Hoeng-2016-Use of Nanocellulose in Printed Ele

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Use of nanocellulose in printed electronics:

Cite this: Nanoscale, 2016, 8, 13131
a review
Fanny Hoeng,a,b Aurore Denneulina,c,d and Julien Bras*a,c,d
Since the last decade, interest in cellulose nanomaterials known as nanocellulose has been growing.
Nanocellulose has various applications ranging from composite reinforcement to rheological modifiers.
Recently, nanocellulose has been shown to have great potential in flexible printed electronics appli-
cations. The property of nanocellulose to form self-standing thermally stable films has been exploited for
Received 13th April 2016, producing transparent and smooth substrates for printed electronics. However, other than substrates, the
Accepted 29th May 2016
field of printed electronics involves the use of inks, various processing methods and the production of
DOI: 10.1039/c6nr03054h flexible electronic devices. This review aims at providing an overview of the use and potential of nano-
www.rsc.org/nanoscale cellulose throughout the printed electronics field.
1. Introduction lose known as nanocellulose have attracted considerable atten-

tion. The nanocellulose obtained via chemical or mechanical
Cellulose is the most abundant renewable and biodegradable treatment of cellulose fibers can be divided into two cat-
polymer on earth (1011−1012 tons produced annually). During egories: cellulose nanocrystals (CNC) and cellulose microfibrils
the past few decades, nano-scaled particles coming from cellu- (MFC), also called cellulose nanofibrils (CNF). Both CNF and
CNC are found to be effective in various applications such as
mechanical reinforcements in nanocomposites,1–3 barrier
a
1Univ. Grenoble Alpes, LGP2, F-38000 Grenoble, France. membranes,4 rheological modifiers,5 fluorescent labeling
E-mail: julien.bras@grenoble-inp.fr
b agents in medical imaging6,7 and drug delivery systems.8,9 The
Poly-Ink, 27, Boulevard Louise Michel, 92230 Gennevilliers, France
c
CNRS, LGP2, F-38000 Grenoble, France number of published books10 and reviews11–13 on the different
d
Agefpi, LGP2, F-38000 Grenoble, France nanocellulose applications indicates the interest in such
Fanny Hoeng is a research engin- Dr Aurore Denneulin holds an

eer with a master’s degree from engineering degree from the
the International Engineer International Engineer School of
School of Paper, Print Media Paper, Print Media and Bio-
and Biomaterials (Grenoble materials (Grenoble INP-Pagora,
INP-Pagora, France). She cur- France). After completing her
rently works as a research engin- PhD in materials science and
eer for Poly-Ink (France) in process engineering, she became,
collaboration with the Labora- in 2012, associate professor and
tory of Pulp and Paper Science expert in complex fluid design
(LGP2). Her current research for functional printing at the
focuses on using bio-based French Laboratory of Pulp and
Fanny Hoeng materials for conductive ink Aurore Denneulin Paper Science (LGP2). She is
applications. part of the research team
“Surface functionalization by printing processes” and her research
focuses mainly on the design of innovative functional inks based
on high performance materials such as carbon nanotubes, metallic
nanowires, nanocelluloses for different deposition processes
( printing, coating, 3d printing, etc.).
This journal is © The Royal Society of Chemistry 2016 Nanoscale, 2016, 8, 13131–13154 | 13131
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Fig. 1 Non-cumulative evolution of the annual number of publications and patents on nanocellulose and nanocellulose in electronics. Source:
SciFinder & Espacenet – descriptors: cellulose microfibrils, cellulose nanofibrils, nanofibrillated cellulose, microfibrillated cellulose, cellulose
nanofibers, cellulose (nano)whiskers, cellulose nanocrystals – associated with electronics, conductive, electric and printed electronics. Sorting of
the resulting papers has been done to keep only relevant papers and patents.
materials. Recently, the desire to combine the outstanding nentially increased in the last 15 years. Printed electronics can
properties and abilities of nanocellulose for designing flexible be defined as the combination of printing processes and ink
and sustainable electronics has attracted significant interest. chemistry for the manufacture of electronic components. Com-
Flexible electronics and, more generally, printed electronics pared to the conventional lithographic processes used in
is an important and promising area of research exhibiting microelectronics, this combination would lead to the pro-
strong developments. Interest in printed electronics has expo- duction of flexible, cost effective and environmentally friendly
electronic products due to the large variety of printing pro-
cesses possible. Printed electronics processes include tra-
ditional printing processes, such as inkjet, flexography or
Dr Julien Bras (H index: 27; 92 screen-printing, and coating processes such as bar coating,
scientific papers, 9 patents) is spin-coating or sputtering for producing conductive tracks and
Associate Professor at Grenoble layers. Recently, additive processes like 3D printing have also
Institute of Technology (Grenoble been considered for complex electronics designs.
INP-Pagora). He is head of the As can be seen from Fig. 1, interest in the use of nanocellu-
“Multiscale Biobased Material” lose in printed electronics has recently been growing.
group (ab. 40 pers.) at LGP2 However, its use in printed electronics is still very limited as
(Laboratory of Pulp & Paper compared to the other applications of nanocellulose. Among
Science). He has directly super- the 1000 papers and patents related to nanocellulose pub-
vised 16 PhD and 12 Post-doc lished in 2015, only 11 were related to printed electronics. Pub-
After engineer diploma in Chem- lications dealing with nanocellulose and printed electronics
istry and a PhD on Renewable only represent 1% of the total number of papers with 75% of
Julien Bras Materials. He worked in industry publications and 15% of patents. These papers focus mainly
for a few years as Innovation on two areas: (i) the blend of conductive particles and nano-
Manager within Ahlstrom Specialty Paper and then left industry to cellulose and (ii) the use of nanocellulose as a substrate.
become associate professor in 2006. His expertise deals particu- Recently, a few reports presented the use of nanocellulose as
larly with nanocellulose, biobased and smart materials. More substrates,14 conductive composites15 and their integration in
precisely, he has proposed new ways for the production, electronics devices.16 To the best of our knowledge, no com-
characterization and functionalization of nanocellulose for several prehensive and exhaustive review has reported on the use of
applications during the last 10 years. He has already coordinated nanocellulose in all the areas of printed electronics compris-
or supervised several industrial and European projects in FP6, FP7 ing inks, substrates, and the associated processes and appli-
and Marie-Curie calls. He is involved in the Labex & Carnot insti- cations as illustrated in Fig. 2.
tute organization and is associate editor of an Elsevier journal This review aims at giving the first global overview of the
(Industrial Crops and Products). He is a member of Institut Uni- use of nanocellulose in printed electronics: (i) the potential
versitaire Français (IUF) from 2016 to 2021. of nanocellulose in functional conductive inks, (ii) the use
13132 | Nanoscale, 2016, 8, 13131–13154 This journal is © The Royal Society of Chemistry 2016
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Fig. 2 Use and interest of nanocellulose within the printed electronics field (illustration extracted from ref. 96, 139, 185).
of nanocellulose as a substrate in printed electronics and are flexible ribbons obtained by a mechanical treatment of cel-
(iii) electronics applications of nanocellulose. Analysis was per- lulosic fibers and are composed of both amorphous and crystal-
formed on both publications and patents. The first part of the line domains. This section focuses on the preparation,
review focuses on a brief description of nanocellulose prepa- properties, and applications of CNC and CNF.
ration and properties besides introducing the materials and 2.1.1 Cellulose nanofibrils (CNF). Extraction of CNF was
processes used in printed electronics. Further parts would reported first by Turbak et al.17 who observed the formation of
focus on the use of nanocellulose in printed electronics and a viscous gel after mechanical disintegration of the cellulosic
emphasize the benefits of using cellulose nanomaterials. fibers. CNF can be produced from different sources such as
cotton, wood and annual plants by mechanical disintegration
of the cellulosic fiber suspension with an induced high shear.
2. Fundamentals of nanocellulose The high mechanical shear progressively causes a longitudinal
and printed electronics cleavage of the cellulose fibers to obtain nanofibrils. Processes
commonly involved in mechanical fibrillation are grinding,
2.1 Nanocellulose preparation and properties microfluidization and homogenization18 and the cellulose sus-
The structure of cellulosic fibers can be represented as a succes- pension passes several times through the apparatus before
sion of cellulosic filaments of different length scales as schema- CNF isolation. These processes generally involve many passes
tized in Fig. 3. Individual cellulose molecules are assembled to and are really energy consuming. Consequently, pre-treatment
form elementary cellulose fibrils (width ∼3–5 nm), which are methods, such as enzymatic treatment19,20 and 2,2,6,6-tetra-
aggregated to form bundles of cellulose nanofibrils (CNF) methylpiperidine 1-oxyl (TEMPO) oxidation,21 can facilitate the
(width ∼20 nm) composing the cellulose fiber. Cellulose with a fibrillation of cellulose fibers and reduce the number of
fibrillary nature and a hierarchical structure is at the origin of passes. The reduction of energy consumption using these pre-
cellulose nanomaterials known as nanocellulose. Two types of treatment methods has allowed the industrialization of CNF
nanocellulose can be extracted from cellulosic fibers differing since 2010. A recent review focused on recent advances in CNF
in the steps involved in their isolation and in their structure. preparation.22 The structure of CNF is composed of both amor-
While CNC are rigid rod-like particles obtained by chemical phous and crystalline parts. CNF fibers possess a high aspect
treatment of cellulose and are mostly crystalline in nature, CNF ratio (∼100) with dimensions of 2–60 nm in diameter and a
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Fig. 3 Schematic length-scale representation of networks obtained with different cellulosic materials (up) compared to specific dimensions of
different conductive particles (down).188
few microns in length depending on the processing and pre- works to form self-standing films or coatings has attracted sig-
treatment methods. Abundance of hydroxyl groups on the CNF nificant interest. A CNF network can be seen as a nanoporous
surface associated with their high aspect ratio induce the for- web-like structure of highly entangled nanofibers. Resulting
mation of strong hydrogen bonds between each nanofiber, films appear smoother and less porous than the traditional
resulting in the unique properties of CNF such as enhanced cellulosic papers and have a certain level of transparency (light
mechanical properties, gel-like behavior and the ability to transmission) depending on the CNF dimensions.27 These
form flexible self-standing films on drying. Presence of enhanced surface properties make CNF very interesting for
hydroxyl moieties also offers a very reactive chemistry for printing applications28 and in the development of flexible elec-
surface modification. Oxidation23 or grafting24 can be tronic devices.14 CNF can also be used for functional aerogel
implemented for introducing new functional or charged preparations29,30 and in 3D printers,31,32 but these points will
groups on the CNF surface. not be detailed in this review.
Other than the abovementioned vegetal sources, certain 2.1.2 Cellulose nanocrystals (CNC). Unlike flexible CNF,
bacteria can also secrete cellulose nanofibers; these are called CNC are rigid rod-like nanoparticles corresponding to crystal-
bacterial nanocellulose.25 Bacterial nanofibers are very pure line parts of cellulose fibers. CNC visualization was first
and exhibit properties such as higher crystallinity, higher cellu- reported in the 1950s by Rånby et al.33 who observed a birefrin-
lose concentration (about 100%) and a finer web-like structure gence of cellulose suspension after an acid hydrolysis, and the
as compared to that of CNF obtained from vegetal sources. material was then extensively studied in the 1960s.34 CNC can
However, redispersion of bacterial nanofibers is more difficult. be isolated by a chemical treatment of cellulose with a mild
The structure, mechanical properties and surface reactive acid hydrolysis. Acid infiltration into the accessible amorphous
chemistry of CNF have been utilized in a large range of appli- regions of the cellulose fibers leads to the cleavage of the
cations, such as drug release,9 paper coating26 and as glycoside bonds. Thus, amorphous parts are dissolved, leading
reinforcements in composites.2 Recently, the use of CNF net- to the formation of crystalline CNC. Various acids, such as
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hydrochloric35 and hydrobromic36 acids, have been used for ment of annealing (∼150–250 °C for several minutes) is
CNC isolation. However, isolation using sulfuric acid is by far usually required. This leads to the formation of a continuous
the most common method, as it can introduce negatively interconnected phase between the metallic particles after the
charged half-ester sulfate groups on the CNC surface. These elimination of all the insulating components present in the
groups induce repulsive forces between the CNC, leading to an ink (stabilizing agents, other additives, etc.). Silver has been
electrostatic stable colloidal suspension in water. Many the most widely used metal so far owing to its high bulk con-
research studies have focused on the isolation conditions37,38 ductivity and high resistance to oxidation. However silver is
and the effect of the raw material for producing CNC in terms expensive (∼500 $ kg−1), resulting in a high cost of the inks.
of its yield, dimensions, and properties. Most of the conductive silver inks are based on spherical nano-
The structure of CNC differs from that of CNF. CNC have a particles or flakes. These inks exhibit a high conductivity but
rice-like structure rather than a filament-like one. Dimensions the obtained printed tracks and layers are usually opaque and
of CNC can vary from 10 to 50 nm in diameter and from 100 to brittle. Copper has also been of interest owing to the high con-
500 nm in length depending on the starting material.37 The ductivity of bulk copper and the lower price compared to silver
high surface area of the CNC induces great mechanical pro- (∼5 $ kg−1). However, instability of the copper particles under
perties and offers a good surface reactivity, allowing the intro- environmental conditions is a major drawback to the use of
duction of functional groups by means of grafting39,40 or copper in conductive metallic inks, and several research
oxidation.41,42 Additionally, CNC can organize themselves in a studies have focused on the protection of copper particles.50–52
chiral nematic way in suspensions leading to the formation of Recently, nano-structured metal particles, such as metal
iridescent films once dried, unlike CNF.43 However, even nanowires and nanofibers, have attracted significant interest
though the films produced by CNC are transparent, they are in the manufacture of flexible transparent conductive layers
usually more brittle than those of CNF due to their crystalline owing to their high aspect ratio.53,54 These elongated particles
nature. Recently, the use of CNC as a stabilizer in pickering can form a percolated network at very low concentrations,
emulsion has been reported and seems very promising.44 The resulting in printed layers with a high level of light
applications of CNC have focused on mechanical reinforce- transmission.
ments in composites,45 iridescent films,43 and emulsions44 Conductive polymer and carbon particle inks differ from
but its use in functional inks has recently been reported. metal inks as they possess a moderate conductivity (about 100
These aspects would be detailed later. times lower as compared to silver), but can exhibit trans-
parency and flexibility. These inks do not require any annealing
2.2 Materials, processes, and applications of printed treatment, allowing the printing on flexible substrates such as
electronics plastics, which cannot withstand high temperatures.55,56 Con-
The field of printed electronics constitutes a combination of cerning conductive polymers, poly(ethylene-dioxythiophene):
conductive material formulation and printing processes for poly(styrene sulfonate) (PEDOT-PSS) is the most commonly
the manufacture of electronic components. Printed electronics used one for processing conductive layers owing to its good
is a growing field and the market is estimated to be $73 billion processability and stability in water. As an example, a perform-
in 2025.46 Due to the above-mentioned advantages in terms of ance of 35 Ω □−1 at 80% transparency has been reported for
productivity and waste production as compared to the tra- spray-coated conductive PEDOT-PSS films.57 Regarding carbon
ditional processes (vapor deposition or lithography), the use of particles, graphite has been largely used in flexible batteries
flexible substrates is one of the crucial breakthroughs in the while carbon nanotubes and graphene are common materials
area of printed electronics. A brief overview of the materials, for the processing of conductive and transparent layers. CNTs
processes and applications of printed electronics is summar- and graphene sheets with unique properties such as high
ized in the following sub-sections. intrinsic current mobility, high mechanical properties and
2.2.1 Materials. Conductive materials for conductive inks optical transparency have raised much interest for the develop-
can be divided into three categories: conductive polymers, ment of low-cost printed electronics applications.58–60 For
metallic particles and carbon-based particles (carbon nano- example, a conductivity of 286 Ω □−1 with a transparency of
tubes, graphene, etc.). The conductivity, flexibility and trans- 92% has been reported for carbon nanotubes.61
parency of these materials are different. Fig. 3 summarizes the 2.2.2 Processes for printed electronics. Many printing pro-
conductive particles and their length scales as compared to cesses such as flexography62,63 and gravure printing,64,65 have
nanocellulose. The conductive particles are generally selected been used in printed electronics. However, recent studies have
by (i) the printing process due to specific physico-chemical ink mostly focused on inkjet printing and screen-printing pro-
properties and particle dimensions and (ii) the required per- cesses owing to the possibility of using additive processes and
formance for end-use application in terms of flexibility, trans- a large amount of deposited materials, respectively. Inkjet
parency and conductivity. Some reviews have provided details printing is a non-contact and additive process in which the ink
of specific conductive materials dedicated to inkjet print- is ejected through micrometric nozzles onto the printing sub-
ing47,48 and to opto-electronic applications.49 strate. Advances in inkjet printing in the field of printed elec-
Metallic particle inks offer the highest level of conductivity. tronics relies on the possibility of depositing a thin layer
To obtain a high level of conductivity, an additional post treat- (∼0.8–0.2 µm) at a high printing speed with a high flexibility
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(no printing form is needed) and resolution. The limitations of solar cells77 have also been produced using printing and
inkjet printing are especially due to the specific ink physico- coating techniques.
chemical property requirements for allowing droplet ejection
and the restriction in the particle size (<1 µm) for avoiding
nozzle clogging.66 The use of inkjet printing to manufacture 3. Use of nanocellulose for
printed electro-active components is growing rapidly. For conductive inks
example, Hun Eom et al. used inkjet for printing a conductive
polymer layer for solar cell applications.67 Mäntysalo and Conductive ink functionality is usually achieved by the
Mansikkamäki deposited an antenna on a polyethylene tere- addition of conductive fillers within the ink formulation. As
phthalate (PET) substrate using a catalytic ink.68 Recently, mentioned earlier, three types of conductive materials are
Sowade et al. have demonstrated a completely printed transis- commonly used to formulate conductive inks: metallic nano-
tor using inkjet on flexible PEN using an industrial inkjet particles or flakes (mainly silver, gold, and copper), carbon
printer.69 The screen printing process has also been largely particles (nanotubes, graphene, graphite, carbon black, fuller-
implemented for printing electronic devices. In the screen enes) and conductive polymers (PEDOT-PSS, polypyrrole (PPy),
printing process, the printing is performed by passing the ink polyaniline (PANI), etc.). Major issues in the formulation of
through a screen mesh using an applied pressure by a squee- conductive inks are (i) controlling the raw conductive material
gee. A polymer emulsion covers the non-printed zone of the synthesis and (ii) the ink formulation for improving the
screen while the printed zone is exposed, allowing the ink to stability, dispersion and physico-chemical properties of the
pass through the mesh. Screen-printing can be used for depos- suspension.
iting layers with a thickness of several micrometers but the Recently, nanocellulose has exhibited great potential in the
maximal resolution (∼100 µm) is lower compared to that of the synthesis of raw conductive materials and the ink formulation
inkjet printing. Screen-printing has been employed in various as schematically described in Fig. 4. Nanocellulose is a promis-
printed electronics applications such as solar cells,70 sensors71 ing bio-based material in the synthesis of conductive particles
and transistors.72 as it can act as (i) a bio-template for the synthesis of tubular
Coating techniques such as slot die, bar and blade coating conductive particles using nanocellulose with a high aspect
and spray techniques can be used for processing transparent ratio and (ii) a capping agent in the synthesis of metallic par-
conductive layers with an easy, fast and large scale process. ticles. Nanocellulose can also be useful in ink formulation as
These processes can be easily scaled up and are adaptable to (iii) a dispersing and stabilizing agent or (iv) a binding agent.
roll-to-roll production. An overview of coating techniques for Most of the currently published papers on nanocellulose and
solar cell applications73 was reported by Frederik Krebs. The conductive materials mainly focus on composite applications.
limitations of the coating techniques are the high waste pro- Here, we provide an overview of conductive materials based on
duction and the impossibility of processing a detailed pattern. nanocellulose that could have a strong potential in conductive
2.2.3 Applications of printed electronics. Printed elec- ink applications.
tronics have various applications, which can be divided into
the manufacture of electronic components, such as antennas 3.1 Nanocellulose as a bio-template
or transistors, which usually requires patterning, and the man- For use as a template, either cellulose nanocrystals or cellulose
ufacture of conductive electrodes requiring conductive layers. nanofibers are used as raw materials. The high aspect ratio of
Requirements can vary depending on the application. Elec- nanocellulose is of interest for using nanocellulose as a tem-
tronic components require highly conductive materials while plate. The use of nanostructured particles with a high aspect
the performance of a conductive electrode depends on the tar- ratio would allow a low functional loading. Most of the papers
geted application. Conductive electrodes integrated in devices reported a templating method using nanocellulose and con-
such as sensors or energy storage devices should have a high ductive polymers. However, metallic particles like silver, gold,
conductivity. Opto-electronic devices such as displays, organic and copper had also been a subject of interest. Table 1 pro-
light emitting diodes (OLEDs), and solar cells consist of con- vides an exhaustive overview of nanocellulose associated with
ductive and transparent electrodes in a multilayer system and conductive materials that can have potential application in
would generally be a trade-off between transparency and con- conductive inks.
ductivity. As presented earlier in the conductive material 3.1.1 Conductive polymers. Conductive polymers are semi-
section, the combination of a high conductivity and a high conducting materials owing to their conjugated bonds in the
transparency is difficult to achieve. polymer structure. Mostly used conductive polymers are
Printed electronics have been realized using both rigid sub- PEDOT-PSS, PANI and PPy, which are usually obtained by an
strates like glass and flexible substrates like paper or polymeric oxidative polymerization of the corresponding monomers.78 As
films. Processing of flexible devices or components is one of mentioned earlier, most of the papers dealing with conductive
the most important aspects in printed electronics. Electronic polymers and nanocellulose focus on achieving conductive
components such as antennas or transistors have been printed nanofibers as a filler in composite applications. For printed
on flexible paper substrates74 and more recently on 3D electronics applications, the templated nanofibers are
objects.75 Opto-electronic devices like flexible displays76 and expected to be promising for achieving high aspect ratio
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Fig. 4 Schematic representation of potential nanocellulose use for conductive ink applications.
conductive particles to develop conductive inks at a low solid previously been employed on CNF–PPy nanocomposites to
content. increase the PPy–cellulose interaction.87 An optimum Py to
Polypyrrole is the most conductive synthesized polymer hydroxyl group ratio of 16 has been found for controlling the
used in this regard. Oxidative polymerization is usually pro- polymerization and obtaining the highest electrical properties
cessed on the nanocellulose surface directly by the grafting (conductive CNC with a conductivity of about 4 S cm−1). While
from approach. The polymerization of PPy on the cellulose polymerization parameters need to be controlled to ensure a
surface occurs via strong hydrogen bonds between –OH groups total coverage of the conductive polymer on the cellulose
of cellulose and –NH groups of the Py monomer.79 Although surface, one advantage of using nanocellulose for synthesizing
covalent bonds were not formed, strong interactions with the PPy is the production of a water dispersible PPy material,
network structure seem to happen. A disadvantage of this tech- usually insoluble in water. The use of CNC has been reported
nique is the release of the non-adsorbed polymer. CNF and to enhance the PPy stability in water as compared to that of
CNC have been used as templates for PPy polymerization as pure PPy.88 Wu et al. prepared redispersible conductive
conductive fillers in the insulating matrix80 or in cellulose powder after freeze-drying, which was suitable for tunable con-
composites.81 Flandin et al. studied and patented the PPy ductive inks.86 However, obtaining a uniform PPy layer free of
polymerization on CNF for composite applications for the first polypyrrole aggregates onto the cellulose surface is still
time.80,82 Following that, several studies have aimed at under- difficult. They also reported a new method for coating the CNC
standing the influence of polymerization conditions such as surface with a smooth and uniform thin layer of PPy using
the polymerization time83 and the rinsing conditions during polyvinylpyrrolidone (PVP) to produce a PPy/PVP/CNC core–
the synthesis.84 The amount of pyrrole (Py) monomer intro- shell structure, by oxidizing CNC beforehand.89 PVP was found
duced is found to be one of the most influencing parameters to not only act as a stabilizer for avoiding PPy aggregates but
on the conductivity and the template surface coverage. Müller also provide a uniform hydrophobic layer on the CNC surface
et al. determined the effect of the Py ratio on the electrical con- for favoring the polymerization of PPy.
ductivity of the obtained bacterial CNF composites and Combining the PANI conductive polymer with nanocellu-
observed a plateau starting from a given amount of Py.83 The lose was first demonstrated by Van Den Berg et al. Adsorption
successful templating of PPy on bacterial CNF was verified by of two conductive polymers, PANI and poly( p-phenylene-
scanning electron microscopy (SEM) and Fourier transform ethynylene) (PPE), on CNC was investigated for developing
infrared spectroscopy (FTIR) analyses. Zhang et al. used electro-active composites with high mechanical properties.90
polymerization of PPy on tunicate CNC for manufacturing con- Composites were prepared by direct adsorption of the polymer
ductive films.85 SEM images indicated well attached PPy on by mixing a polymer suspension with CNC. Electro-conductive
the nanocrystal template as can be seen in Fig. 5-a, as com- composites using PANI–CNC have been successfully manufac-
pared to the neat CNC. The PPy particle size and the electrical tured with a PANI content (0.6%) lower than that calculated
performances were also found to depend on the amount of for the fully recovered CNC (20%). Thus, CNC were not fully
introduced Py. Following this, Wu et al. examined the effect of covered by PANI; however, the electrical percolation threshold
the cellulose hydroxyl groups to Py ratio on the polymeriza- was decreased due to the partial templating onto CNC.
tion using TEMPO oxidized CNC.86 TEMPO oxidation has Although their study focused on the adsorption of the
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Table 1 Overview of nanocellulose use for conductive particle synthesis
Nanocellulose Nanocellulose Conductive

type process structure Application Process Conductivity Ref.
Conductive polymers
Publications
TEMPO CNC Commercial PPy Supercapacitor Polymerization Up to 4 S cm−1 86
CNC Commercial PPy Supercapacitor Adsorption + Up to 36 S cm−1 89
polymerization
CNC Acid hydrolysis PPy Conductive paper/film Polymerization 1.4 10−3 S cm−1 85
Bacterial CNF — PPy Composite Polymerization Up to 4 S cm−1 84
CNC Acid hydrolysis PPy Water solubility of PPy Polymerization — 88
CNF Sulfite softwood pulp PPy Composite: ion Polymerization 1.5 S cm−1 81
– refiner + exchange and
microfluidizer energy storage
Bacterial CNF — PPy — Polymerization Up to 0.33 Ω cm 83
CNC Acid hydrolysis PANI Conductive composite Polymerization Up to 10−1 S m−1 189,
190
CNC Acid hydrolysis PANI Hybrid structure Sonochemical 0.075 S cm−1 91
investigation polymerization
CNF Bleached birch pulp PANI Composite paper + Polymerization 2.6 × 10−5 S cm−1 96
refiner + fluidizer coating
CNC Acid hydrolysis PANI + PFE Composite Adsorption onto CNC 0.01–0.5 S cm−1 90
CNC Acid hydrolysis PANI Shape memory Polymerization Up to 2.7 × 1010 S cm−1 94
composite of PU/CNC
CNC Acid hydrolysis PANI — Polymerization 10−2 S cm−1 191
CNC Acid hydrolysis PANI Flexible conductive film Polymerization 2.6 × 10−5 S cm−1 93
CNC Acid hydrolysis PEDOT Conductive composite Polymerization Up to 97 Ω □−1 97
(films, aerogel)
CNC Acid hydrolysis PEDOT Conductive composite Adsorption Up to 700 S m−1 98
Patents
CNF — PPy Composite Polymerization 80,
82
CNC Acid hydrolysis PPy Bio-sensor Polymerization <10−8 S cm−1 192
CNC Acid hydrolysis PPy Composite Polymerization Up to 1.88 × 10−2 S m−1 193
Bacterial CNF — PPy Composite Polymerization — 194
CNC Acid hydrolysis PANI Conductive iridescent Electro-chemical Up to 2 S cm−1 193
film polymerization
CNC Acid hydrolysis PANI Conductive film Polymerization — 95
Bacterial CNF — PANI Composite Polymerization — 195
Bacterial CNF — PEDOT Composite Polymerization — 196
CNC Acid hydrolysis PEDOT, PANI, Composite Polymerization — 197
PPy
CNC Acid hydrolysis Thiophene Electrode Polymerization + chemical Up to 1000 Ω □−1 119
Au, Ag, Pt, Cu synthesis
Metallic particles
CNF Homogenizer Silver Thin film Chemical synthesis 5 S cm−1 117
Ag(NH3)2
CNC Acid hydrolysis Silver, copper, — Chemical synthesis — 113
gold
CNC Acid hydrolysis Copper — 1. Silica coating — 111
2. Mix with AuHCl4
Bacterial CNF — Gold Biosensor Chemical synthesis — 115
CNC Acid hydrolysis Silver — Chemical synthesis — 118
Hybrid
TEMPO NFC Domestic blender PPy/silver Electroconductive Polymerization + chemical 10−5–10−6 S cm−1 120
antimicrobial synthesis with AgNO3
composite
conductive polymer on the CNC template, a similar trend was has also been reported for producing conductive films with a
reported by Casado et al. using direct polymerization on CNC conductivity of 2 S cm−1.95 Surface coverage of nanocellulose
where composites with a higher electrical performance were using direct oxidative polymerization has been successful with
obtained when using PANI coated CNC compared to neat Luong et al. demonstrating a uniform coating of PANI on
PANI.91 Direct oxidative polymerization of PANI onto the nano- CNF.96 Different ratios of PANI to cellulose were investigated to
cellulose surface has been implemented for applications such determine the morphology and the mechanical and electrical
as flexible conductive films92,93 and addition of an electrical properties of the composite paper. Electrical percolation
stimulus.94 An electro-chemical polymerization on a CNC film threshold was found at 4.57 vol% of PANI and conductivity
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Fig. 5 Examples of nanocellulose applications for conductive inks: as a template for (a) conductive PANI polymer (left) compared to neat CNC
(right)191 and (b) for silver nanoparticles on oxidized CNF with associated I–V curve;117 (c) as a dispersing agent for carbon nanotubes in a suitable
inkjet ink127 and (d) as a binding agent for PPy particles to produce CNF–PPy films (right) compared to neat crackled PPy films (left).132
was in the range of 2.6 × 10−5–1.8 S cm−1 depending on the vol% as compared to that of CNC (2.31 vol%) for the pristine
PANI content. Interestingly, stable concentrations of PANI : PEDOT-PSS composite. Thus, CNC acts as an effective scaffold
CNF suspensions were obtained at a concentration of 1 mg ml−1 for the PEDOT-PSS polymer, which preferentially organizes
in the pH range of 1–7 as opposed to 2–3 for PANI par- itself depending on the CNC network. The templating mechan-
ticles alone, emphasizing the increase in the stability of CNF : ism of CNC by PEDOT-PSS is not yet fully understood.
PANI suspensions. Thus, CNF can also act as a stabilizing However, a decrease in absorbance of CNC–PEDOT-PSS solu-
agent for the PANI polymer and even though the authors have tion as a function of time suggested an adsorption of
used the suspension for processing composites, the enhanced PEDOT-PSS onto CNC.
stability and conductivity might be of interest for conductive In conclusion, these strategies allowed the preparation of
ink applications. conductive films and some suspensions could be used for
Fewer papers dealing with the PEDOT-PSS conductive printing processes. The main drawbacks of such in situ
polymer have been reported. Mendez et al. were among the polymerization methods lie in controlling the polymerization
first to report the use of CNC for synthesizing conductive for obtaining a continuous layer free of aggregates and in
PEDOT-PSS nanorods.97 Based on the studies of other conduc- releasing the adsorbed polymer layer.
tive polymers, they examined the oxidative polymerization of 3.1.2 Metallic particles. Numerous studies have taken advan-
the EDOT monomer onto CNC by implementing two different tage of nanocellulose surface chemistry for synthesizing metallic
methods. In the first method, polymerizations with iron(III) particles on the nanocellulose surface for antibacterial,99–102
p-toluenesulfonate-doped PEDOT-PSS using methanol : water bio-imaging,103 and catalytic104 applications or for enhancing
as the solvent were investigated, which led to the formation of the mechanical and thermal properties of the polymer compo-
PEDOT aggregates on the nanocellulose surface despite modi- site.105 A very recent review by Kaushik et al. gave an exhaustive
fying the cellulose : EDOT and the solvent ratio. The aggregate overview of the use of nanocellulose as a support for metallic
formation was probably due to the interaction between iron(III) particle synthesis.106 However, unlike in the case of conductive
p-toluenesulfonate and CNC. Polymerization using PSS as the polymers, templating of nanocellulose using metallic particles
counter ion and polystyrene sulfonate as the main oxidative for conductive applications has been less examined probably
agent was then investigated. This second strategy resulted in a due to the difficulty in obtaining a percolated network
uniform polymerization without the formation of aggregates. between the metallic particles. Although several studies have
Conductive properties were examined for different cellulose : reported on the synthesis of organized conductive metallic par-
EDOT ratios and the optimal ratio led to a cast film with a ticles on the nanocellulose surface,107–111 the conductivity of
surface resistivity of 97 Ω □−1. Tkalya et al. used a CNC– the network has not been reported.
PEDOT-PSS system for producing conductive fillers for the However, attempts to determine the set of experimental
polystyrene matrix. In this case, the templating was carried out conditions for achieving the best coverage of the nanocellulose
not by using in situ polymerization, but by the adsorption of surface by the synthesized metallic particles were investigated.
PEDOT-PSS onto CNC.98 The use of CNC as a template resulted Metallic particles are usually synthesized by sol–gel chemistry
in the lowering of the electrical percolation threshold to 0.42 methods using metallic salt as a precursor followed by a
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chemical or thermal reduction. Mechanisms involved in the The hybrid system of conductive polymer/metallic particles
particle synthesis are the classical nucleation and growth of has also been studied119,120 and no improvements in the con-
the metallic particles. Many parameters influence the particle ductivity compared to that of the neat metal or the polymer
synthesis and the coverage. Padalkar et al. were among pio- network was observed. As summarized in Table 1, most of the
neers with a study and a patent deposition112 on the synthesis published reports using the templating method on nanocellu-
of different conductive metallic particles113 (such as gold, lose focus on conductive polymers for producing conductive
copper, and silver) as well as semi-conducting particles114 composites. Metallic materials are less commonly used due to
(such as cadmium sulfide and zinc sulfide) using tunicate the difficulties in controlling the synthesis and obtaining an
CNC as a template. Sol–gel parameters such as the reaction electrical percolating network pathway. Most of these conduc-
time, the pH of the suspension, and the concentration of the tive applications focus on composites and industrial appli-
reactants were evaluated. Zhang et al. reported the optimum cations as conductive inks have not been reported so far.
conditions of the pH and the surfactant concentration for pro- However, we believe that nanotemplating on both CNF and
ducing gold nanoparticles on bacterial cellulose nanofibers.115 CNC would be efficient in producing conductive inks with
The abovementioned synthesis parameters and the inter- a lower functional solid content and a certain level of
actions of metallic ions with the cellulose surface affected the transparency.
templating coverage. Electrostatic interactions between the
positively charged metal ions and the negatively charged nano- 3.2 Capping and nucleating agents for metallic particle
cellulose were not enough for ensuring the complete coverage synthesis
of the cellulose surface and an increased particle organization Metallic nanoparticles are one of the most widely used raw
on using surfactant molecules was observed. Padalkar et al. materials in formulating conductive inks. However, the control
reported the preferential deposition of different metallic par- of particle size remains challenging and surfactant molecules
ticles on CNC obtained from tunicates using the cetyltri- are usually needed. Recently, the use of nanocellulose as both
methylammonium bromide (CTAB) surfactant during the enhancing and capping agents during the chemical synthesis
synthesis of metallic particles. In a similar manner, Zhang of metallic particles121,122 has been reported. Although the use
et al. used polyethyleneimine and demonstrated a higher cov- of nanocellulose with the aim of controlling the synthesis of
erage of gold particles on the CNF fibers.115 Mechanisms metallic particles has not been reported, this section details
involved in the higher coverage are not yet fully understood. an interesting sustainable way for producing metallic particles
However, the interactions between the hydroxyl groups of cel- with controlled size, which may be used as raw materials in
lulose and the ionic ammonium group of the surfactant seem the conductive ink formulation.
to play a crucial role. As previously mentioned, many research studies have used
Instead of using additional molecules or polyelectrolytes for oxidized nanocellulose for anchoring metallic ions on the cel-
enhancing the metal ion–nanocellulose interactions, some lulose surface and enhanced the amount of synthesized par-
researchers have focused on introducing new functional ticles.99,104,116,123 Charge density of nanocellulose seems to be
groups on the cellulose surface by oxidation. Presence of car- a key parameter in the synthesis of metallic nanoparticles,
boxylate and aldehyde groups has been reported to enhance even though few studies have focused on the comprehensive
the metallic particle synthesis on the nanocellulose mechanisms of capping and nucleating actions of nanocellu-
surface.108,116 Ifuku et al. suggested the occurrence of an ion lose during the metallic particle synthesis. Lokanathan et al.
exchange between the Na+ counter ion of the carboxylate studied the mechanism of silver nanoparticle synthesis in the
groups and Ag+, resulting in higher immobilization of silver presence of silver nitrate, sodium borohydride and CNC.122
nanoparticles on the oxidized nanocellulose surface.116 Wu They showed that despite a decrease in the particle size, the
et al. synthesized silver particles on CNF, which was oxidized number of synthesized silver particles increased on increasing
by periodate to introduce aldehyde groups for increasing the the CNC concentration, suggesting the nucleation controlling
interaction between silver and cellulose.117 Scanning trans- action of CNC. The ionic interactions between the negatively
mission electron microscopy (STEM) analysis indicated a charged sulfate groups on the CNC surface and the silver
better ability of the periodate oxidized CNF in reducing the nanoparticles were assumed to cause a capping action of CNC.
Ag+ ion via a thermal treatment compared to that of the neat Thus, the sulfate group impact on the synthesis of silver nano-
CNF. Fig. 5-b illustrates the templated CNF along with the elec- particles was investigated. Surprisingly, an optimum in the
trical properties of the system. The intensity–voltage curve surface concentration of sulfate groups was obtained, minimiz-
revealed a nearly ohmic behavior with a conductivity of about ing the synthesized silver particle size dispersion. High
5 S cm−1. Even though this value is far less than the bulk silver amounts of sulfate groups may hinder the hydroxyl–metal par-
conductivity value (about 6 × 106 S cm−1), the formation of a ticle interactions, reducing the control on the nucleation and
percolated metallic nanoparticle thin film onto the CNF growth processes. A very small amount of sulfate groups
surface using a metal bio-templating method was first reported would, on the contrary, induced aggregation of CNC leading to
in this study. More recently, Hoeng et al. proposed optimum a loss in the capping ability. Uddin et al. followed this investi-
conditions of CNC oxidation for a better longitudinal gation by carrying out a comprehensive study on the role of
covering.118 carboxylate groups in the silver nanoparticle synthesis using
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TEMPO oxidized CNC. The CNC charge densities obtained by Fig. 5-c. This study demonstrated, for the first time, the ability
modifying the reaction time and varying the carboxyl content of nanocellulose to be used as a dispersant in conductive
between 0 and 1.5 mmol g−1 were examined. A combination of inkjet inks. Similar mechanisms were assumed by Li et al.129
transmission electron microscopy (TEM) and UV-vis spectral in the dispersion of 2D materials, such as molybdenum di-
analyses indicated that the presence of carboxyl groups sulfide (MoS2) and boron nitride (BN), using CNF. TEMPO
enhanced the CNC ability to stabilize the silver nanoparticles, CNF were used to stabilize the MoS2 and BN flakes by mixing
leading to lower size dispersion with an increased number of CNF with mineral particles followed by centrifugation to
small particles. By examining the UV-vis kinetic measure- recover a stable supernatant suspension. The affinities
ments, the nucleation rate was found to be inversely pro- between CNF and 2D materials are supposed to occur due to
portional to the carboxyl content of CNC, suggesting that the the hydrophobic–hydrophobic interactions between the hydro-
action of TEMPO CNC occurs during the growth phase as a phobic face of CNF and hydrophobic flakes of MoS2 and BN.
capping agent rather than during the nucleation phase as a Stable suspensions were obtained due to the electrostatic
nucleation enhancer. However, Hoeng et al. have recently repulsive forces of CNF and additional steric hindrance as in
suggested that the capping action of TEMPO CNC for silver the case of CNT mentioned above. In addition to stabilizing
nanoparticles was effective in both the nucleation and growth properties, the authors also reported higher mechanical pro-
phases.118 Evaluation of both the size and amount of syn- perties of CNF–MoS2 and CNF–BN composites compared to
thesized silver particles, with CNC at different charge den- that of other MoS2 and BN composites reported, and these
sities, indicates that the carboxylate groups acted as a composites were successfully integrated into sodium-ion bat-
nucleation enhancer and a capping agent. teries. Recently, the stabilizing properties of nanocellulose
Even though the capping mechanism of CNC is not fully have proved their effectiveness in industrial applications
understood, the charged groups on the nanocellulose surface (two announced patents by a company (Poly-Ink)) by using
are found to be essential for controlling the synthesis of met- CNF and CNC for obtaining stable suspensions of silver
allic particles. Although only CNC action was studied in the nanoparticles.130,131
comprehensive previous publications, CNF were also used for The use of nanocellulose as a binder in ink formulations is
producing metallic particle sizes. However, although no less common. However, some studies reported enhanced pro-
specific studies have evaluated the role of CNF in metallic par- perties in conductive coating when using CNF. Sasso et al.
ticle synthesis, the tight and bundled CNF network as well as studied the use of CNF mixed with PPy suspensions in
their easier aggregation might limit the capping action as com- forming conductive films and coatings, as compared to pure
pared to that of CNC. Recent studies demonstrate the ability of PPy suspensions. A binding action of CNF132,133 by obtaining a
nanocellulose in controlling the metallic particle size distri- homogeneous film when using CNF in the suspension formu-
bution. Nanocellulose can thus be regarded as a renewable lation was observed (Fig. 5-d). Pras et al. reported the ability of
and greener alternative to the surfactant molecules commonly mixed copper/CNF slurry to be processed by filtration, coating
used for this purpose. and screen printing methods for conductive applications.134
While films obtained by vacuum filtration were conductive
3.3 Stabilizing and binding agents without any treatment, resistive patterns were obtained by
Good dispersion of hydrophobic conductive particles, such as printing and coating methods. Zinc addition combined with a
graphene and carbon nanotubes, is usually achieved by using calendering and corona treatments on the printed films
surfactants or chemically modifying the particle surface. resulted in the formation of a conductive pattern with a con-
Recently, the potential for using nanocellulose as a dispersing ductivity of 95 S m−1 and 570 S m−1 for coated and screen-
agent for organic and inorganic particles has been reported printed films, respectively. These results indicated the proces-
on. Dispersion of inorganic particles using CNF was reported sability of the CNF/copper suspension by coating and printing
in the case of titanium dioxide particles (TiO2) for producing to obtain conductive patterns.
opaque CNF films.124 Among conductive particles, the stabiliz- To conclude, CNC and CNF seem to be very promising in
ation of carbon nanotubes has been especially studied.125–128 producing highly conductive organic and inorganic inks even
Mechanisms involved in the stabilization of carbon nanotubes though only a few studies have used nanocellulose for achiev-
are not yet fully understood but Oliver et al. recently reported ing this goal. Most of the published papers focus on the use of
that interactions between the hydrophobic face of the (200) nanocellulose as substrates.
crystalline plane of CNC and the hydrophobic carbon nano-
tubes could occur. These interactions combined with the
electrostatic repulsions of negatively charged CNC result in a 4. Nanocellulose as a substrate for
stable dispersion of carbon nanotubes in water. Following printed electronics
their study, Koga et al. described the ability of TEMPO oxidized
CNF to stabilize single wall carbon nanotube suspensions.127 One major breakthrough in printed electronics was the possi-
They used the hybrid suspension for manufacturing conduc- bility of designing flexible devices. Flexible and transparent
tive films by casting and inkjet printing on the PET films and substrates, such as paper and polymer films, constitute key
obtained a conductivity of about 1.2 kΩ □−1 as illustrated in materials in the development of the future flexible electronic
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devices like solar cells, screens, and sensors. However, sub- with the nanopaper. The authors highlight the higher ability
strates for printed electronics have specific requirements. of CNF nanopaper to withstand high sintering temperatures
Printed electronics require a smooth and non-porous substrate (up to 200 °C) as compared to that of the plastic substrate,
in order to avoid cracks and discontinuities in the printed which was confirmed by thermogravimetric analysis. Thus, the
films. Ink infiltration owing to the substrate structure or suitability of CNF nanopaper for the printing of conductive
roughness would increase the probability of conductive path tracks was comparable to the polymer film. Similar results
breakage, thereby reducing the electrical conductivity. In were obtained by Nogi et al. by mask printing of silver nano-
addition, sintering of the samples at high temperatures (up to wires on traditional paper137 and inkjet printing of silver
250 °C) might be needed in some applications and the sub- tracks on plastics138 as compared to CNF nanopaper. Printing
strate should withstand such high temperatures without on traditional paper resulted in a higher resistance compared
undergoing deformations. to printing on plastic films but similar conductivity values
Nanocellulose films, which fulfill all these requirements were obtained when printing silver nanowires on the CNF
while being recyclable, have a great potential as a substrate in nanopaper. Even higher conductivities were obtained with the
printed electronics. The different uses of nanocellulose sub- nanopaper as compared to plastic substrates with the inkjet
strates for printed electronics are summarized in Table 2 and silver tracks.
more details are provided in the following sub-sections. As can The abovementioned results can be attributed to the tightly
be seen, most of the nanocellulose substrates for printed elec- closed structure and smoothness that can be obtained with
tronics are based on CNF rather than CNC. Therefore, we the CNF structure. Oxidation of nanocellulose is known to
focus on CNF based substrates and their properties. strongly affect the nanocellulose dimensions, leading to a
Nanocellulose substrates can be divided into two categories: highly entangled network as can be seen in Fig. 3. Chinga-
(i) nanocellulose for enhancing the substrate surface pro- Carrasco et al. were the first in 2012 to evaluate the possibility
perties and (ii) nanocellulose for flexible and transparent of using 100% CNF film as a substrate for printed electronics
films. and studied the effects of CNF treatment on the produced
films.139 Conductive tracks have been printed on three kinds
4.1 Nanocellulose for enhancing the substrate surface of CNF films obtained by casting evaporation: CNF with no
properties treatment, carboxymethylated CNF and TEMPO CNF. The
CNF exhibit the required properties for a printed electronic inkjet printing process was chosen due to the low material
substrate. Numerous studies have demonstrated that CNF consumption and the non-contact approach offered by this
films, also called nanopaper, possess better smoothness and technique. The higher porosity of the untreated CNF network
lower porosity than the traditional paper, approaching as compared to that of TEMPO-CNF induced ink absorption in
polymer film properties.135 Hsieh et al. emphasized the advan- the untreated CNF substrate. Therefore, a higher printing
tages of using CNF nanopaper rather than the traditional resolution was obtained when printing on the TEMPO-CNF
papers for producing conductive lines using two different substrate rather than the untreated CNF. However, lines
deposition techniques, namely sputtering and inkjet print- printed on the TEMPO CNF films exhibited ink spreading due
ing.136 Two different functional inks were printed: a silver ink to the high surface energy. As the TEMPO-CNF film was also
and a metal organic deposition ink (MOD). The sputtering brittle in nature, carboxymethylated CNF films treated with
process was performed on a plastic polyimide substrate, tra- hexamethyldisilazane (HMDS) were used for reducing the
ditional paper and CNF nanopaper. Resistance of the printed surface energy and obtaining a more flexible film. In this case,
line on the traditional paper was quite high (6430 Ω) while a good printing resolution was achieved with the treated
that on the CNF substrate was 180 times lower (34 Ω). This carboxymethylated film (conductivity of 3 Ω □−1) owing to the
drastic decrease in the resistance can be attributed to the low porosity and smooth surface of the treated CNF film.
lower porosity of the CNF nanopaper as compared to that of While 100% cellulose films offer advantages in terms of
the traditional paper, resulting in a reduction in ink infiltra- sustainability, some studies evaluated the possibility of using a
tion and cracks as can be seen on the photographs of printed blend of mineral fillers and CNF for developing substrates
lines in Fig. 6-a. However, the resistance was still higher than suitable for printed electronics. Ketoja et al. studied the effect
that of the printed line obtained on a polyimide substrate of filler addition (kaolin and precipitated calcium carbonate –
(1 Ω) even when increasing the sputtering time. The inkjet print- 50 to 90 wt%) on the roughness and porosity of the
ing process was evaluated following a similar protocol. Similar CNF films for developing a suitable substrate for printed
results as in the case of sputtering for the traditional paper electronics.140–142 A combination of kaolin fillers with the CNF
were obtained, with an infiltration of both inks (silver and suspension in addition to calendering of the film leads to a
MOD) in the substrate leading to no conductivity. However, roughness similar to that of a photo paper. Printing of silver
the conductivity obtained with inkjet on a nanopaper was ink on this nanopaper resulted in a similar conductivity to
similar to that obtained on the polyimide substrate (i.e. ≈1 Ω) that on PET (0.3 Ω).140 A better understanding of the filler
as can be seen from Fig. 6-a. This superior conductivity network was provided by simulating the packing of different
obtained with inkjet printing on the nanopaper might be fillers. Porosity at the sub-microscale was found to largely
attributed to the additional sintering step that is only possible affect the conductivity of the printed tracks and, therefore, the
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Table 2 Electronic devices integrating nanocellulose
Nanocellulose Nanocellulose
type process Nanocellulose treatment Nanocellulose use Application Conductive process Conductive material Ref.
Nanocellulose as a substrate for printed electronics

CNF Commercial Mixing with mineral fillers Substrate Roughness/porosity Inkjet printing Silver ink 2000–13 Ω 141
simulation for
conductive line
CNF Commercial Mixing with mineral filler Substrate Conductive lines Inkjet printing Silver ink 0.03–1.77 Ω 140
CNF Water-jet system — Substrate Conductive lines - Sputtering Gold, silver 1–34 Ω 136
- Inkjet printing
- Metallo-organic
decomposition (MOD)
CNF Grinder Blend with silver NP + silver High dielectric Antenna Inkjet printing Silver ink 164
nanowires substrate
CNF Water-jet system — Substrate Foldable antenna Mask printing Silver NW 0.16 Ω 137
CNF Microfluidizer TEMPO oxidation + mix with Substrate RFID printing Gravure printing Silver ink 0.3 Ω □−1 153
glutaraldehyde
CNF Grinder — Substrate Conductive lines Inkjet Silver ink 2–5 Ω □−1 138
CNF Homogenizer TEMPO Substrate OLED Meyer rod coating CNT 185
Bacterial CNF — — Substrate OLED Process for OLED — 184
CNF Grinder Acetylation Substrate OLED Process for OLED ITO 144
CNC Acid hydrolysis Mixing with glycerol Substrate OLED Process for OLED — 186
CNF Grinder — Substrate Transistor Lithography/spin — 165
coating
CNC Acid hydrolysis — Dielectric layer and Transistor Lithography — 167
(2.5 N H2SO4, 45 °C, substrate
130 min)
CNF Homogenizer TEMPO Substrate Transistor Meyer rod coating — 166
CNF — — Substrate Transistor Lithography — 198
CNF Grinder CNF, TEMPO CNF, Substrate Printed transistor Inkjet Silver ink 2–5 Ω □−1 139
carboxymethylated CNF
CNC Acid hydrolysis Mixing with glycerol Substrate Solar cell Shadow-mask of Ag — 156,
200
CNF Water-jet system — Substrate Transparent Vacuum filtration/ Silver NW/CNT 12–70 Ω □−1 155
conductive electrode coating/spin coating
CNF Microfluidizer TEMPO oxidation + mix with Substrate Tunable haze Silver ink — 151
TEMPO cellulose microfibers substrate + transistor
CNF Homogenizer Carboxymethylation Substrate Transparent electrode Coating, sputtering Silver NW/ITO/CNT 148
CNF Homogenizer — Substrate Transparent electrode Extrusion of mixed Silver NW 1 Ω □−1 178
silver NW/CNF
Nanoscale, 2016, 8, 13131–13154 | 13143
CNF Domestic blender TEMPO – mix with glycerol Substrate Conductive Film Spin coating PEDOT-PSS 201
CNF Microfluidizer TEMPO Substrate Electronic Transfer printing — 157
components
Bacterial CNF — — Conductive Supercapacitor Vacuum filtration CNT 7 Ω □−1 172
electrode
Nanocellulose for printed electronics devices
Publications
CNF Water-jet system — Conductive Solar cell Rod coating/casting Silver NW Up to 17 Ω □−1 199
electrode
Bacterial CNF — — Conductive Battery Template PPy 173
electrode polymerization of PPy
Review
Bacterial CNF — Cationic: Conductive Supercapacitor Template PPy 175,
3-glycidyltrimethylammonium electrode polymerization of PPy 176,
chloride + NaOH. Anionic: TEMPO 202
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Review
Table 2 (Contd.)
Nanocellulose Nanocellulose
type process Nanocellulose treatment Nanocellulose use Application Conductive process Conductive material Ref.
CNF Homogenizer TEMPO Conductive Supercapacitor Dipping in conductive — 177

electrode polymer
−1
CNF Microfluidizer TEMPO Carbonized Li-ion battery Extrusion of Graphene oxide 649 S cm 203
conductive fibers conductive fiber
for anode
CNF Microfluidizer — Conductive Li-ion battery Mixing with graphite — 168
electrode
CNF Microfluidizer — Reinforcement for Li-ion battery — 0.3 S cm−1 169
electrolyte
membrane
CNF Microfluidizer — Filler in polymer Li-ion battery — — 204
membrane
CNF Refiner + — Binder Li-ion battery Spray Graphite/carbon black 170
homogenizer
CNF Homogenizer TEMPO Dispersant + matrix Battery Spray coating/ MoS2 Molybdenum 129
filtration/casting disulfide
CNF Refiner + — Binder Conductive coating Screen printing/ Commercial copper 134
homogenizer coating/filtration particles
CNF Grinder TEMPO oxidized Ink – dispersing Conductive patterns Inkjet CNT 127
agent
CNF Microfluidizer — Aerogel Conductive Aerosol transfer CNT 73 Ω □−1 205
transparent film
CNF Commercial — Transferred layer Electrochromic paper Transfer Silver NW 0.75–630 Ω □−1 206
CNF — TEMPO + NaIO4 oxidation + Functional layer Flexible memory Electrochemical — 160
decoration with AgNP reaction of silver
CNF Microfluidizer Anionic (carboxymethylation) Functional layer Electronic sticker for Casting PEDOT-PSS 163
removable layer
CNF Commercial — Matrix for crumble Strain sensor Embedding Crumbled graphene 162
graphene
CNF Grinder — Matrix Transparent Vacuum filtration Silver NW 70–4 Ω □−1 145
conductive electrode
CNF Microfluidizer — Electrolyte support Aerogel membrane for Screen printing — 182
aerogel dye solar cells
CNF Grinder — Water transfer decal Electronic decal Shadow-mask of 10–40 Ω 159
This journal is © The Royal Society of Chemistry 2016
gold/modified- coating
of silver
CNF Microfluidizer TEMPO Pressure sensitive Electroactive Spray deposition CNT 161
nanopaper transparent paper 2 kΩ cm−2
CNF Refiner + Cationic: Ionic transport Nanopaper based Drying — 183
homogenizer 3-epoxypropyltrimethylammonium diode
chloride + NaOH.
Anionic: oxidation NaIO4 +
sulfonation NaHSO3
Patent
CNF Grinder — Binder Li-ion battery Mixing with Carbon 171
conductive material
CNF — — Porous separator Battery — — 207
Nanoscale
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Fig. 6 Examples of CNF substrates for printed electronics: (a) comparison of sputtered silver lines on paper (up) and nanopaper (down) with the
associated electrical resistance;136 (b) comparison of CTE value for pure CNF and CNF acrylic resin composites;145 (c) haze-tunable transparent CNF
substrate according to the CNF amount compared to PET151 and (d) illustration of fungal degradation of the nanocellulose substrate for flexible
transistors.198
best fillers for CNF nanopaper should provide a low porosity CTE of the composite was observed: the addition of CNF with
rather than a high smoothness.141 a high Young’s modulus decreased the CTE of the matrix with
a low Young’s modulus while increasing the flexibility of the
4.2 Nanocellulose as transparent flexible substrates composite. The concentration of CNF in the final composite
As nanocellulose substrates offer several advantages owing to was fixed at 30–40 wt% and the impregnation processing time
their surface properties in the printing of conductive tracks, was quite high (12 h). Nevertheless, the obtained flexible trans-
nanocellulose films are promising for processing transparent parent substrate was suitable for depositing conductive
conductive flexible films either by coating or by impregnation materials for OLED production. Recently, Zhang et al. used
of the composites. Currently, plastic substrates are mostly similar impregnation methods in acrylic resin silver nano-
used owing to their flexibility and transparency, the simplicity wires/CNF to obtain similar results145 (Fig. 6-b). However, the
of the processing methods and their low cost. However, poor conductive electrode was directly produced by vacuum fil-
thermal stability is the limiting factor in using plastic tration of silver NWs in CNF sheets followed by impregnation
substrates. in the resin. The resin impregnation improved the silver NW
The flexibility, thermal stability and biodegradability of adhesion, surface roughness, and the total transmittance of
transparent nanocellulose substrates provide an alternative to the composite as compared to the neat silver NW/CNF film.
plastic substrates. This section gives an overview of the pro- The best opto-electrical performances were obtained with a
perties of such substrates for printed electronics. Applications density of 134 mg m−2 of silver nanowires (T% = 85%, Rsh =
with associated processes involved in using such substrates are 6 Ω □−1) making it suitable for opto-electronic device appli-
reported in Table 2. cations. While thermal expansion is improved when using
Yano et al. first reported the use of CNF in flexible elec- CNF, Nogi et al. demonstrated an increased stability of
tronics for the deposition of an OLED, on the bacterial CNF thermal transparency of CNF as compared to that of plastic
composite in 2008 and on the wood CNF composite in substrates.146
2009.143,144 The substrates were not made with 100% CNF In addition to thermal stability, another critical parameter
films but by the impregnation of dried CNF sheets in a trans- for transparent substrates in printed electronics is the haze.
parent resin matrix. Since OLED processes require substrates The haze property is directly linked to the light scattering of
with a low coefficient of thermal expansion (CTE), they aimed the substrate and should be different according to the targeted
at reducing CTE as compared to the plastic substrate while application. Haze is defined as the percentage of light trans-
maintaining the transparency of the matrix. A decrease in the mitted through a specimen that deviates the incident light
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beam by a scattering of more than 2.5° angle on average.147 parameter when using such films in applications like OLED
Recently, Hu et al. were the first to compare the light scattering and displays, where the conductive layer should not damage
of transparent CNF films, plastic films and traditional the overlying layer.
paper.148 The angular reflection and transmission were
measured and compared with those of the plastic substrate. 4.3 Sustainability of nanocellulose substrates
CNF substrates exhibited both transmitted and reflected light A major advantage of using 100% cellulose films is the sustain-
scattering, as opposed to the plastic substrate, which could be ability of the devices. While several studies have focused on
attributed to the nanoscale diameter of the CNF leading to a the properties and performances of the nanocellulose sub-
high porosity structure, as compared to the dense plastic substrates, some researchers have evaluated the sustainability of
strate. As the dimensions of the fibers play a major role in such electronic components. Zhou et al. studied the possibility
light scattering,149,150 a much higher light scattering of the of recycling a transparent smooth CNC substrate used in a
transparent CNF substrate was obtained. Thus, CNF substrates solar cell device.156 Recycling was done by a simple immersion
can scatter light (unlike plastic substrates) while being trans- of the solar cell in water leading to the swelling and dis-
parent (unlike traditional papers). The diameter dependence solution of the CNC substrate. The solar cell components can
of the scattering fibers has been used for producing functional then be separated by washing and filtration. This recycling
substrates with a tunable haze by mixing TEMPO oxidized process is very easy and green. They also burned the solar cell
microfibers and CNF.151,152 The effect of tunable haze is illus- to turn the cellulose substrate into ashes at a flame tempera-
trated in Fig. 6-c. Haze of the film was tuned while maintain- ture and recover the metal components. Recently, Jung et al.
ing its transparency and the flexibility by introducing different demonstrated a new method for the degradation of nanocellu-
amounts of CNF (from 20 to 80 wt%) into the TEMPO oxidized lose substrates by biological degradation.157 The electronic
microfiber suspension. The haze was directly linked to the components consisted of CNF coated epoxy substrates. Fungus
ratio of CNF to cellulose microfibers introduced into the film degradation was evaluated for 100% CNF films and epoxy
due to the high diameter of the microfibers. The high dimen- films and was found to be efficient for both films. After an
sion of the cellulose microfibers causes light scattering and a extended time (84 days), the encapsulated electronic com-
high haze while smaller diameters induce a low haze. Sub- ponent can be recovered. In the same way, Seo et al. studied
strates with haze varying from 18% to 60% have been pro- the fungal degradation of a transistor based on a CNF sub-
duced and successfully integrated into devices such as strate as can be seen in Fig. 6-d.158
transistors and solar cells. Sustainability of nanocellulose substrates has been proven
Although the optical, surface and thermal properties of for CNF and CNC based electronic components, offering a
CNF substrates have been extensively studied, a few papers promising way to replace plastic and glass substrates.
have focused on other important properties such as yellowing However, the performances of the electronic components inte-
or water swelling of the CNF substrate. The shape stability grating nanocellulose inks and substrates are still difficult to
against water is quite important in avoiding cracks in the con- compete with the conventional electronics.
ductive path upon drying of the aqueous conductive inks. Hu
et al. mentioned this swelling problem in printed electronic
applications and developed a transparent and stable CNF sub- 5. Applications of nanocellulose in
strate using cross-linking agents.153 The obtained substrate printed electronics
was transparent and stable when immersed in water, exhibit-
ing a swelling of only 33 µm against 6 mm for the neat nano- Papers dealing with the integration of nanocellulose in flexible
paper. Yellowing of transparent nanopaper has been electronics devices and the associated applications are sum-
mentioned recently by Yagyu et al.154 marized in Table 2. Nanocellulose in electronic devices is
Koga et al. compared vacuum filtration, coating, and spin mostly based on CNF rather than CNC and is used as a flexible
coating methods on the CNF transparent nanopaper.155 (transparent) substrate. This is probably because the CNC
While coating and spin coating are widely used in the depo- films are more brittle in nature than CNF films, making it
sition of conductive materials, vacuum filtration cannot be more suitable for flexible substrates. It is worth mentioning
implemented on traditional substrates. The nanoporous CNF that the brittleness of the CNC film can be solved by the
film acts as a filter for depositing silver nanowires and CNT. addition of plasticizers. In addition, the CNC iridescence pro-
The vacuum filtration method provided the best results in perty might provide an interesting additional functionality
terms of conductivity in the case of silver nanowires and combined with conductive application for security or anti-
CNT as compared to coating and led to a decrease in the counterfeiting applications.
roughness of the conductive layer due to the embedding of Major applications of nanocellulose in organic electrical
the conductive structure. This embedding likely occurs due devices and conductive printed lines and less common appli-
to the hot pressing drying on the wet CNF substrate while cations have been examined. Daniele et al. used the CNF sub-
coating was performed on dry substrates. This decrease in strate for developing an electro-active water slide decal using
the roughness (30 nm for silver NW films obtained by the pullulan film as a water-soluble support and the on-top
vacuum against 75 nm for coated films) is an important CNF layer as a transparent transfer layer.159 Gold and silver
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Fig. 7 Examples of nanocellulose integration in printed electronics devices. (a) A transparent CNF–pullulan circuit board with LEDs on a full-sheet
and the same CNF–pullulan-LEDs circuit excised and transferred onto a flower;159 (b) transparent CNF nanopaper based OTFT array and photo-
graphs of the OTFT array in bending and folding states165 and (c) foldable conductive nanopaper for LED lighting (up) and foldable solar cells
(down).199
tracks were deposited onto this double layer support and were Gravure printing has been implemented owing to its high
successfully transferred onto a finger and onto a biological printing speed and the possibility of using low-viscosity inks.
substrate as can be seen in Fig. 7-a. Conductivity measure- Printing resolution on the CNF substrate appeared to be suit-
ments indicated a high resistance to strain and twist with able and a great wettability and a sheet resistance of 0.3 Ω □−1
effective conductive circuits present even after the transfer. were achieved. Antenna performances were measured for two
This provided the first study on electro-biocompatible devices line resolution and the maximum gain was obtained for a fre-
and their properties (water vapor, oxygen barrier and thermal quency of 683 MHz and the insertion losses were measured to
properties) indicated the suitability of CNF for this appli- be −37 and −38 dB for 100 and 120 lpi resolution, respectively.
cation. The use of cellulose nanofibrils in applications such as Inui et al. used CNF substrates to print antennas using a modi-
electro-memory,160 transparent electro-interactive nanopaper fied CNF substrate with silver nanowires to produce a high
for anti-fake systems,161 strain sensors162 and electronic dielectric constant (k) substrate. This high-k substrate reduced
sticker layers with a reusable functional layer163 has also been the antenna size (17 mm against 30 mm) compared to the neat
investigated. However, this section focuses on the conventional nanopaper without changing antenna optimal performances
applications of printed electronics and the obtained perform- at 2.60 GHz frequency.164
ances using nanocellulose. 5.1.2 Transistors. The low surface roughness and the flexi-
bility of transparent CNF substrates have been exploited for
5.1 Functional printing on nanocellulose substrates the fabrication of flexible thin film transistors (TFTs). Fujisaki
5.1.1 Electronic component printing. CNF substrates, et al. used CNF substrates for fabricating an organic thin film
offering a low porosity and surface roughness with increased transistor (OTFT) and demonstrated improved properties of
thermal properties, are ideal for the printing of conductive the sub-layers owing to the low roughness of the nano-
tracks. Successful printing of electrical conductive lines on paper.165 The dielectric layer, which was spin-coated on the
nanocellulose substrates has been reported.136,139 Hu et al. CNF substrate, exhibited a low surface roughness of about
printed radio frequency identification (RFID) antennas using 1.9 nm leading to a low current leakage (below 10−8 A cm−2).
silver ink on their shape stable CNF transparent nanopaper.153 The crystalline structure of the top spin-coated organic
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semiconducting layer was similar to that obtained on a glass 5.3 Opto-electronic devices
substrate owing to the smoothness of the dielectric layer. The
OTFT performances were comparable with those obtained on Achievement of the best conductivity–optical transmittance
plastic substrates with an on/off ratio of 106–108 and a mobi- combination is still challenging in the development of trans-
lity of 1 cm2 V−1 s−1. Fig. 7-b indicates the device flexibility parent electrodes. Given the benefits of using CNF substrates,
by illustrating a foldable and bendable transistor. No degra- many researchers have tried to combine different conductive
dation in the mobility was observed after the device func- materials with CNF in order to compete with the mostly used
tioned under 1 H of bending. Huang et al. used a CNF material in conductive and transparent layers: indium tin
substrate in an organic transistor device.166 The transparent oxide (ITO). ITO thin films possess excellent properties with a
conductive gate was made with bar coated SWNTs on the sub- light transmittance of more than 75% and a conductivity of
strate and the dielectric layer was spin coated. Flexibility tests about 104 S cm−1 depending on the layer thickness. However,
indicated a decrease of 10% in the carrier mobility. Transistor the sustainability and the price of indium as well as the brittle-
performances of 4.3 × 103 cm2 V−1 s−1 and an Ion/Ioff ratio of ness of the material are the disadvantages of using ITO.
up to 200, respectively, were obtained. Fortunato et al. manu- Opto-electrical properties comparable with those of ITO
factured a flexible field effect transistor using a transparent have recently been achieved by Song et al. Vacuum filtration of
flexible nanocellulose substrate using CNC as both a dielec- a silver nanowire–CNF mixture resulted in a transparent nano-
tric layer and a substrate.167 The obtained performances paper with a sheet resistance of 1.9 Ω □−1 and a transmittance
were comparable with those obtained on a traditional paper of 86%.178 The following sub-sections provide an overview of
with a high mobility of 7 cm2 V−1 s−1 and an Ion/Ioff ratio of the obtained performances of opto-electronic devices integrat-
above 105. ing a nanocellulose based electrode.
5.3.1 Organic solar cells. Kippelen et al. studied the use of
5.2 Energy storage devices CNC as a substrate for organic solar cells.156,179,180 The advan-
Energy storage devices have been developed using CNF sub- tage of using the CNC substrate compared to CNF is the low
strates. Beneventi et al. were the first to exploit CNF for flexible surface roughness. The authors first developed an organic
lithium-ion (Li-ion) battery applications. In this case, CNF was solar cell made of a thermal evaporated modified-Ag layer as a
used either as a reinforcement for polymer electrolyte mem- semi-transparent bottom electrode. The top electrode was pre-
branes168 or as a binding agent for producing flexible and self- pared by evaporating MoO3/Ag onto a photoactive layer. An
standing graphite anodes.169,170 Slurry made using CNF to open circuit voltage (VOC) of 0.65 V, a photocurrent density
perform as a binding agent in Li-ion batteries had also been ( JSC) of 7.5 mA cm−2, a fill factor (FF) of 0.54, and a power con-
patented by Hayashi et al.171 Kang et al. studied the use of bac- version efficiency (PCE) of 2.7% were obtained for the solar
terial cellulose as a substrate.172 Electrodes for supercapacitor cell. Interestingly, solar cells of the same structure using the
were prepared using bacterial CNF substrates with a top trans- glass substrate and ITO exhibited similar values for Voc and FF.
parent CNT conductive layer obtained by vacuum filtration. However, the PCE of 2.7% is still low as compared to the glass/
The ionic liquid based polymer gel was used as an electrolyte ITO solar cell (PCE of 6.6%) and to actual performances of the
between two conductive CNF–CNT electrodes. Electrochemical organic solar cell. This is probably due to the lower transmit-
characteristic measurements indicated a specific capacitance tance of the CNC substrate/Ag compared to that of glass/ITO.
of 20.2 mF cm−2 and the bending test indicated that the super- However, a different solar cell structure made of CNC/
capacitor maintained its performances over 200 bending PEDOT-PSS and a different photoactive layer were explored
cycles when using the CNF substrate and the electrolyte ionic and a PCE of 4% was obtained, similar to the solar cell made
gel. Recently, Wang et al. focused on PPy–CNF electrodes for on a polyethersulfone substrate. Thus, CNC films can be used
battery173 and supercapacitor applications.174–176 First, PPy- in solar cells. Chiappone et al. used CNF as a light-scattering
coated bacterial CNF compressed composites were examined filler to improve the performance of a dye sensitive solar
and were found to be effective in supercapacitor applications, cell.181 CNF were mixed with a light-cured polymer matrix to
even though they were rigid in nature (or not bendable). Flex- produce an electrolyte membrane for the solar cell. Improved
ible graphene oxide covered PPy–CNF has also been tested as a solar cell performances were observed with an increased PCE
supercapacitor electrode and moderate performances were of 60% on the addition of 30% CNF to the membrane partly
obtained (C = 107 F g−1). Recently, Wang et al. tested anionic due to a light scattering enhancement. CNF increased the
and cationic modified CNF–PPy as electrodes. Optimum mecha- device stability by acting as a shield to protect the electrolyte
nical and electrical performances were obtained for a cationic agent. In the same way Miettunen et al. used CNF as an elec-
modified CNF substrate with a capacitance of 122 F cm−3 at a trolyte membrane in dye solar cells by using a porous screen-
current of 33 A g−1, probably due to the highly packed network printed and freeze-dried aerogel for absorbing and transferring
structure of the cationic CNF. While vacuum filtration and the electrolytes.182 Similar solar cell performances were
templating methods have been used for producing the con- obtained to those of the reference cell with this technique. In
ductive structure, a simple dipping into the conductive addition to the transparency and haze, the flexibility of CNF
polymer appeared to be effective in producing flexible CNF nanopaper has recently been exploited for producing foldable
electrodes.177 solar cells (Fig. 7-c).137 The solar cell based on a CNF/silver
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nanowire electrode exhibited a power conversion during and plastics. Regarding these performances, the low roughness of
after folding. the nanopaper is obviously an important parameter allowing
Even though the performances of the solar cells using the printing of conductive tracks with higher printing quality
nanocellulose were found to be lower than those of the conven- and conductivity compared to those obtained on classical
tional organic solar cells, these studies indicate the potential papers and similar to those obtained on plastic substrates.
of using nanocellulose in these applications. The increase in The performances of multilayer devices integrating such sub-
the light scattering and the flexibility of nanocellulose substrates have been more various but some studies reported
strates are promising in the development of flexible solar cells. similar or even increased performances thanks to the use of
5.3.2 Diodes and organic light emitting diodes (OLEDs). A nanocellulosic paper.165,180
paper-transparent diode was developed by Zhang et al. using Few papers have evaluated the cost of the prepared nano-
two types of modified CNFs.183 They used a combination of cellulose substrates. Fang et al. evaluated the cost of nanopaper
anionic and cationic transparent CNF films for creating a p–n but the energy consumption quantification appeared very
junction, which on wetting created a gate for ionic transport complex because of the numerous steps required for produ-
needed for current circulation. This 100% bio-based CNF cing transparent nanopaper.187 Industrialization and the pro-
diode was then sandwiched between two conductive transpar- perties and price of nanocellulose should be considered to
ent ITO electrodes for examining its electrical performances. evaluate the possible breakthrough of cellulose nanopaper in
Moisture content, the thickness of the nanopaper, and the the future market of printed electronics. Table 3 compares the
scanning frequency were found to affect the diode perform- properties of conventional substrates used in printed elec-
ances. For instance, moisture content especially affected the tronics with a 100% CNF nanopaper and a TEMPO-CNF
current rectification of the diode since water was required for (T-CNF) nanopaper. Since the commercial price of nanopaper
ionic transport. is not available, the given prices are based on the raw material
Nogi and Yano reported the manufacture of an OLED in cost of CNF and T-CNF (ranging from 0.7 to 7 $ g−1) for a low
2008 using bacterial nanocellulose composites but the pro- weight nanopaper (20 g m−2). As can be seen from the table,
duced OLED was not flexible.143 Following that, flexible com- the mechanical and thermal properties of nanopaper are
posites of bacterial CNF–polyurethane184 and CNF–acrylic much greater than those of conventional printed electronic
resin144 have been produced for fabricating flexible OLEDs. papers and plastic substrates. Thermal stability is of particular
While these devices were based on composite substrates, flex- interest as the electronic component and conductive tracks
ible OLEDs have also been reported on 100% CNF185 and must withstand high temperatures. However, the price of
100% CNC substrates.186 Zhu et al. compared the potential of nanopaper is much higher compared to the classic substrates.
regenerated cellulose film and 100% CNF as transparent sub- Even though nanopaper exhibits transparency, flexibility and
strates in flexible electronics.185 The top-layer of CNF was improved mechanical and thermal properties, 100% CNF films
made of bar coated CNT and the hole transport layer was are quite expensive. However, the nanocellulose price is
made of evaporated molybdenum oxide and spin-coated expected to decrease with industrialization. Nanocellulose can
PEDOT-PSS while the light-emitting layer was made of green then be used to provide a low-cost, renewable and biodegrad-
polyfluorene. The manufactured OLED on nanopaper able paper with improved properties for printed electronics.
appeared to be stable in the bending state with a similar elec- Hence, other aspects of nanocellulose such as the humidity
trical performance to that of the flat state. sensitivity, yellowing of CNF/CNC films upon drying and their
shelf life should be precisely investigated. Indeed, while the
surface properties and thermal stability of the nanocellulosic
6. Perspectives and conclusions substrate are key advantages of nanocellulosic substrates, the
time-stability of such films might be, above its cost, an impor-
Nanocellulose is promising in the development of renewable tant issue. Indeed, upon considering opto-electrical appli-
and biodegradable devices. As described in this review, nano- cations like OLED or solar panels, a film yellowing or humidity
cellulose is mostly used as a substrate in printed electronics. sensitivity will not be acceptable. Thus ageing, under precise
The majority of the published results compared the conductive conditions, of such nanocellulosic substrates should also be
performances obtained using nanocellulose substrates with studied according to targeted applications. In the same way,
those obtained with conventional substrates like glass and the shelf life of such substrates should be precisely evaluated
Table 3 Comparison of classical printed electronics substrates and CNF based substrates in terms of cost and properties
Young modulus Coefficient of thermal Price

Material Roughness (nm) (GPa) expansion (ppm K−1) Transparency (€ m−2) Scale up
PET ≈0.5–2 (ref. 208 and 209) ≈2–2.5 (ref. 210) 50–200 Yes 4–6 Yes
Printed electronics paper ≈10 (ref. 211) ≈2 — No 6–7 Yes
Nanopaper (NFC) ≈2–40 (ref. 145 and 212) ≈10 (ref. 213) ≈8–13 (ref. 145 and 214) Yes 15–200 No
Nanopaper (T-NFC) ≈0.2–0.5 (ref. 215) ≈10–13 (ref. 23) ≈7.2–7.9 (ref. 154) Yes 200–500 No
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and compared to that of classical printed electronics sub- 6 S. Dong and M. Roman, J. Am. Chem. Soc., 2007, 129,
strates before considering a possible substitution of plastic 13810–13811.
sheets by nanopapers. 7 A. Quarta, A. Ragusa, S. Deka, C. Tortiglione, A. Tino,
Coating of nanocellulose is also one way to decrease the R. Cingolani and T. Pellegrino, Langmuir, 2009, 25, 12614–
final substrate cost while taking advantage of the nanocellu- 12622.
lose properties. Coating of both CNF and CNC has been 8 N. Lavoine, I. Desloges, C. Sillard and J. Bras, Cellulose,
studied for printing applications but no study has evaluated 2014, 21, 4429–4442.
the impact of such coating on functional printing. 9 R. Kolakovic, T. Laaksonen, L. Peltonen, A. Laukkanen
As of now, considering the price of CNF and CNC, we and J. Hirvonen, Int. J. Pharm., 2012, 430, 47–55.
believe that their use in printed electronics should be focused 10 A. Dufresne, Nanocellulose: From Nature to High Perform-
on low-amount additives and high added value applications. ance Tailored Materials, 2012.
The use of nanocellulose in conductive inks can be promising 11 N. Lavoine, I. Desloges, A. Dufresne and J. Bras, Carbo-
in this respect. Indeed, the use of nanocellulose as an additive hydr. Polym., 2012, 90, 735–764.
in ink formulation can be promising given the cost of the con- 12 Y. Habibi, L. a. Lucia and O. J. Rojas, Chem. Rev., 2010,
ventional conductive raw material (10 $ g−1 for silver particles 110, 3479–3500.
and 300 to 800 $ g−1 for silver nanowires for example). Using 13 C. Salas, T. Nypelö, C. Rodriguez-Abreu, C. Carrillo and
their properties for providing green dispersing and stabilizing O. J. Rojas, Curr. Opin. Colloid Interface Sci., 2014, 19, 383–
agents would enhance the suspension stability while only 396.
having a small impact on the ink price. The use of nanocellu- 14 H. Zhu, Z. Fang, C. Preston, Y. Li and L. Hu, Energy
lose as templates is also promising since only a small amount Environ. Sci., 2014, 7, 269.
of nanocellulose is needed to achieve the percolation 15 Z. Shi, G. O. Phillips and G. Yang, Nanoscale, 2013, 5,
threshold. The amount of conductive material needed would 3194–3201.
then be decreased, thereby decreasing the production cost 16 G. Zheng, Y. Cui, E. Karabulut, L. Wågberg, H. Zhu and
when adding a small amount of cellulose materials. L. Hu, MRS Bull., 2013, 38, 320–325.
In conclusion, nanocellulose possesses very promising pro- 17 A. F. Turbak, F. W. Snyder and K. R. Sandberg, US
perties for various applications in flexible electronics ranging 4374702, 1983.
from inks to substrates. High added value applications can 18 K. L. Spence, R. A. Venditti, O. J. Rojas, Y. Habibi and
easily compensate for the actual price of nanocellulose and J. J. Pawlak, Cellulose, 2011, 18, 1097–1111.
not be a restraint for their use in up-scaled applications. Even 19 M. Henriksson, G. Henriksson, L. A. Berglund and
though properties such as ageing and humidity resistance still T. Lindström, Eur. Polym. J., 2007, 43, 3434–3441.
need to be evaluated, the enhanced properties of nanocellu- 20 S. Janardhnan and M. M. Sain, BioResources, 2007, 1, 176–
lose films such as their high thermal stability, high smooth- 188.
ness and high light transmittance are very promising for 21 T. Saito, Y. Nishiyama, J.-L. Putaux, M. Vignon and
developing natural based substrates. A. Isogai, Biomacromolecules, 2006, 7, 1687–1691.
22 O. Nechyporchuk, M. Naceur and J. Bras, Ind. Crops Prod.,
2016, DOI: 10.1016/j.indcrop.2016.02.016.
Acknowledgements 23 A. Isogai, T. Saito and H. Fukuzumi, Nanoscale, 2011, 3,
71–85.
Authors thank the French National Research Agency (ANRT) 24 K. Missoum, M. Belgacem and J. Bras, Materials, 2013, 6,
and Poly-Ink for the financial support. LGP2 is part of the 1745–1766.
LabEx Tec 21 Investissements d’Avenir – grant agreement no. 25 D. K. Miguel Gama, Paul Gatenholm, Bacterial NanoCellu-
ANR-11-LABX-0030) and of the Energies du Futur and PolyNat lose: A Sophisticated Multifunctional Material, CRC Press,
Carnot Institutes. 2012.
26 R. Bardet and J. Bras, in Handbook of Green Materials, ed.
K. Oksman, A. P. Mathew, A. Bismarck, O. Rojas and M.
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Use of nanocellulose in printed electronics:

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