due to the high

cost, low efficiency, and feature sizes that must be larger than Andy Tran was born and
100 nm. Therefore, research now focuses on a bottom-up self- raised in Ontario, Canada. He
assembly process as it is easier to perform, is more time and completed his B.Sc. honors
cost efficient, and allows access to smaller feature sizes. This degree in chemistry (special-
method relies on the physicochemical interactions of simple izing in chemical biology)
building blocks to produce hierarchical structures in a manner at McMaster University.
that is analogous to how nature synthesizes complex materials. He worked with the
For the fabrication of synthetic photonic crystal-based mate- Saravanamuttu (McMaster
rials, the majority of the research has employed synthetic opals, University) and Aizenberg
such as SiO2 and polystyrene, and inverse opals to achieve (Harvard University) groups
structural color.[14–17] However, we are not limited to synthetic in developing reversibly
materials to produce photonic crystals; biorenewable materials self-trapping hydrogel sys-
such as cellulose and chitin nanocrystals have been demon- tems. He started his Ph.D. work in the fall of 2015 in the
strated to form colored, iridescent materials. In this progress MacLachlan group working on cellulose-based nanomate-
report, we focus on the application of cellulose nanocrystals rials. His work focuses on understanding the self-assembly
(CNCs) to prepare photonic materials with visible color, but process in developing cellulose nanocrystal films.
also briefly discuss recent activity to construct similar materials
with hydroxypropyl cellulose and chitin nanocrystals.
Charlotte E. Boott graduated
from the University of York
2. Introduction to Cellulose Nanocrystals in 2012 with an M.Chem.
in chemistry with a year in
Cellulose is the most abundant polymer in the biosphere with industry. In 2012, she joined
an annual production of more than 90 billion metric tons.[18] the Chemical Synthesis
Found in trees, plants, fungi, and bacteria, cellulose fibers are Centre for Doctoral Training
comprised of b-(poly-1,4-d-glucose) chains, which are stabilized at the University of Bristol.
by hydrogen bonding.[19] The cellulose fibers are comprised of After completing three dif-
both crystalline and amorphous domains. In the early 1950s, ferent lab rotations as part of
Rånby et al. demonstrated that, due to their lower density, the the Chemical Synthesis CDT
amorphous regions could be selectively hydrolyzed with acid to training period, Charlotte
leave only the crystalline domains, termed cellulose nanocrys- decided to undertake a Ph.D. project in the Manners group
tals (CNCs) (Figure 2).[20] Many different acids have been based on the solution self-assembly of block copolymers,
employed to prepare CNCs including sulfuric, hydrochloric, which she completed in October 2016. Charlotte joined the
phosphoric, and hexanoic acids. However, sulfuric acid is most MacLachlan lab in May 2017 as a postdoc. Her research
commonly used since the resulting CNCs have the highest col- is on the functionalization and self-assembly of cellulose
loidal stability, owing to the electrostatic stabilization provided nanocrystals.
by the negatively charged sulfate half-ester groups incorporated
onto the surface of CNCs.[21,22] The surface chemistry of CNCs
can also be modified through other synthetic strategies to con-
trol their interactions and colloidal stability.[23,24] Mark J. MacLachlan
Wide-angle X-ray scattering (WAXS) of CNCs reveals a completed his B.Sc. at
highly crystalline structure with the main diffraction peak at the University of British
2θ = 22.5°.[25] WAXS measurements show that the crystallinity Columbia, and then his Ph.D.
of the cellulose in CNCs is around 75–80%, depending on the at the University of Toronto
acid hydrolysis conditions used.[26] CNCs are chiral due to the on inorganic materials,
D-glucose units in the cellulose and this is manifested in the polymers, and molecules
screw-shape morphology adopted by CNCs.[27,28] The dimen- under the supervision of Ian
sions of CNCs are dependent on the cellulose source and the Manners and Geoff Ozin.
acid hydrolysis conditions but can be 50–1160 nm long with a He then moved to MIT as an
diameter of 3–50 nm.[29] The high aspect ratio (>10), low den- NSERC Post-doctoral Fellow
in the lab of Tim Swager,
sity (≈1.6 g cm−3), high axial stiffness (≈150 GPa), and high
where he worked on organic materials. Mark started his
tensile strength of CNCs (estimated at 7.5 GPa)[30] make them
independent career at the University of British Columbia
ideal candidates for nanoreinforcement of composites.[31]
in 2001 and has been a full professor since 2011. Mark’s
Due to the potential of CNCs to be used in a range of applica-
research interests span supramolecular chemistry (macro-
tions, several reviews have covered how CNCs can be employed
cycles, molecular machines), photonic materials, biomate-
in photonic materials,[32] templating,[33] nanoreinforcement,[34]
rials, and solid-state nanomaterials.
hydrogels and aerogels,[35] and other areas. In this review, we
focus on the self-assembly of CNCs into structures with chiral

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Figure 1. Examples of structural color in the natural world arising from chiral nematic organization: a) photographs of a scarab beetle (Chrysina gloriosa)
under a left-handed circular polarizer (left), no polarizers (middle), and a right-handed circular polarizer (right).[1] b) Photograph (left) of a single Pollia
condensata fruit from dried herbarium specimen collected in Ghana (Kew Herbarium: Faden and Lock 74/37, 1974). Transmission electron micrograph
(right) of cellulose microfibrils present in P. condensata. The chiral nematic twist is denoted by a pink dashed line. c) Bragg reflection is responsible for
many examples of structural coloration. d) 3D representation of the cellulose microfibril organization that produces structural color in P. condensata,
demonstrating how the fruit transmits circularly polarized light. a) Reproduced with permission.[1] Copyright 2017, Elsevier. b,d) Reproduced with
permission.[8] Copyright 2012, National Academy of Sciences.

nematic order and how this process can be controlled and liquid crystalline phase, sometimes referred to as a mesophase
manipulated to prepare photonic materials with visible color. (“intermediate phase”), exists, which displays properties of both
a crystalline solid and a free-flowing liquid, mainly depending
on temperature or concentration (Figure 3).[36] Therefore,
3. Liquid Crystalline Phase of Cellulose liquid crystals can flow, reminiscent of liquids, while also
exhibiting birefringence, which is characteristic of the crys-
Nanocrystals
talline phase. Birefringent materials have a refractive index
Liquid crystals are a state of matter between a liquid and a that is dependent on polarization and propagation of light.
solid.[36] For instance, when certain solid compounds (e.g., Liquid crystals are of great interest for electronic devices and
p-azoxyanisole and p-pentyl-p′-cyanobiphenyl) are heated, they have been the topic of extensive study since their discovery at
do not directly transition into a liquid phase.[37,38] Rather, a the end of the 19th century.[39,40] Generally, liquid crystals are

Figure 2. Preparation of CNCs from wood: Wood pulp can be hydrolyzed with sulfuric acid to selectively remove amorphous regions, leaving behind
crystalline cellulose nanorods. Typical dimensions of CNCs range from 50 to 1160 nm in length and 3 to 50 nm in diameter, depending on the cellulose
source and acid hydrolysis conditions.

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Figure 3. Schematic representation of the arrangement of rod-like mesogens in liquid crystalline phases. Liquid crystals are typically categorized as
thermotropic or lyotropic liquid crystals, depending whether mesogens form through variations in temperature or concentration, respectively. Liquid
crystalline phases can be classified, depending on the alignment of the mesogens, such as nematic, chiral nematic, or smectic, among others.

categorized as thermotropic or lyotropic liquid crystals. Ther- the affinity of CNCs to Congo red. They found that the dye
motropic liquid crystals find use in liquid crystal displays as showed a CD signal at the dye absorption wavelength, sug-
they exhibit liquid crystallinity over a finite temperature range. gesting that the Congo red assumes the chiral nematic struc-
Lyotropic liquid crystals, such as a tobacco mosaic virus sus- ture of the CNCs. Chiral nematic order gives rise to unique
pension, transition into the liquid crystalline phase above a optical properties and has been found in crab shells, plant cell
critical concentration in a solvent. Liquid crystal phases (e.g., walls, and suspensions of viruses, polypeptides, and DNA.[49–53]
nematic, smectic, chiral nematic, etc.) exist within each cat- There has been considerable interest in this growing field ever
egory to describe the organization of liquid crystalline compo- since the discovery of liquid crystals, leading to the successful
nents, which take on a variety of forms including rods, discs, incorporation of liquid crystals in display applications. Fur-
and plates, among others. The Onsager model predicts that the ther understanding of the liquid crystalline components and
aspect ratio of colloidal particles is critical for determining the assembly is crucial to expand the field for future liquid crystal-
onset of liquid crystallinity as well as the volume fraction of the line materials and applications.
individual phases.[41] Following the Onsager model, the rod-
shaped morphology of CNCs suggests that CNCs will behave as
a lyotropic liquid crystal.[42] Indeed, CNCs undergo phase sepa- 4. Chiral Nematic Films of Cellulose Nanocrystals
ration into an isotropic and anisotropic phase above a critical
CNC concentration and the anisotropic phase adopts a chiral Revol et al. made a surprising discovery when they found that
nematic structure.[43,44] chiral nematic liquid crystalline order in a cellulose nanocrystal
Chiral nematic order, also named cholesteric order, was first suspension could be preserved in a solid film.[46,54] The authors
observed in cholesterol derivatives.[45] Revol et al. uncovered the evaporated the water from a CNC suspension (≈3.5 wt%),
helical structure in CNCs when they observed periodic struc- leaving behind a film with chiral nematic order. They found
tures in both CNC suspensions and films by polarized optical that the films were birefringent under POM, and the structures
microscopy (POM) and transmission electron microscopy were easily disrupted by shear forces. Analogous to a suspen-
(TEM).[46] In this chiral nematic phase, CNCs align parallel to sion of CNCs, the chiral nematic orientation embedded in solid
the director, whose orientation rotates through the liquid crystal films produced a positive signal when measured by CD spec-
along an axis perpendicular to the director, forming the helix troscopy.[55] The helical twist of the CNCs is always left-handed,
(Figure 4a,b). In 1951, De Vries developed a theory to bridge confirmed by the positive CD signal for the transmitted light;
the link between optical rotation and the pitch of the helix.[47] the reflected light is left-handed circularly polarized. When
Owing to the chiral nematic structure, CNC films selectively the pitch of the helix is on the order of the wavelengths of vis-
reflect left-handed circularly polarized light, thus producing ible light, CNC films display vivid iridescent structural colors.
a positive circular dichroism (CD) signal for transmitted light In essence, chiral nematic CNC films behave as 1D photonic
(Figure 4c,d). This phenomenon was further investigated by crystals. Photonic crystals are materials with periodically
Dong et al. to study induced CD activity and the possibility of changing refractive indices that diffract light in one, two, or
CD transfer to other systems.[48] The authors showed that an three dimensions. 1D photonic crystals are the simplest type,
induced CD signal could be produced by taking advantage of and an example of this is a Bragg grating. For chiral nematic

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Figure 4. Structure and optical properties of a chiral nematic CNC film. a) Photograph of a chiral nematic CNC film showing the iridescence due to
structural color. b) Scanning electron micrograph showing the helical twist of CNCs in a film. Dashed-line inset is a schematic representation of the
helical pitch (P). c) Circular dichroism spectrum of a typical chiral nematic CNC film. d) Chiral nematic CNC film viewed under natural light (left),
left-handed circularly polarized light (middle), and right-handed circularly polarized light (right). Reproduced with permission.[66] Copyright 2014,
American Chemical Society.

structures, the wavelength of reflected light in CNC films is experiments, they postulated that intermediate structures with
dependent on the average refractive index, n, of the film, the chiral nematic organization are already formed when CNC rods
helical pitch P, and the reflection angle θ with respect to the are ≈50 nm apart in water. Until recently, tactoids have only
surface of the film (Equation (1)).[47] The reflected light is cir- been viewed under POM; however, Wang et al. imaged, for the
cularly polarized, where the handedness and pitch is the same first time, tactoids using scanning electron microscopy (SEM)
as the chiral nematic structure. The other handedness trans- (Figure 5).[58] In this work, tactoids were captured by a photo­
mits through the material, therefore, the maximum reflectance polymerization method in which acrylamide and crosslinker
achievable is 50%. In the case of CNCs, the reflected light will N,N′-methylenebisacrylamide were irradiated by ultraviolet-B
be left-handed circularly polarized light. The resulting hydrogel was broken apart and the struc-
ture of tactoids, their growth, and formation of chiral nematic
λ = nP sin θ (1) order was studied by SEM.
Building on the research in tactoid formation, Dumanli
Changing the helical pitch of CNC films affects the color of et al. proposed that the self-assembly of CNCs to form chiral
the film, and tuning this structural color has been a topic of nematic CNC films progresses through three stages: a) phase
interest for many research groups over the last decade.[31,33,42] separation; b) kinetic arrest; and c) film formation (Figure 6).[59]
Understanding the self-assembly process of CNCs, and espe- Upon phase separation (≈3 wt%) and the formation of tactoids
cially the formation of the chiral nematic liquid crystalline (step a), evaporation of water concentrates the CNC suspension
phase, is imperative in the development of functional photonic until a viscous liquid or gel forms. At higher CNC concentra-
materials. Briefly, a dispersion of CNCs diluted in water forms tions (≈8 wt%), kinetic arrest occurs, reducing the mobility
an isotropic phase with CNCs well dispersed in the suspension. of tactoids in the anisotropic phase and locking the chiral
Above a critical CNC concentration (≈3 wt%), CNC rods can nematic structure in place (step b). Upon complete evaporation
aggregate and form ordered structures called tactoids, which of water, a solid film of CNCs is formed with chiral nematic
fuse and precipitate to form an anisotropic phase. Tactoids structure and vivid iridescence (step c). Further work by Tran
are liquid crystalline droplets that are spherical or ellipsoidal et al. showed that an intermediate stage of self-assembly, called
in shape and are a transition state between an isotropic liquid tactoid annealing, likely exists between phase separation and
and a liquid crystalline phase.[56] Schütz et al. investigated the kinetic arrest.[60] When given prolonged evaporation time, tac-
phase separation process of the upper isotropic phase and toids can fuse and reorganize, which reduces the interfacial
lower anisotropic phase, and found the process to be time and tension between the anisotropic and isotropic phases. In this
concentration dependent.[57] The authors found that at longer way, CNC films with improved chiral nematic order can be
phase separation times (≈91 h) and higher CNC concentra- produced.
tions (φ = 4.5 vol%), a suspension of CNCs could be fully ani- Drying CNC suspensions also display the “coffee-ring”
sotropic. Using data from small-angle X-ray scattering (SAXS) effect[61] where CNC rods preferentially migrate to the edge

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Figure 5. Tactoids viewed by SEM. a) Initial tactoid with no chiral nematic bands. b) Tactoid with a single chiral nematic band. c) Tactoid with three
complete chiral nematic bands. d) Two tactoids captured just before coalescence. Reproduced with permission.[58] Copyright 2016, Springer Nature.

boundaries, resulting in films with distinct edge defects.[62] In leads to a decrease in the electrostatic repulsion between CNC
this report, Mu et al. proposed that a CNC droplet concentrates crystallites, which in turn is responsible for the smaller helical
at the edges due to outward flow of CNCs during evaporation, pitch. In another study, Dong et al. found that the role of the
which leads to an iridescent coffee-ring residue. Films with counterion in suspension greatly influenced the self-assembly
unpredictable optical properties form from these disordered process, where larger counterions delayed the onset of liquid
edge conditions, and they have been considered for aestheti- crystallinity.[65] In both examples, small changes in the suspen-
cally pleasing artforms.[63] Current research cannot fully explain sion resulted in drastic changes to the self-assembly process of
or control the optical properties at these disordered boundaries, CNCs, which will have ramifications on the preparation and
but much attention has been given to controlling the helical development of CNC films.
pitch away from the edges. To develop CNC films with precise optical properties, many
The self-assembly process of CNCs is influenced by the parameters have been studied, leading to the development
properties of the suspension such as ionic strength, which has of a variety of tunable photonic CNC materials and technolo-
a significant impact on the resulting chiral nematic CNC film. gies. In developing CNC films, the effects of water evapora-
For example, Dong et al. studied the role of ionic strength of tion and initial CNC concentration have been investigated by
a drying CNC suspension and found that an increase in ionic several groups.[60,66–68] Dumanli et al. varied the dynamics of
strength decreased the helical pitch in the resulting film upon color formation by evaporating CNC suspensions at different
complete evaporation of water.[64] Increasing the ionic strength relative humidity, ranging from 10% to 80% relative humidity,

Figure 6. Schematic representation of the self-assembly process of CNC from suspension to film. Self-assembly progresses through three key stages:
a) CNCs in suspension are initially isotropic; b) upon phase separation (≈3 wt%), a lower anisotropic layer is formed; c) CNCs are locked into place
beyond the critical concentration during kinetic arrest (≈8 wt%), which forms a solid film upon complete evaporation of water.

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Figure 8. Tuning the helical pitch and structural color of CNC films.
a) A vacuum-assisted self-assembly method produced CNC films with
different colors depending on the applied vacuum. b) Inputting energy
to the CNC suspension through ultrasonication resulted in films span-
ning the visible range. Scale bar represents 1 cm. c) Addition of 1-allyl-
Figure 7. Patterning CNC films by differential evaporation. a) Gradient 3-methylimidazolium chloride at different concentrations leads to CNC
film (right) prepared by restricted evaporation when a lid with a small films with different reflection wavelengths. d) Post-treating of CNC films
opening is placed on a drying CNC suspension. A control film (left) with sodium hydroxide blue-shifts the resulting color of the film. a) Repro-
without evaporation is also shown. b) Cellulose acetate masks placed on duced with permission.[67] Copyright 2014, American Chemical Society.
CNC suspensions at varying times produce patterned films. Reproduced b) Reproduced with permission.[75] Copyright 2011, American Chemical
with permission.[69] Copyright 2018, American Chemical Society. Society. c) Reproduced with permission.[86] Copyright 2017, American
Chemical Society. d) Reproduced with permission.[87] Copyright 2017,
American Chemical Society.
and were able to obtain CNC films covering most of the visible
spectrum.[59] The authors followed the time evolution of the The surface upon which a CNC suspension is cast can signif-
reflectance peaks starting from a suspension to a solid film, a icantly influence the color of the film. To address this, Nguyen
process that took 16 h at lower humidity to over 27 h at higher et al. cast CNC suspensions on a variety of surfaces, including
humidity. For each humidity condition, they saw a similar trend aluminum, silicon wafers, mica, and polystyrene among
for the reflectance peaks, with an initially fast blue-shift corre- others, and the optical properties of each resulting film were
sponding to evaporation of water, followed by a plateau likely studied.[70] Significant shifts in the reflection wavelength were
due to kinetic arrest, and finally a rapid blue-shift to the final observed, demonstrating that substrate surface properties influ-
film’s reflection wavelength from the complete loss of water. ence the self-assembly behavior. O’Keeffe et al. showed that
Using a similar approach, Tran et al. investigated decorative chiral nematic CNC films nucleated at the liquid–surface inter-
patterns by simply modifying the evaporation time of CNC face of hydrophilic substrates but at the air–liquid interface on
suspensions.[69] In developing CNC films, slow evaporation of hydrophobic substrates.[71] This has been expanded further by
suspensions resulted in blue-shifted films.[60] Utilizing differen- Tardy et al. in the development of a microtemplating approach
tial evaporation, CNC films with gradients could be designed to prepare tessellated chiral nematic CNC films.[72] In this
(Figure 7). Furthermore, the application of a cellulose acetate work, they manipulated the wettability of surfaces using a com-
mask on top of a drying CNC suspension led to patterns with bination of meshed and rigid substrates to produce films with
higher resolutions. These patterns could be tuned, from red to higher order structures and distinct topological domains. The
blue, depending on the stage of self-assembly when the masks hydrophobicity of the surface can certainly affect the properties
were applied. of the films, but the role of CNCs assembling and anchoring on
Despite their ability to produce films with vivid irides- different substrates is still not completely understood.
cent colors, CNCs have limitations that lead to restricted
throughput. The self-assembly process is sensitive to perturba-
tions and can require many days to completely evaporate the 4.1. Chiral Nematic Films Developed Under External Influences
water. Chen et al. devised an interesting evaporation method,
using a vacuum filtration apparatus, that yielded a CNC film on Thus far, we have focused on the effects of modifying CNC
a filter paper in 12 h (Figure 8a).[67] In this protocol, pretreat- suspensions on the properties of the chiral nematic CNC films.
ment of CNC suspensions with ultrasonication was required to However, external influences, such as temperature and addi-
produce films and the authors found that ultrasonication time, tives, can dramatically affect the properties of the films. Input-
suspension volume, and applied vacuum were key contributors ting energy through heat[73,74] or sonication[75–77] produced CNC
to preparing iridescent CNC films. Compared to slower evap- films with an increased helical pitch, enabling films with tun-
oration techniques, the chiral nematic order is expected to be able chiral photonic properties to be made. Beck et al. varied
compromised, but the films obtained show vivid colors. the temperature for drying CNC suspensions from 30 to 75 °C

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regions were red-shifted when compared to regions evaporating

under ambient conditions. Furthermore, heating wires with
unique patterns were used to create other patterned CNC films.
The red-shift observed in CNC films upon the input of
external energy through heating has been explained in a few
different ways. However, it is likely that kinetic entrapment of
water molecules between layers of CNC rods leads to increased
helical pitch values, while also introducing significant disorder
in the resulting chiral nematic structure. In another study per-
formed by Beck et al., varying amounts of energy were pro-
vided, through sonication, to CNC suspensions before casting
and developing films (Figure 8b).[75] At higher input energies,
the resulting films were significantly red-shifted. The authors
propose that this red-shift is a result of raising the critical CNC
concentration and may involve either expulsion of ions from
the bound-water layer, or a gel layer of sulfated oligosaccharides
on the CNC particle surface.
Due to the diamagnetic anisotropy of cellulose nanocrystal
rods, the use of magnetic[44,78,79] and electric fields[80–83] has been
Figure 9. Patterned CNC films by heat. a) A heated coil (left) can be
shown to align CNC rods in suspension. When a constant field
placed under a Petri dish containing a CNC suspension and, upon com-
plete evaporation, a patterned film is made (right). b) A metal ring is is applied to a drying CNC suspension, CNC rods align perpen-
heated under a Petri dish and areas exposed to heat are significantly dicular to the applied field, and this helical orientation can be
red-shifted. The red-shift of the patterned area increases with increasing preserved in solid films. Frka-Petesic et al. demonstrated that an
temperature. Reproduced with permission.[74] Copyright 2013, Springer applied magnetic field could be used to develop ordered CNC
Nature. films with a degree of control of the nanostructures depending
on the direction and angle of the applied field.[84] The authors
and found that higher temperatures resulted in red-shifted applied a weak magnetic field (≈0.5–1.2 T) to a drying CNC sus-
films.[74] The authors observed that when differential heating pension and were able to manipulate the helical structure by
is selectively applied to regions of a drying CNC suspension, changing the location of the magnet (Figure 10a–c). CNC films
photonic patterns emerged (Figure 9). Specifically, heated with a radial pattern were prepared by casting suspensions on

Figure 10. Patterning CNC films by applying a magnetic field. a,b) Examples of films that were cast spanning two magnets, as indicated by the sche-
matic in (c). d) CNC suspension was cast on a polydomain magnet. Interesting patterns are created upon film formation. e) SEM image of a CNC film
prepared in the absence of a magnetic field. f) SEM image of a CNC film prepared in the presence of a vertically aligned magnetic field, denoted by
H↑. Reproduced with permission.[84] Copyright 2017, John Wiley & Sons, Inc.

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a polydomain magnet (Figure 10d). The absence of magnetic DMAPS. As the amount of DMAPS incorporated into the film
fields resulted in chiral nematic structures with various tilts was increased, the color of the composite films was red-shifted,
and angles (Figure 10e). Conversely, highly ordered structures due to an increased helical pitch. The CNC-DMAPS films
were developed when the magnetic field was perpendicular to prepared had a maximum tensile strength of 63 MPa and are
the film surface (Figure 10f). The authors demon­strated that significantly more flexible than a pure CNC film. The authors
magnetic fields can be used to improve the homogeneity of the attribute the improved mechanical properties to the fact that
cholesteric structure and to orient its domains. the DMAPS molecules act as small springs that interact with
the CNC surface without disrupting the chiral nematic organi-
zation. In this system, the color of the films could be tuned by
4.2. Chiral Nematic Films Developed with Additives varying the CNC-to-DMAPS ratio.
and Post-treatment In a similar approach, Yao et al. reported in 2017 that by
adding polyethylene glycol (PEG) to CNC suspensions and
The photonic properties of CNC films can be elevated and further controlling the evaporation conditions, CNC/PEG-films could
tuned with the use of additives that can provide another dimen- be prepared with uniform color.[91] The films were also flex-
sion of functionality. Additives can be introduced to a drying ible and changed color when exposed to water. A similar result
CNC suspension, or they can be introduced after a solid film has was reported by Xu et al. in 2018[92] in which glycerol was used
already formed as a post-treatment step. Early work with addi- as an additive to prepare red-shifted CNC/glycerol films that
tives involved adding sodium chloride to a drying CNC suspen- were flexible and responsive to water addition (Figure 11a). In
sion, which resulted in a blue-shifted film.[75] Beck et al. showed general, the addition of neutral hydrophilic additives to CNC
a decrease in reflection wavelength from 550 to 390 nm at higher suspensions results in the preparation of chiral nematic CNC
salt concentrations (up to 0.4 wt%).[75] In a different study, Mu composites with improved flexibility. Furthermore, the color of
et al. looked at the influence of adding glucose to a drying CNC these films can be tuned by varying the CNC-to-additive ratio,
suspension, which produced a red-shifted CNC film.[85] The but additive addition always results, with the exception of salt
authors postulated that the addition of glucose lowers the CNC (see Section 4.2), in red-shifted materials due to an increase
concentration required to enter kinetic arrest, thus locking in the in helical pitch. As well, there is a threshold level of additive
structures at a larger helical pitch. Despite being able to control that can be incorporated without destroying the chiral nematic
the optical properties of CNC films using additives, the addition of organization of CNCs. It is also possible to prepare CNC/
salt and glucose did not impart any additional functionality. Pure polymer composite films with less hydrophilic polymers such
CNC films are stiff and brittle, which make these materials unde- as polystyrene (PS), poly(methyl methacrylate) (PMMA) and
sirable for applications requiring flexibility and adaptability.[31] polycarbonate (PC).[93] For the successful coassembly of these
Liu et al. added an ionic liquid, 1-allyl-3-methylimidazolium chlo- polymers with CNCs, the CNC suspension must be prepared
ride, to a CNC film and found that the ionic liquid uniformly in DMF (a good solvent for the polymers mentioned) instead
penetrated throughout the film (Figure 8c).[86] By increasing the of water.
concentration of ionic liquid, from 5 to 30 wt%, they produced In 2016, Wu et al. prepared a CNC-based photonic film to
red-shifted films with increased flexibility. Nan et al. treated CNC mimic beetle shells of the genus Chrysina (Figure 11b).[94]
films with sodium hydroxide and were able to increase the ten- To achieve this goal, they sandwiched a unidirectional poly-
sile strength and toughness of films (Figure 8d).[87] A blue-shift amide-6 layer in between two CNC/polyethylene glycol dia-
was observed with prolonged alkali treatment. In addition to tun- crylate (PEGDA) layers. The polyamide-6 layer was included
able optical properties, CNC materials developed with additives as a half-wave retarder to enable hyper-reflection to occur. As a
open doors to several applications, including flexible sensors, and result, the reflectance intensity of the obtained nanocomposite
crack-free coatings. film exceeded 50% (hyper-reflection) at a certain wavelength.
The wavelength reflected could be tuned by varying the CNC/
PEGDA ratio (with increasing PEGDA producing red-shifted
5. CNC Composite Materials with Structural Color materials) or through the absorption of water. The hydrophi-
licity of the PEGDA not only results in a change in the structural
CNC films are brittle and have static optical properties that are color of composite, but it also induces humidity-responsive
fixed at the film formation step;[88] therefore, researchers have actuator behavior. The actuation occurs from asymmetric
tried to improve these features by increasing film flexibility swelling of the CNC/PEGDA layers, with the layer exposed to
through the incorporation of various additives. Early work the water expanding and causing the structure to bend.
focused on the coassembly of CNCs with hydrophilic polymers Other methods used to incorporate functionality into CNC
such as sodium polyacrylate and poly(ethylene glycol),[89] but films, while retaining the chiral nematic structure include post-
this approach can disrupt the chiral nematic organization of the modification of the CNC surface[95] and more extensively coas-
CNCs, reducing the iridescence. sembly with monomer precursors and subsequent thermal[96,97]
Recent work by Guidetti et al. demonstrated that zwitterionic or photopolymerization.[98] Using the in situ polymerization
surfactants can be used to prepare flexible CNC films without approach, Khan et al.[96] and Giese et al.[97] reported in 2013
compromising the structural color.[90] In this work, they used that CNC composites could be prepared from phenol-formal-
the surfactant 3-(N,N-dimethylmyristylammonio)propane- dehyde (PF) and amino-formaldehyde (AF), respectively. For
sulfonate (DMAPS) and a sodium CNC (Na-CNC) to prepare the PF system, the color of the resulting film could once again
a range of CNC-DMAPS films with different amounts of be controlled by tuning the CNC-to-PF ratio;[96] the resultant

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Figure 11. Examples of CNC composites with structural color. a) CNC/glycerol (70:30) composite film under various deformation conditions. b) The
folding and blooming procedure of an artificial flower supported on a metal iron-mesh driven by wet air; the wet air was provided by a Petri dish with
deionized water under the mesh. c) AF-CNC composite film after synthesis (left), after imprinting of the crest (middle), and imprinted AF-CNC in front
of a sheet of paper to show the transparency of the composite material (right). a) Reproduced with permission.[92] Copyright 2018, Royal Society of
Chemistry. b) Reproduced with permission.[94] Copyright 2016, Royal Society of Chemistry. c) Reproduced with permission.[97] Copyright 2013, American
Chemical Society.

films are highly robust but brittle. For the AF system, the to coat a range of materials, such as stainless-steel mesh, nylon
colored composite film could be prepared if salt was added to mesh, nickel foam, and carbon cloth, with CNC/polymer film.
the system.[97] Furthermore, the freshly prepared CNC-AF films Sensing properties of these structures were investigated in a
are flexible and therefore can be manipulated and processed range of solvents (water, DMSO, DMF, DMA, acetic acid, alco-
(Figure 11c). If mechanical pressure is applied to the fresh hols, and acetone), which showed the film would either swell or
composite film, a color change is induced in the material from shrink depending on the solvent polarity. Finally, an anticoun-
red to blue due to compression of the helical pitch of the chiral terfeiting QR code with a composite film was prepared that can
nematic structure. The material can then be thermally cured only be read when irradiated with right-handed circularly polar-
again to lock in the new structure. However, for this system it ized light.
was not possible to obtain a reproducible color change when Mesoporous photonic cellulose was prepared by Giese et al.
the same force was applied. in 2014 in a two-step protocol.[100] In this report, a cellulose
Kelly et al. demonstrated in 2013[98] that responsive photonic nanocrystal suspension was mixed with a urea formaldehyde
CNC hydrogels could be prepared using the in situ polymeriza- (UF) precursor then the resulting CNC-UF film was ther-
tion method. In this approach, monomer precursors and a photo­ mally treated at 120 °C to complete the polymerization. The
initiator were added to an aqueous CNC suspension and cast composite was then treated with 15% aqueous KOH at 70 °C
into a Petri dish. Water evaporation was allowed to occur until to remove the UF. It is worth noting that these conditions are
the desired CNC wt% was achieved (minimum of 10 wt% to usually used to remove CNCs from composites but, surpris-
ensure chiral nematic organization occurred). The solution was ingly in this work, the UF was removed instead. This produced
then photopolymerized to give the desired CNC hydrogel. This a chiral nematic mesoporous photonic cellulose film, which
was successfully achieved with different polymers including was no longer furnished with the surface sulfate ester groups
polyacrylamide, poly(2-hydroxyethylmethacrylate), and poly- making it unsusceptible to redissolution in water. The color
acrylic acid. All hydrogels exhibited iridescence and the color of the film could be tuned by altering the CNC/UF ratio or
could be blue-shifted through salt addition (see Section 4.2) or through the addition of salt. Using these techniques, materials
red-shifted by adding more monomers. The color of the chiral with a pitch of 500–1300 nm could be accessed. In addition,
nematic CNC hydrogels can be changed in response to external the reflection wavelength could be controlled by tuning the
stimuli such as solvent, pH or temperature, depending on the ethanol/water ratio used to swell the films, for example, from
chosen polymer. 430 nm in pure ethanol to 840 nm in pure water (Figure 12b).
Chen et al. in 2018 reported the preparation of a self- The swollen films could then be compressed using an applied
healable photonic hydrogel film comprised of CNCs and force of 0 to 7.8 × 106 N m−2 which resulted in a ≈100 nm shift
poly(vinyl alcohol)–polyacrylamide hydrogel.[99] The hydrogel in the color from 630 to 520 nm with increasing pressure. In a
was crosslinked using boronic esters and the dynamic nature separate report it was also demonstrated that gold nanoparticles
of these covalent bonds furnished the material with self- can be loaded into the mesopores to yield plasmonic chiroptical
healing properties. The color of the composite could be tuned activity,[101] which may expand the range of sensing applications
by varying the polymer concentration, with higher loadings possible for this system.
producing red-shifted films. The self-healing behavior was The responsive color of CNC films has been of interest
employed to prepare multistacked films (Figure 12a) as well as in sensing applications with several devices fabricated for

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Figure 12. Responsive chiral nematic CNC-composites with tunable color. a) The 3D structure constructed by five triangular patterns (from bottom to
top, mPVA–PAM/mCNC = 7%, 14%, 30%, 40%, and 20%, respectively) stacked together through the self-healing process. b) Photos of mesoporous
photonic cellulose films soaked in ethanol/water at 100% (blue), 90% (green), 80% (orange), and 60% (red) ethanol. c) Photos of a CNC sensor for
aldehyde gases before and after exposure to formaldehyde gas. d) Schematic representation demonstrating the selectivity of a CNC-based aldehyde
sensor against other possible contaminants. e) Photos of the CNC-E stretched by 0%, 65%, 250%, and 300% (left to right). a) Reproduced with permis-
sion.[99] Copyright 2018, Royal Society of Chemistry. b) Reproduced with permission.[100] Copyright 2014, John Wiley & Sons, Inc. c,d) Reproduced with
permission.[104] Copyright 2018, American Chemical Society. e) Reproduced with permission.[112] Copyright 2020, John Wiley & Sons, Inc.

humidity sensing.[102,103] Expanding on this work, Song et al. of the glucose-CNC film into the desired CNC elastomer. The
employed CNC films for the detection of aldehyde gases such resulting CNC-elastomer is colorless when relaxed but its color
as formaldehyde and propanal.[104] Chiral nematic CNC films changes from red-to-green-to-blue when it is stretched up to
were prepared on a silicon substrate using a dip-and-pull pro- 300% elongation. This color change is due to the compression
cess with an aqueous suspension of CNCs and the ionic liquid, of the helical pitch of the chiral nematic structure upon the
1-butyl-3-methylimidazolium chloride (BmimCl). BmimCl application of mechanical stress. Patterned elastomers could
was used as a charge-screening agent to enable the CNCs to also be prepared by either water-droplet patterning of the glu-
pack tightly. The color and thickness (100–300 nm) of the films cose-CNC film or by using a glucose-CNC film with a gradient
could be controlled by changing the pulling speed, with slower of helical pitches (see Section 4). The resulting CNC-elastomers
pulling speeds resulting in red-shifted and thicker films. The were again colorless in their relaxed state, but became colored
films were then functionalized with amine groups using the and their pattern revealed when stretched.
reagent 3-aminopropyltriethoxysilane (APTES), which reacted
with the surface hydroxyl groups. The successful modification
was confirmed by X-ray photoelectron spectroscopy (XPS) and 6. Hydroxypropyl Cellulose
no change in the color of the films was observed. Incorpora-
tion of amine groups onto the film surface enabled fabrication Hydroxypropyl cellulose (HPC) is a water-soluble cellulose
of colorimetric sensors that could distinguish between aldehyde derivative that has been used in colloidal stabilizers and flow
gases and other possible contaminants such as chloroform, iso- modifiers. It is produced by the etherification of cellulose,
propanol, and xylenes (Figure 12c,d). which introduces hydroxypropyl groups onto the polymer
The integration of photonic crystals into elastomers enables chain. In 1984, Werbowyj and Gray reported that HPC can self-
their color to be manipulated with the application of mechan- assemble into a chiral nematic structure in solution[114] and
ical stress, producing materials with dynamic optical properties the organization is preserved when the solution is cast into a
that have potential applications as mechanical sensors,[105–107] film.[115,116] Unlike CNCs, the solution temperature has a sig-
optical coatings,[108,109] soft displays,[110] and biosensors.[111] nificant effect on the liquid crystal phase obtained for HPC. For
Very recently, we reported the preparation of a CNC-elastomer example, concentrations above ≈65 wt% are required to access
that shows reversible visible color when mechanical stress is the chiral nematic phase at room temperature, but at 0 °C,
applied (Figure 12e).[112] In this report we built on previous 40 wt% HPC produces a chiral nematic structure while 20 wt%
work from our group demonstrating that a CNC-elastomer remains isotropic between −10 and 35 °C.[117] Another signifi-
could be prepared that showed a change in birefringence when cant difference between HPC and CNCs is that HPC forms the
stretched and viewed through crossed-polarizers.[113] In our right-handed chiral nematic structure that reflects right-handed
new report we optimized the conditions for CNC-elastomer circularly polarized light, whereas CNCs organize into a left-
preparation and also used slow evaporation to produce the most handed structure that reflects left-handed circularly polarized
blue-shifted glucose-CNC film (see Section 4 for more details). light.[118]
A three-step protocol of DMSO pre-treatment, monomer A recent report by Liang et al. demonstrated that roll-to-roll
infiltration, and polymerization enabled the transformation printing can be used to fabricate HPC-based pressure sensors

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Figure 13. Examples of materials prepared from hydroxypropyl cellulose and chitin. a) Black PET-backed product rolls of red, green, and blue HPC
laminates with HPC concentrations of 63, 66 and 70 wt%, respectively. b) Photos of tunable iridescence of deacetylated chiral nematic chitin nanocrystal
films in water during drying of the film. These samples were obtained directly from a crab shell. a) Reproduced with permission.[119] Copyright 2018,
Springer Nature. b) Reproduced with permission.[120] Copyright 2014, John Wiley & Sons, Inc.

with a visible color readout (Figure 13a).[119] In this approach, Chitin can be obtained from waste crustacean (e.g., crab,
an aqueous solution of HPC is slot-die coated, the edges are lobster, shrimp) shells by removing the mineral and protein
sealed with glue, which is selectively polymerized, and then by treatment of the shells with acid and base, respectively.
the film is laminated to encapsulate the HPC. Red, green and Remarkably, the chitin film obtained shows chiral photonic
blue HPC laminates can be prepared by varying the initial properties! In fact, chitin nanocrystals organize into a left-
concentration of the HPC solutions. The pressure response handed chiral nematic structure within the shell, generating
of the HPC laminates was investigated using a film that was a structure that closely resembles the organization of CNCs
at the boundary between infrared and visible reflection when in iridescent films. Nguyen et al. showed that the films reflect
no force was applied (0 kPa). As pressure was applied to the left-handed circularly polarized light and the wavelength of the
film, the color shifted from red (1–3 kPa), to green (3–5 kPa), reflected light red-shifts when films of chitin are swollen in
and to blue (5–10 kPa), giving a shift of ≈275 nm over a 10 kPa water (Figure 13b).[120]
range. The use of this material for pressure mapping was dem- After extracting the chitin from a crab shell, it may be
onstrated using the real time recording of the pressure profiles converted into chitin nanocrystals by treatment with boiling
of footprints. The scale of the fabrication of these films plus 3 m HCl. The resulting solution is washed with water until
the pressure responsiveness makes this the most sophisticated a neutral pH is obtained and a colloidal suspension of chitin
material prepared from HPC with visible color. nanocrystals is obtained. In 1993, Revol et al. reported that
when a critical concentration (≈5 wt%) of chitin nanocrystals
was reached, phase separation into an isotropic phase and a
7. Moving Beyond Cellulose: Chitin Nanocrystals chiral nematic liquid crystalline phase occurred.[121] Building
on this pioneering work, Narkevicius et al. systematically
This progress report has focused on the development of chiral investigated how the properties of chitin nanocrystal suspen-
photonic materials based on cellulose nanocrystals. But, it is sions influences the self-assembly behavior.[122] In this report,
worth a brief discussion of chitin nanocrystals since they have they found that acid hydrolysis with 3 m HCl for 9 h followed
similar properties to CNCs and the knowledge obtained from by tip sonication of 100 kJ g−1 produced chitin nanocrystals
studying CNCs can be employed to produce chiral photonic with low polydispersity and high surface charge. Using these
materials based on chitin. Chitin is one of the most abundant chitin nanocrystals they then found that by changing the ionic
biopolymers—it is found in fungi, insect exoskeletons, and strength and pH of the suspensions they could prepare chiral
the shells of shrimp, lobsters, crabs, and other organisms. nematic chitin nanocrystal films with helical pitches between
Chitin is structurally similar to cellulose, having b-(poly-1,4-N- 650 and 3720 nm, determined by SEM.
acetylglucosamine) chains, comprised of the glucose derivative
N-acetylglucosamine. N-Acetylglucosamine has an acetamide
group in the two positions instead of the hydroxyl group found 8. Conclusion and Outlook
in glucose, which increases the number of hydrogen bonding
units in the chitin polymer chains and makes chitin a stronger In this progress report, we have outlined how the discovery of
material than cellulose. the micro- and nanostructures responsible for structural color

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in nature dating back to the 1940s and the preparation of CNCs provide scalable, chiral photonic films with high optical quality
in the early 1950s have been applied to fabricate CNC-based remains to be seen, but the innovations and science that are
materials with chiral photonic properties. Early work focused arising across the globe in this field will help to inform the next
on the synthesis of CNCs and the effect of the cellulose source generation of optically responsive materials.
on the properties of the CNCs, but in the last 10 years much
research has centered around understanding the self-assembly
process and the preparation of functional materials. By stud- Acknowledgements
ying the self-assembly process, the intermediate tactoid struc-
ture was identified, which has also been observed in many We thank NSERC for funding and are grateful to Wadood Hamad for
liquid crystalline substances. This discovery helped researchers getting us into the CNC field, and for a long-term collaboration. A.T.
thanks UBC for a 4YF Fellowship and C.E.B. thanks the Government of
optimize the self-assembly conditions to reduce defect forma- Canada for a Banting Fellowship.
tion and produce CNC films with improved chiral nematic
order and, thus, enhanced optical properties. We also under-
stand how the surface chemistry plays a critical role in film for-
Conflict of Interest
mation. Pure CNC films are interesting, but they have limited
uses due to their static optical properties and brittleness; to The authors declare no conflict of interest.
address this, research has focused on making CNC composites
in which the structural color is preserved. This goal has been
achieved through the simple addition of neutral, hydrophilic Keywords
additives such as polyols (e.g., glycerol and glucose), surfactants cellulose nanocrystals, chirality, chitin, photonic materials, structural
and polymers, or through more intricate synthetic protocols colors
that involve the in situ preparation of polymers to embed the
CNCs in a composite or through sandwiching a CNC film Received: September 8, 2019
between two polymer layers. Although these methods have Revised: November 26, 2019
enabled the fabrication of a range of responsive materials with Published online: February 3, 2020
reversible visible color changes, the long evaporation times
required for film formation may limit the large-scale produc-
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