Review
DOI: 10.1002/elan.201500361
Rapid Prototyping of Sensors and Conductive Elements by
Day-to-Day Writing Tools and Emerging Manufacturing
Technologies
Nicol! Dossi,*[a] Fabio Terzi,[b] Evandro Piccin,[c] Rosanna Toniolo,[a] and Gino Bontempelli[a]
Abstract: The growing demand for low cost and easy to
use analytical devices requires the development of relia-
ble and rapid deposition strategies suitable for changing
easily planned designs and applicable to a wide range of
materials for assembling conductive tracks and sensitive
elements. Further important challenges to be pursued are
the possibility of using readily available instrumentation
and reducing power consumption and hazardous chemical
waste. This review provides an overview of the use of
portable day-to-day writing tools, such as pencils and
Keywords: Pencil-drawn sensing devices · Pen-drawn sensitive elements · Conductive filament deposition · 3D printed sensors ·
Direct writing · Contact and non-contact deposition methods
1 Introduction
Nowadays, a great interest is addressed to simple and af-
fordable strategies enabling rapid patterning of conduc-
tive circuits intended for integration in advanced elec-
tronics and sensors. Reduction of the time required for
prototype fabrication, as well as the possibility of rapidly
changing materials and planned designs using at the same
time chemicals and instrumentation characterized by low
cost and reduced environmental impact, are important
features which make deposition processes ideal candidate
for scalable production [1, 2].
Conventional production approaches frequently require
several time consuming fabrication steps, high consump-
tion of energy and reagents, such as conductive materials
to cover the entire substrate surface and chemicals for
etching and/or electroplating, with consequent production
of large volumes of waste [3]. Moreover, sophisticated in-
strumentation and facilities, such as clean rooms managed
by skilled operators and expensive optical masks contain-
ing the layout of planned circuits are needed when micro-
fabrication technology is adopted to achieve high preci-
sion and definition [4].
Alternatively, conductive materials can be profitably
patterned as electrical conducting thin films and tracks
with either indirect deposition methods, which require
the use of additional tools such as masks or screens con-
taining the layout design to be replicated, or direct depo-
sition methods, whose carrying out does not require any
additional tool.
In general, materials to be deposited should display
good conductivity as well as good chemical and physical
compatibility with both substrates and deposition technol-
www.electroanalysis.wiley-vch.de Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
pens, for the rapid and on-demand deposition of conduc-
tive patterns on different substrates, with particular em-
phasis on the assembly of “Do It Yourself” sensors.
Moreover, layer-by-layer deposition of simple or even
complex three dimensional (3D) circuits, resorting to
pressure driven extrusion of conductive filaments is con-
sidered. Future perspectives and potentiality of these
emerging technologies for assembling sensors are also ex-
plored.
ogy, so that precise and repeatable patterning with opti-
mal adhesion can be achieved.
Inks or pastes, consisting of solid conductive particles
such as graphite powder, carbon nanotubes, metal parti-
cles and nanoparticles suspended in mixtures of solvents
and additives, such as polymeric stabilizers, wetting
agents and adhesion promoters, were profitably adopted
for this purpose [4, 5]. Inks based on the use of organo-
metal compounds or metal precursors were also pro-
posed, but they require additional heat-treatment to ach-
ieve reduction to metallic species, so as to achieve con-
ductivity [6]. Moreover, relatively large amounts of the
organic backbone residues could adversely affect the con-
ductivity of films thus fabricated [7].
Electrically conducting polymers, polymer electrolytes
and ion jells also show attractive features to be exploited
for these purposes. However, electrically conducting poly-
mers are characterized by relatively low conductivity, as
in the case of poly(3,4-ethylenedioxythiophene) [8], while
[a] N. Dossi, R. Toniolo, G. Bontempelli
Department of Food Science, University of Udine, via
Cotonificio 108, I-33100 Udine, Italy
phone : (+ 39) 0432 558835
fax: (+ 39) 0432 558803
*e-mail: nicolo.dossi@uniud.it
[b] F. Terzi
Department of Chemical and Geological Science, University
of Modena and Reggio Emilia, via Campi 183, I-41125
Modena, Italy
[c] E. Piccin
Department of Chemistry, Federal University of Minas
Gerais, 31270–901 Belo Horizonte, Brazil
Electroanalysis 2016, 28, 250 – 264 250
Review
Nicol! Dossi obtained his PhD in
Food Science from the University of
Udine in 2006. He is currently Assis-
tant Professor of Analytical Chemis-
try at the Department of Food Sci-
ence, University of Udine. His area
of interest includes fabrication and
application of microfluidic systems,
electrochemical sensors and paper-
based analytical devices.
Fabio Terzi is Assistant Professor at
the University of Modena and
Reggio Emilia, Italy. His main scien-
tific interests are: i) modification of
electrode surface using conducting
polymers, self assembled monolayers,
(nano)particles and graphene; ii)
spectroscopic and microscopic char-
acterisation of electrode coatings; iii)
synthesis and characterisation of (nano)particles; iv) electrocatal-
ysis applied to amperometric sensors.
Evandro Piccin received his PhD
degree in Analytical Chemistry from
University of S¼o Paulo (Brazil) in
2008. Since 2009 he is at the Depart-
ment of Chemistry of Federal Univer-
sity of Minas Gerais (Brazil) where
he is currently Adjunct Professor. His
main research activities include the
development of technologies for fab-
ricating microfluidic devices, micro-
chip electrophoresis, and chemical
analysis in paper-based analytical de-
vices coupled with electrochemical
sensors and mass spectrometry.
Rosanna Toniolo is an Associate Pro-
fessor of Analytical Chemistry at the
Department of Food Science, Univer-
sity of Udine. She graduated in
Chemistry from the University of
Padova in 1986. Her research interest
is in the area of electroanalysis and
sensor devices, with special attention
to gas sensors and their practical ap-
plications.
Gino Bontempelli is a retired Full
Professor of Analytical Chemistry at
the University of Udine. He graduat-
ed in Chemistry from the University
of Padova in 1967. His research inter-
est covers electroanalysis, electroana-
lytical and chemical devices, as well
as biosensors.
www.electroanalysis.wiley-vch.de
Fig. 1. Classification of possible deposition approaches.
polymer electrolytes and ion jells provide ionic conductiv-
ity.
Different techniques based on non-contact or contact
deposition, can be exploited for assembling conductive
circuits [9], as illustrated in Figure 1.
The non-contact approach, comprehending methods
based on vapor deposition, sputtering, lithography, screen
printing, inkjet and aerosols printing, enables conductive
materials to be dispensed without contacting the target
substrate. Contact techniques, including methods based
on stamp transfer, flexography and gravure, instead ex-
ploit deposition tools contacting directly substrate surfa-
ces to be patterned. In some cases (i.e. screen printing),
the contact of blades or squeegees, spreading the conduc-
tive material, with the substrate is only prevented by the
thickness of masks used to define the final layout of con-
ductive circuits.
Non-contact approaches, such as screen printing or con-
tact deposition techniques as stamp transfer and flexogra-
phy, all exploiting a template or a screen containing the
layout-design to be transferred onto substrates, are widely
used approaches for patterning quite easily conductive
materials onto planar substrates, with relatively low cost
instrumentation. However, they suffer from limitations if
changes of the planned design are required and, as in the
case of screen printing, large amounts of conductive ma-
terial are required [4, 10, 11].
Direct writing techniques, simply exploiting deposition
on target surfaces of a layer of material with the desired
geometry by a computer controlled mechanical stage,
provide a suitable deposition strategy for the fabrication
of microcircuits, electrodes and arrays in electronic devi-
ces and sensors. In fact, they are characterized by high
precision, and require no etching or material removal. In
these approaches a single direct step stands between
output-design and circuit fabrication. In addition, the cir-
cuit layout can be easily modified by the computer aided
design (CAD) software enabling easy design iterations.
Conventional direct writing methods can be classified
in four main groups: droplet-based, filament-based, tip-
based and laser-based approaches [12]. In particular,
these approaches make possible the direct and selective
deposition of conductive patterns without resorting to
Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Electroanalysis 2016, 28, 250 – 264 251
Review
masks, stamps or screens, thus offering many advantages
in terms of production speed and reduced environmental
impact.
Some direct writing approaches are coupled to sophisti-
cated techniques such as atomic force microscopy (AFM)
or require high power sources such as a laser to deliver or
deposit materials, thus limiting their portability and their
use in resource limiting settings. However, there are sim-
pler strategies enabling easy direct deposition of layers
and structures of conductive materials on planar and flex-
ible substrates at relatively low cost. Thus, for instance,
droplet based approaches such as inkjet printing and aer-
osol jet processes have received great attention in the last
decades [13]. The inkjet printing approach, based on the
most commonly used impulse mode, implies ink ejection
towards the substrate as droplets through suitable nozzles.
Nozzle dimension, ink viscosity (below 20 mPa s [14]),
surface tension, particle size and loading are important
parameters to be controlled as they markedly affect preci-
sion and conductivity of deposited lines [15].
Alternatively, filament based deposition methods, ex-
ploiting a pressure to extrude fluid materials through
a small nozzle directly onto substrate surfaces, provide an
efficient alternative to solve many constraints coming
from rheological properties of inks. In fact, material vis-
cosity can be varied in a very wide range, from liquid inks
to pastes [16–19]. Moreover, the possibility of controlling
carefully the pneumatic pressure by using fine valves ena-
bles precise flow to be achieved even onto non uniform
and curved surfaces. Notwithstanding these peculiarities,
the use of this approach for assembling sensing elements
of functional devices is still unexplored enough.
More recently, by profiting from the concept of deposi-
tion of continuous filaments, the use of portable writing
tools such as pencils and pens for direct contact writing of
electronic circuits and sensitive elements of analytical de-
vices have been proposed [20, 21]. In fact, pen reservoirs
can be filled by tunable inks which can flow out continu-
ously during writing and pencils are made of graphite
leads which can be regarded as solid writable carbon
based filaments.
These day-to-day office tools enable rapid drawing of
conductive lines by sliding in contact with the substrate in
an easy and repeatable enough way. Furthermore, con-
ductive tracks can be deposited only where required.
Despite limited precision, portability makes these
simple writing tools particularly attractive for assembling
“Do It Yourself” devices, particularly when immediate
applications are needed. Moreover, this approach can be
profitably exploited to pattern conductive lines onto con-
ventional or unconventional substrates by both manual
drafting or CAD assisted three dimension position con-
trollers.
It is important to note that, even if more complex in-
strumentation and external pneumatic apparatus are re-
quired, filament extrusion is preferred when ink flowing
through pen nibs is limited by its rheological properties
(viscosity up to 1000 Pa s [14]).
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In order to overcome restrictions of traditional two di-
mensional fabrication approaches and to make possible
the construction of both multilayered and full 3D struc-
tures without resorting to subtractive construction pro-
cesses, emerging technologies were recently developed,
such as additive manufacturing [22–25], i.e. processes en-
abling objects with even complex three-dimensional (3D)
shapes to be constructed by joining materials layer-by-
layer, exploiting the concept of filament-based extrusion.
In particular, these manufacturing processes include
a wide range of emerging technologies, such as laser sin-
tering, fused deposition modelling (FDM) and stereoli-
thography. Among them, FDM enables precise position-
ing and alignment of layers onto substrates (similarly to
previously described direct writing methods exploiting
continuous filaments) and offers great potentiality for the
fabrication of 3D layer-by-layer conductive structures
[26].
The aim of this review is to highlight the potentiality
offered by these new emerging fabrication methods based
on deposition of continuous filaments exploiting pens,
pencils and emerging extrusion-based approaches for as-
sembling simple or even complex 2D and 3D conductive
circuits on both planar and curved flexible substrates. It
must be however underlined that the potentiality of these
approaches for assembling sensitive conductive elements
in analytical devices is still scarcely explored.
2 Direct Deposition of Conductive Patterns by
Common Writing Tools
2.1 Pen Drawing
Unlike other deposition methods often requiring the use
of sophisticated instrumentation and skilled operators,
direct hand-drawn writing by pens, day-to-day tools, rep-
resents a suitable method to deposit bidimensional con-
tinuous conductive patterns with the desired design
(Figure 2) [20, 27, 28].
Pens can be classified in the following three main
groups: i) soft-tip pens (called also markers or felt-tip-
pens) which are provided with relatively soft porous-writ-
ing or felt-like tips made of absorbent plastic material,
while reservoirs consist of fibrous material acting as
a sponge for ink. During writing, ink is continuously
drawn from the reservoir onto the surface where lines
must be marked; ii) capillary pens (called also fountain-
pens) where the ink, contained in a reservoir connected
to a nib through a quite narrow tube, flows out by gravity
or by capillary action; iii) ball pens (called also rollerball,
ballpoint or gel ink pens) in which ink is dispensed on the
writing substrate through the rolling motion of a metal
ball located in the final part of the pen nib. The use of
such day-to-day writing tools makes possible the delivery
of tunable liquid inks from reservoirs onto substrates, ex-
tending significantly the nature of deposited materials by
simple direct writing.
Electroanalysis 2016, 28, 250 – 264 252
Review
Fig. 2. a) Optical image of a rollerball pen loaded with a con-
ductive silver ink. The background shows conductive text written
on office paper. b and c) SEM images of the side and top views
of the rollerball pen. d) Optical image of the rollerball pen tip,
captured during writing a conductive silver track on office paper.
Images reproduced from ref. [20].
More recently, much effort has been made to develop
liquid inks suitable to fill these portable writing tools with
the aim of making them suitable for both rapid drawing
of functional patterns on a wide range of substrates and
easy assembly of analytical and electronic devices. Thus,
for instance, a “Biopen” filled with a functional ink con-
taining nucleic acids, proteins and living cells was used to
draw on nitrocellulose membranes or printing paper devi-
ces suitable for the detection of nucleic acid associated to
human disease [29]. Moreover, pens containing inks
based on metal nanoparticles were adopted to construct
surface enhanced Raman scattering (SERS) paper-based
substrates and platforms for multiplexed label-free biode-
tection [30, 31].
These remarkable examples suggest that the develop-
ment of portable writing tools for patterning interconnec-
tions and electrical circuits in foldable, stretchable and
flexible electronics or even sensitive elements for sensors
is particularly challenging.
In particular, conductive inks suitable for pens can be
produced by resorting to mixtures of conductive poly-
mers, organometallic compounds, and metal precursors
[32]. Unfortunately, these inks are characterized in most
cases by low conductivity, so that additional treatments at
high temperature are often required to reduce organome-
tallic species to metals [33, 34].
Carbon and metal-based nanomaterials make possible
the profitable fabrication of flexible and conductive lines
[20, 33, 35–40]. As a matter of fact, the development of
new inks requires the optimization of their formulation to
achieve good dispersion of nanoparticles in viscous solu-
tions and proper alignments of nanoparticles in deposited
lines, as well as the overcoming of cracking problems
[33]. The use of nanoparticles with small dimensions can
reduce the temperature needed for sintering, when this
operation is required to achieve higher conductivity
[36, 41]. The elimination or reduction of heating steps
[42] and development of cost-effective sintering proce-
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dures are crucial aspects when inks are projected and rep-
resent important challenges for the development of writ-
ing tools suitable for on field applications and in resource
limited settings.
Finally, it must be mentioned that liquid metals and
alloys displaying low melting points, such as gallium and
indium mixtures, showing good conductivity and biocom-
patibility, were also proposed as suitable inks to fill pen
reservoirs [43–45].
Rheological properties of inks and their viscosity play
an important role during writing processes as they affect
ink flowing from pen nibs and ink adhesion to the writing
surface, also in view of the substrate porosity. In fact, an
optimal ink should flow at room temperature, without
leakages, skipping and coagulation [20, 34]. It is worth
noting that many water based inks adopted in conven-
tional writing instruments are characterized by a near-
newtonian behavior with a viscosity between 1 and some
mPa s which remains constant also when the shear rate is
increased [38, 46]. On the other hand, the dispensing of
inks displaying a decreasing viscosity with increasing
shear rates (about 1000 s¢1) produced by writing [38]
(force during writing is about 0.6–1.6 N [29]) is more con-
trollable [46]. In this case, flow stop during writing pauses
and suitable feeding during fast writing is achieved, thus
allowing increased precision of applied marks. A viscosity
in the range of 1–10 Pa s at a share rate of 1 s¢1 was mea-
sured in rollerball pens filled with silver nanoparticles-
based inks with solid loading of 45–55%. A viscosity de-
crease with increasing shear rates was observed and this
behavior was enhanced by increasing the silver nanoparti-
cles content up to 65% ( … 100 Pa s at 1 s¢1) [20]. A simi-
lar trend was also observed in fountain pens containing
carbon nanofiber-based inks where viscosity decreased
from … 26 mPa s at 1 s¢1 to … 1.1 mPa s at 1000 s¢1 [38]. In
general, rheology of inks is affected by particle-particle
attrition and by the presence of additives such as poly-
meric binders and adhesives.
As mentioned above, both rollerball and capillary pens
were used to deposit conductive inks. It is important to
note that the pressure required by rollerball pens to gen-
erate friction between the ball and the writing surface
could limit the range of writing substrates, because in
some cases they could be damaged [47]. Thus, sufficiently
enough rough surfaces are required to enable friction
when these writing systems are used. Despite these limits,
precise lines characterized by width of some hundreds of
microns and thickness of tens of microns, were drawn by
roller ball pens with tip ranging from some hundreds to
one thousand of microns with both metal nanoparticles-
based and liquid metals inks [20, 36, 39, 42, 43].
Despite a more difficult control of the ink amount dis-
pensed, especially when porous supports are used, capilla-
ry pens make also possible to pattern soft and smooth
surfaces [47].
In general, capillary-induced spreading depends on
rheological characteristics of ink, substrate properties, nib
diameter and writing speed [29, 48]. The volume of ink
Electroanalysis 2016, 28, 250 – 264 253
Review
Table 1. Pen patterns used as simple conductors. 1 (mW cm) and R (KW cm¢1) are resistivity and resistance, respectively.
Pen type Ink composition Substrate 1, R Application Ref
a
Rollerball pen Ag nanoparticles in HEC water- Office paper, wood, scotch 199 mW cm rt, 4.34 mW cm Conductive track [20]
a
methanol solution tape, alumina Š 1708C
Rollerball pen Ag nanoparticles, ammonia aque- Weighing paper 6.8 mW cm a200 8C, 60 min Conductive track [28]
ous solution (pH = 10), ethylene
glycol
Rollerball pen Cu nanosheets or Ag nanoparti- Office paper … 12 mW cm (Cu) Conductive track [33]
cles coated Cu nanosheets in … 8.9 mW cm (Cu-Ag)
CMC water-methanol solution
Rollerball Pen Silver acetate, ethanol, ethylene Sulphuric paper 326 mW cm a200 8C, 60 min Conductive track [34]
glycol, ethanolamine, oleic acid
Rollerball pen Cu nanoparticles, water, ethanol, Photo paper 13.4 œ 0.4 mW cm a160 8C, Conductive track [35]
glycerol, ethylene glycol 120 min (Ar atmosphere)
Rollerball pen Cu nanoparticles, water, ethanol, Photo paper 7.2 œ 0.6 mW cm a160 8C, Conductive track [36]
glycerol, ethylene glycol 120 min (Ar atmosphere)
Rollerball pen Ag nanoparticles, graphene-Ag Photo paper 19 mW cm a100 8C, 60 min Conductive track [39]
nanosheets, ethanol, ethylene
glycol, glycerol
Rollerball pen Ag nanoflakes, aqueous solution Weighing paper 9.4 mW cm a200 8C, 20 min Conductive track [40]
(pH = 10), ethylene glycol, 2-
butoxy-ethanol, ethanol
Rollerball pen Ag nanoparticles, ammonia aque- Sulphuric paper 214 mW cm a200 8C, 60 min Conductive track [41]
ous solution (pH = 10), diethylene
glycol, Triton X-100
Rollerball Pen Ag nanoparticles, ethanol, ethyl- Photo paper 14.3 mW cm a120 8C, 25 MPa, Conductive track [42]
ene glycol, glycerol 15 min
Rollerball pen Ga-In24.5 Flexible polymers … 29.8 mW cm Conductive track [43]
Rollerball pen Ga-In10 Epoxy resin board, glass, 34.5 mW cm Conductive track [44]
plastic, silica gel, paper,
textile
Printer with Ga-In24.5 PVC, office paper … 29.8 mW cm Conductive track [45]
roller-bead
Rollerball pen SWCNTs, polyethylene oxide, Paper, PET 8.8x104 mW cm Conductive carbon [50]
water, SDS fibres
Rollerball pen C8-BTBT semiconductor in ani- SiO2/Si substrate (HMDS Unspecified OFET [52]
sole a50 8C coated)
Marker Silver carbonate, glycol, water, Polyimide 18 mW cm a150 8C, 60 min Conductive track [32]
isopropylamine
Capillary pen PEDOT:PSS, PTAA, TIPS_PEN SiO2/Si substrate (HMDS 6.6 x 106 mW cm for PE- OFET [47]
in chlorobenzene or dichloroben- coated) PVP coated poly- DOT:PSS
zene arylate
Fountain pen SWCNTs, water, SDBS Office paper, paper ob- 1 KW cm¢1 Conductive track [37]
jects
Fountain pen Carbon nanofibers, gellan gum Photo paper 97 œ 20 KW cm¢1 (for Conductive track [38]
water solution 1 layer) 3.4 œ 0.1 KW cm¢1
(for 10 layers)
Fountain pen FeCl3 aqueous solutionb Office paper, cotton < 1 KW cm¢1 Conductive track [51]
threads
a
Curing temperature and time, if specified (rt: room temperature). b Polypyrrole is deposited on the written ink by exposure to pyr-
role vapors. PVC: polyvinylchloride; PET: polyethylene terephthalate; HEC: hydroxyethyl cellulose; CMC: carboxymethyl cellulose;
C8-BTBT: dioctylbenzothienobenzothiophene; HMDS: hexamethyldisilazane; PEDOT-PSS: poly(4-styrene sulphonate) doped
poly(3,4-ethylenedioxythiophene); PTAA: poly(dimethyl-triarylamine); PVP: poly-4-vinylphenol; TIPS PEN: 6,13-bis(triisopropylsy-
lilethynil)pentacene; SDBS: sodium dodecylbenzenesulphonate; SDS: sodiumdodecylsulphonate.

used can be simply evaluated by calculating the reduced
weight of the pen after writing 100 cm lines under con-
stant conditions [29].
Electrical resistivity is the key feature when inks are
developed for assembling devices where current conduc-
tion or transfer is needed. In fact, as it can be observed in
Table 1, suitable resistivity values were achieved by pat-
terning conductive tracks with copper and silver-based
inks, which displayed a strict dependence from the
number of ink layers applied. These values turned out to
be greater than in bulk copper or silver which are
1.72 mW cm and 1.6 mW cm, respectively [20, 35, 36].
In conclusion, by profiting from this approach, deposi-
tion of tunable functional inks is possible onto a wide va-
riety of substrates, not only with roughness similar to
paper but also onto smoother surfaces or unconventional

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Review
Table 2. Pen patterns used as sensitive elements. R is resistance.
Pen Ink composition Substrate R Application Ref
¢1
Fountain pen SWCNTs, water, SDBS Office paper 1 KW cm Chemical sensor [37]
Fountain pen FeCl3 aqueous solutionb, FeCl3 Office paper 1 KW cm¢1 Temperature, chemi- [51]
and PSS aqueous solutionb cal, light sensor
Rollerball pen Graphite, PEG, water, chitosan, Office paper, alumina, skin, … 15 KW cm¢1 art, 30 min Electrochemical bio- [49]
xylitol, methylene green, enzyme plant leaves or 50 8C, 5 min sensor
Rollerball pen Commercial graphite ink C10H paper Unspecified Electrochemical [53]
ELISA
Rollerball pen Commercial graphite ink Office paper, Whatman 2.26 KW cm¢1 Electrochemical [54]
paper, Millipore paper, sensor
paper objects, skin
a
Curing temperature and time, if specified (rt: room temperature). b The deposition of the ink is followed by exposure to pyrrole
vapors. PSS: poly(4-styrene sulphonate); SDBS: sodiumdodecylbenzenesulphonate.

materials such as plant leaves, skin, wood and soft poly-
mers [20, 49]. Thus, by taking advantage from this simple
one-step patterning procedure, the deposition of conduc-
tive or semiconducting materials can be easily achieved
also by untrained operators even when immediate availa-
bility is required.
Recent applications exploiting this deposition tech-
nique for the construction of simple conductive tracks for
simple applications, such as to drive power to a light-
emitting diode (LED) or to assemble organic field effect
transistors (OFETs) and antennas, are listed in Table 1.
Even if reported examples are limited to the development
of simply proof-of-concept devices, relevant ink formula-
tions may inspire the design of writing tools aimed at as-
sembling functional conductive elements suitable for
measurements of chemical parameters and physical phe-
nomena.
2.2 Pen Patterns for Sensing Applications
The possibility of preparing inks with specific and tunable
properties opens up new horizons for on-site fabrication
and easily customizable development of “Do It Yourself”
sensing devices applicable to food, biomedical and envi-
ronmental analysis, as summarized in Table 2.
Recently, the use of portable writing instruments such
as fountain pens, filled with either water-based conductive
or semiconducting single wall carbon nanotube (SWCNT)
inks, were exploited for the rapid prototyping of a paper-
based chemosensor for ammonia detection at ppm level
[37].
By profiting from the porosity of paper, which allows
liquid inks to be not only deposited but also easily ab-
sorbed and transferred from one face to another, either
simple dual side or multilayer paper circuits and electrical
interconnections can be constructed by exploiting suitably
the contact time between the pen nib and paper. In par-
ticular, a device consisting of a layer of porous paper pat-
terned with p-type semiconducting carbon nanotubes
(CNTs), acting as ammonia sensing element, was sand-
wiched between two layers containing CNTs electrical in-
terconnections. The presence of an electron donor such as
ammonia, causing the elimination of holes in semiconduc-
tors, lead to a resistance increase of the sensor [37].
A pen-writing technique using fountain pens was
adopted to deposit on paper lines drawn by a FeCl3 aque-
ous solution. Exposure of these marks to vapors coming
from a pyrrole solution at room temperature yielded
polypyrrole circuits with excellent mechanical and electri-
cal properties. Subsequently, taking advantage of the con-
ductivity changes induced by polymer heating or by expo-
sure to suitable chemical species, these lines were exploit-
ed as sensitive elements for thermometers, photometers
and chemical sensors. In particular, an electron donor
species such as ammonia was able to reduce the number
of partially oxidised radicals in the polymer, acting as
mobile carriers, thus causing a change of its conductance.
By adding to the initial ink a suitable doping agent such
as poly(sodium-p-styrenesulfonate), which is prone to
bind Lewis bases such as ammonia, the sensitivity of the
device was improved, making possible the detection of
ammonia down to 1.2 ppm [51].
A rollerball pen filled with commercial graphite ink
was recently used to write counter, reference and working
electrodes suitable to perform electrochemical measure-
ments. The deposition was carried out on paper made hy-
drophobic by vapor phase silanization (C10H or RH). The
pen was installed in an automatic x-y plotter, in order to
improve the deposition precision.
By profiting from this pen-on-paper approach, flexible
and foldable paper platforms were assembled and their
performance was evaluated by electrochemical ELISA
for the detection of antigens associated to human disease
[53]. This device was first tested on rabbit IgG and alka-
line phosphatase-labelled anti-rabbit IgG, used as
a model of antigen and antibody, respectively. Subse-
quently, a test for the quantification of malarial histidine-
rich protein from Plasmodium falciparum (PfHRP2) in
human serum, was developed.
The development of enzymatic ink-based pens suitable
for the rapid patterning of biocatalytic sensors was re-
cently proposed (Figure 3). For this purpose, an innova-
tive, stable and highly conductive ink was developed by
mixing graphite powder, polyethylene glycol (PEG), chi-

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Review
Fig. 3. Epidermal glucose sensors drawn by a rollerball pen
filled with biocatalytic ink. Effect of: (A) twisting; (B) torsional;
(C) stretching and (D) pinching. (E) Sensor after 100 stress
cycles. (F) Sensor coupled with a Bluetooth-enabled potentiostat
for epidermal continuous glucose monitoring; (G) amperometric
response for increasing levels of glucose ranging from 0 (dashed
line) to 10 mM (e). Inset: calibration plot. Working conditions:
phosphate buffer (pH = 7) and applied potential 0.4 V. Images re-
produced from ref. [49].
tosan, xylitol and methylene green acting as conductive
material, binder, additive improving adhesion to the sub-
strate, enzyme stabilizer and electrochemical mediator,
respectively [49].
This formulation, which was used with either glucose
oxidase or tyrosinase, did not require any additional
curing step and enabled renewable, flexible, and inexpen-
sive devices to be constructed for monitoring analytes of
importance in clinical and environmental fields. In partic-
ular, this approach proved to be suitable for the rapid as-
sembly of reliable and robust electrochemical biosensors
not only on conventional planar supports, such as paper
or alumina, but also on unconventional substrates, such as
biological tissues (e.g. human skin and plant leaves).
More recently, a simple but reliable method has been
proposed to overcome, at least partially, ink viscosity lim-
itations when using the pen writing approach for assem-
bling electrochemical platforms. It involves the exploita-
tion of a pressure-assisted ball pen, consisting of a syringe
able to apply a defined pressure. It was installed on the
final opening of the ink reservoir, thus enabling suitable
flowing from the nib to be achieved. In such a way, time
consuming pretreatments (e.g. dilution), often required to
tune suitably commercial inks viscosity, were avoided. By
profiting from this approach, paper-based electrochemical
sensors and biosensors for melamine and glucose detec-
www.electroanalysis.wiley-vch.de Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
tion in food and urine samples, respectively, were devel-
oped. In addition, the possibility to assemble multi-elec-
trode arrays and conductive tracks even on non-planar
surfaces and non-conventional substrates, such as skin,
was successfully explored [54].
It is important to underline that all these devices are
applied to detection problems by resorting to the same
usual procedures adopted when sensors and biosensors
assembled by more difficult construction methods are em-
ployed.
2.3 Pencil Drawing
Pencils, like pens, are widespread and portable writing
tools which make possible the easy patterning of conduc-
tive lines even on non planar and curved structures and
the rapid assembling of prototypes in resource limited
settings with the possibility of rapidly modify devices di-
rectly on field [21].
Unlike pens, pencils enable dry deposition to be ach-
ieved, thus overcoming problems related to drying pro-
cesses, such as solvent evaporation and time and energy
consuming heating steps, as well as risks related to leak-
age, encountered when liquid inks are used on porous
supports [55]. Moreover, limitations connected to rheo-
logical properties of inks such as flowing out and nib
clogging are prevented.
Pencil leads are compressed solid rods consisting of
mixtures of clay or polymeric binders and graphite
(which can be seen as a combination of many layers of
graphene stacked on top of one another and held togeth-
er by van der Waals forces [56]).
The amount of graphite is proportional to the hardness
of pencils, which are classified on scales ranging from 9H
to 1H and 1B to 9B, with a carbon content ranging from
about 40 to 90 % [57, 58]. Abrasion of pencil leads on
a rough enough surface makes possible dry deposition of
continuous patterns of ultrathin graphite particles. Conse-
quently, using the same friction, softer pencils produce
darker lines with higher amounts of graphite, as illustrat-
ed in Figure 4. It is important to note that smoother and
more uniform surfaces improve the exfoliation of graph-
ite, thus resulting in deposition of smaller particles [55].
For instance, thicker layers of graphite deposits were ob-
served by increasing surface roughness in the range from
2 to 10 mm (expressed as root-mean-square) [59].
It is well known that such tracks, consisting of intercon-
nected graphite domains and graphene multilayers, are
optimal electrical conductors [60, 61]. Moreover, patterns
with different properties and characterized by different
conductivity can be obtained by varying both the hard-
ness of pencil leads and roughness or porosity of abrasive
substrate surfaces. In general, softer pencil leads generate
marks with higher graphite contents, thus exhibiting in
principle lower electrical resistance [57] (e.g. a resistance
of 1290, 236 and 127 KW was measured for a 30 mm in
length and 1 mm in width line drawn by HB, B and 2B
pencils, respectively [62]). A strict dependence of line
Electroanalysis 2016, 28, 250 – 264 256
Review
A relatively simple model was developed to estimate
the thickness of non-uniform deposited layers, without re-
sorting to the use of optical microscope, allowing the cal-
culated value to be related to the surface roughness of
the substrate [59]. The model is based on the following
equation:

t ¼ ðV=AÞ ¼ m=ðpAÞ

where t (in cm), V (in cm3), A (in cm2) and m (in g) are
thickness, volume, area and mass, respectively, of the de-
posited layer on the writing surface, whilst p (g cm¢3) is
the particle density.

Drawing of continuous and conductive patterns on cel-

Fig. 4. Energy dispersive spectra of pencil leads relating their
hardness with the carbon fraction. Intensities of all spectra are
normalized vs. carbon peak highlighting the relative fraction of
carbon to the clay binder (softer pencils contain lower quantity
of clay). Optical microscopy images of traces drawn on paper
substrates from pencils with decreasing hardness (b–g). Softer
pencils lead to larger amount of graphite to be deposited. Images
reproduced from ref. [57].
width with the number of pencil layers was observed [63],
(e.g. a resistance of 62 KW and 8 KW were measured for
a 30 mm in length and 1 mm in width line drawn once
and three times, respectively, with a 6B pencil [62]).
Paper, an easily available porous material with low en-
vironmental impact, is a foldable and flexible support
with optimal roughness and tunable porosity, suitable for
exfoliation of pencil leads and consequent deposition of
graphite particles by a soft hand pressure. Moreover,
paper being made out of cellulose fibres, can be easily
wicked by capillarity and displays high chemical resist-
ance, as well as the possibility to be easily modified.
lulose fibres may be profitable for constructing a simple
but efficient new generation of electronic devices. In gen-
eral, pencil traces, which can be considered as continuous
conductive films, can be used as electrical contacts, elec-
trodes, functional electronic materials and sensing devi-
ces. Moreover, the possibility of adding suitably tailored
modifiers to pencil composition can extend the range of
applications, otherwise limited by the use of sole graphite
[64, 65].
Some significant examples of the use of pencil-drawn
conductive tracks, as alternative to other metal-based ma-
terials, are reported in Table 3. In the applications consid-
ered, graphite lines are component of complex devices
but they serve only as current conductors. It is worth
noting that in the case of the reported examples the use
of pencil drawing has high impact on the reduction of
costs and steps required for device construction.
2.4 Pencil Patterns for Sensing Applications
Transducers made of graphite deposited by pencil draw-
ing can be used as sensing elements of devices aimed at

Table 3. Pencil patterns used as conductors.

Lead composition Writing substrate Application Ref
Graphite rods, commercial pencil Office paper or in-house made paper Supercapacitor [55]
(unspecified)
Commercial pencil (unspecified) Conductive glass (ITO) Dye-sensitized solar cell [66]
Commercial pencil (2B) Whatman paper Electrokinetic-driven microfluidic [67]
system
Commercial pencil (HB) Whatman paper Electrokinetic-driven microfluidic [68]
system
Unspecified pencil Whatman paper Supercapacitor (mPPECD) [69]
Commercial pencil (8B)a Office paper Supercapacitor [70]
Commercial pencil (4B)b Office paper Supercapacitor [71]
Commercial pencil (4B) Unspecified paper modified with ZnO powder Photoconductive UV sensor [72]
Commercial pencil (4B) Unspecified paper modified with ZnO nanocrystals Photoconductive UV sensor [73]
Graphite rods Polished n-type CdTe substrate Schottky-type heterojunction [74]
Commercial pencil (HB) Whatman paper Field effect transistor [75]
Commercial pencil (HB) Office paper Field effect transistor [76]
Commercial pencil (HB) Whatman paper Fuel cell [77]
a
Polyaniline or b polypyrrole was grown on the drawn material through an electrochemical deposition process. mPPECD: microfluidic
paper-based photoelectrochemical device.

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Review
monitoring either force and pressure or chemical species
[21].
A simple and flexible paper-based piezo-resistive
system, in which a pencil drawn resistor acts as the device
core, was recently proposed [57, 78, 79]. Briefly, an ap-
plied force generates a mechanical strain/stress causing
expansion or contraction of the graphite network, thus
providing a resistance change proportional to the applied
pressure. Tensile deformation causes a partial separation
of particles within the patterned graphite line, with a con-
sequent resistance increase. Conversely, compressive de-
flection facilitates contact among graphite particles, thus
increasing electrical conduction. Recently, a similar ap-
proach was profitably exploited to assemble sensors with
fast response time (< 110 ms), able to monitor human and
robotic motions and book-folding (e.g. opening/closing
states of doors) [63]. Moreover, it was demonstrated that
the use of different-grade pencils can tune piezoresistive
properties of sensing elements, thus changing sensor sen-
sitivity [78].
Besides mechanical stress, also chemical stimuli can
induce resistance changes of graphite patterns drawn by
carbon-based pencil leads. In addition, the presence of
suitable solid or liquid modifiers, whose chemical-physical
properties can be modified when contacted by specific an-
alytes, can infer specificity to sensing elements, thus also
offering the possibility to assemble arrays of chemiresis-
tors.
In particular, an approach for assembling on paper
chemiresistors consisting of electrodes created by simple
abrasion of compressed pellets composed of graphite or
nanostructured carbon material, such as single wall
carbon nanotubes (SWCNT) or multiple walls carbon
nanotubes (MWCNTs), called process-enhanced nanocar-
bon for integrated logic (PENCILs), was proposed [59].
In more detail, devices consist of sensing elements gener-
ated by mechanical abrasion of pristine SWCNTs, ob-
tained by compression of the nanomaterial into pellets,
within the 1 mm gap of two gold electrodes preliminarily
deposited on a paper substrate. This method was firstly
used to assemble sensitive and flexible paper ammonia
sensors by profiting from the interaction of NH3 with
SWCNTs and consequent change in the measured current
in the drawn sensing zone. A similar procedure was ex-
ploited to draw a uniform graphite coating on silver inter-
digitated electrodes (IDEs) printed on paper, thus
making possible rapid assembling of NO2 sensors [80].
The addition of specific solid or liquid modifiers during
fabrication of pellets made possible the production of
arrays of selective paper-based chemiresistors which
showed selective responses to different gaseous analytes
[81, 82].
The use of commercial pencil leads containing PVC as
binder for graphite particles was exploited to construct
a simple but reliable paper-based chemiresistor sensitive
to some volatile organic compounds (VOCs). In this case,
the polymer binder is swollen, upon exposure to some
gaseous analytes with solvents suitable for PVC. Thus,
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graphite particles are pulled further apart, causing in-
crease of the relevant resistance [57]. The use of laser or
chemical etching made possible the construction of rough
enough patterns to facilitate abrasive deposition of
carbon-based pencil leads on a wide variety of glassy sur-
faces, such as polymethylmethacrylate, silicon, adhesive
tape, glass or alumina. By profiting from this approach,
fully drawn carbon based sensing array sensitive to differ-
ent analytes were developed [82].
More recently, paper platforms containing carbon elec-
trodes drawn by commercial pencils have been used as
capacitively coupled contactless conductivity detectors
(C4D) in microchip electrophoretic separation devices.
The proposed approach was successfully employed for
the quantitative analysis of inorganic cations such as K +
and Na + in tear samples [83].
Pencil drawing was also used for the quick and easy
construction of electrodes for electrochemical circuits on
paper [84, 85]. Onto this inexpensive and flexible porous
material simple or even complex hydrophilic fluidics can
be easily created by patterning hydrophobic boundaries
extending across its thickness by using photoresists, inkjet
or wax inks [86–88].
Consequently, pencil drawing makes quite easy the
design of electrodes suitable for assembling electrochemi-
cal cells or inexpensive amperometric detectors for paper-
based devices. These devices were evaluated as both
simple cells suitable for voltammetric experiments under
static conditions and detectors for thin-layer chromato-
graphic systems where analytes of importance in food
analysis such as ascorbic acid and sunset yellow, a com-
monly used food dye, can be individually detected after
rapid separation [84]. The use of commercial pencil leads
in such modality showed its utility also for the construc-
tion of paper-based platforms to be used for metal deter-
mination by stripping voltammetry [89].
Furthermore, the performance of these pencil-drawn
electrochemical devices was studied using both aqueous
and non aqueous electrolytes. In fact, by easily assem-
bling solvent resistant polydimethylsiloxane boundaries
on paper by a simple stamp printing method, voltammet-
ric and flow-injection analysis coupled to amperometric
detection of ferrocene in acetonitrile was performed [90].
By profiting from the use of pencil drawing, simple but
effective dual electrodes proved to be profitable for the
discrimination in flow systems of comigrating analytes un-
dergoing electrochemical behaviors characterized by dif-
ferent reversibility such as ascorbic acid and paracetamol
[91]. Recently, doped pencils were prepared by mixing at
room temperature controlled amounts of the desired me-
diators with carbon powder (conductive material),
sodium bentonite (binding agent) and sodium silicate
(hardening agent) and subsequently extruding the mix-
ture to form thin rods (Figure 5). This procedure was dif-
ferent enough from that usually employed for commer-
cially available pencils, to avoid undesired heating steps
able to cause modifier decomposition [64]. By profiting
from this approach, it was possible to draw modified elec-
Electroanalysis 2016, 28, 250 – 264 258
Review
Fig. 5. (A) Schematic illustration of the fabrication process of
pencil leads. (a) Graphite-based mixture is loaded inside the ex-
truder; (b) pressure is applied by keeping the extruder outlet
opening plugged up; (c) the plug is removed and the plunger is
pressed to extrude graphite rods which are then cut into pieces;
(d) pencil leads are inserted in commercial holders. (B) Layout
of the pencil-drawn paper-based electrochemical cell (PED). W,
R and C are working, pseudo-reference and counter electrodes,
respectively. Images reproduced from ref. [64].
trodes containing cobalt phthalocyanine as modifier
acting as electrocatalytical mediator for the determination
of cysteine and hydrogen peroxide.
A similar procedure was proposed for preparing pencil
leads by using graphite previously modified with Ag and
AgCl. This approach proved to be suitable for drawing
on paper or other porous supports carbon based Ag/AgCl
conductive lines to be used as reference electrodes [92].
The use of commercial pencils to draw electrodes on
paper was also exploited for assembling electrochemilu-
minescent (ECL) immunosensors [93].
More recently, the use of pencil-drawn paper-based de-
vices for conducting direct electrochemical measurements
in oils was proposed. This device made possible the vol-
tammetric detection of both hydrophilic and lipophilic
electroactive species present in oils by exploiting the
three-boundary phase taking place among pencil drawn
working electrode, electrolyte embedded on paper sup-
port and sample applied over devices [94]. This approach
made possible the development of one-spot tests enabling
olive oil to be easily distinguished from other vegetable
oils.
Recent applications profiting from this simple dry and
solvent-free deposition method on different supports are
collected in Table 4.
3 Extrusion-based Direct Deposition of Conductive
Filaments and 3D Structures
Approaches based on extrusion of conductive materials
offer a powerful route for assembling functional struc-
tures and devices with different design and shape. Despite
the bright prospects, the number of sensing systems as-
sembled by this approach is limited [95].

Table 4. Pencil patterns used as sensors.

Lead composition Writing substrate Application Ref
Commercial pencil (HB), PVC-based Office paper Piezoresistive sensor, chemiresistive [57]
pencil gas sensor
Compressed SWNTs Whatman paper, weighing paper, office paper, Chemiresistive gas sensor [59]
recycled paper
Commercial pencil (2B) Office paper Piezoresistive sensor [63]
Commercial pencil (HB) Office paper Piezoresistive sensor [78]
Commercial pencil (2B) Office paper Piezoresistive sensor [79]
Commercial pencil (8B) Weighing paper Chemiresistive gas sensor [80]
Compressed graphite, SWCNTs, Weighing paper Chemiresistive gas sensor [81]
MWCNTs, modifiers
Commercial pencil (9B), compressed Glass, PMMA, weighing paper, Chemiresistive gas sensor [82]
SWNTs, modifiers adhesive tape, alumina
Commercial pencil (2B) Office paper, Whatman paper C4D for microfluidic devices [83]
In-house made pencil with modifiers Whatman paper Voltammetric sensor [64]
Commercial pencil (3B) Whatman paper Voltammetric, amperometric sensor [84]
Commercial pencil (6B) Whatman paper Voltammetric sensor [85]
Commercial pencil (6B) PVC substrate Stripping voltammetry [89]
Commercial pencil (3B) Whatman paper Voltammetric sensor [90]
Commercial pencil (3B) Whatman paper Dual electrode amperometric detec- [91]
tor
Commercial (3B) and in-house made Whatman paper Voltammetric sensor [92]
Ag/AgCl pencils
Commercial pencil (6B) Whatman paper ECL immunosensor [93]
In-house made pencil Whatman paper Voltammetric sensor [94]

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Review
Fig. 6. Scheme of a fused deposition modeling (FDM) 3D print-
er. In this method, plastic filament is directed into a heating
block where it is heated to a semi-molten state. The molten ma-
terial can be printed onto an adjustable stage to form a layer of
the desired object. Each semi-molten layer is printed after suita-
ble adjustment (lowering) of the stage. Image reproduced from
ref. [96].
This type of deposition is based on the extrusion of
a continuous filament through a single or multi-nozzle
array, by applying a pressure with a syringe pump or an
air-powered dispensing fluid. Alternatively, as in the case
of solid filaments used in 3D printing [96], the material
can be driven by two rollers as illustrated in Figure 6.
Extrusion systems are essentially based on two key
sub-systems which are the deposition head, consisting in
an ink reservoir ending with a nozzle zone and the XYZ
positioner. Computer numerical control (CNC), which is
a system widespread employed in a number of industrial
applications, is exploited to coordinate the three-axis
motion of the positioner and to control the deposition
head during material extrusion on the substrate [97]. In
such a way, position of the head, deposition speed and
amount of the extruded material are precisely controlled.
Dimension of the deposited layer is affected by printing
speed, pressure applied, nozzle diameter, as well as by
properties and rheology of the deposited material.
The most important approaches for the continuous
deposition of electrically conductive paths and structures
profiting from this technologies are reported in the fol-
lowing.
3.1 Deposition of Inks and Pastes
Most of knowledge for the formulations of inks and
pastes comes from inkjet or screen printing technologies.
With reference to this, a number of reviews and books
have summarized the state-of-the-art [98, 99]. Similarly to
what discussed in the case of pens (Section 2), most of
inkjet printing limitations connected to rheological prop-
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erties of inks, in terms of surface tension and viscosity,
are overcome. Furthermore, since the flow is induced by
pressure, clogging problems are reduced. As a result,
even if this approach requires higher technological and
automation level, a large number of inks and pastes, even
possessing high viscosity and disperse particulate, can be
adopted.
Electrochemical platforms have been fabricated ex-
ploiting n-Scrypt [100, 101], which is a deposition system
consisting of a dispensing tip integrated with a pump
mounted onto XYZ motion platforms. This system ena-
bles precise deposition of commercial graphite conductive
inks to be achieved. Electrochemical devices, assembled
by profiting from this method displayed performance
very similar to those obtained with screen printed electro-
des prepared with same inks. The filament-deposition ap-
proach also enables the construction of conductive verti-
cally printed and 3D structures [102]. For instance, a sus-
pension of carbon black particles in silicone oil, also
known as carbon conductive grease, was recently pro-
posed for patterning conductive tracks using an extrusion
based deposition system. The ink, displaying a marked
shear thinning behavior (viscosity decreases from 104 Pa s
to 10 Pa s as the shear rate increases from 10¢2 s¢1 to
103 s¢1), was extruded through thin nozzles to generate
sensitive elements of 3D printed strain sensors [103]. Re-
cently, composites consisting of graphene mixed with
polylactide-co-glycolide or copolymers composed of poly-
methacrylic acid and polyethylene glycol, crosslinked
with ethylene glycol dimethacrylate were developed and
utilized to create 3D graphene conductive structures via
extrusion-based printing [25, 104].
It is worth noting that pencil lead itself is a solid fila-
ment obtained through extrusion of a paste, consisting of
graphite and clay or polymeric material acting as binder
[57, 64, 105].
Different conductive materials can be also patterned by
profiting from the filament extrusion approach. For in-
stance, lithium-based compounds such as Li4Ti5O12 and
LiFePO4 nanoparticles suspended in a solution containing
water, ethylene glycol, glycerol and cellulose based visco-
sifier were extruded to pattern 3D electrodes for Li-ions
microbatteries. A subsequent heating process was neces-
sary for sintering nanoparticles and removing organic ad-
ditives after printing [106].
Metal clays, which are moldable composite materials
based on metal particles and organic binders, can also be
used. They were developed starting from Ð90s [107] for
the fabrication of jewels. These composite materials offer
a number of advantages such as, for instance, the fact that
their deposition can be carried out at room temperature.
By profiting from this approach a number of different
metals can be deposited; in fact, pastes containing both
precious metals, e.g. Ag and Au, and basic metals or
alloys, e.g. Cu, bronze and steel, have been employed.
However, the removal of organic binders must be carried
out in a kiln at high temperature and in some case
Electroanalysis 2016, 28, 250 – 264 260
Review
oxygen should be removed during the firing in order to
avoid metal oxidation.
3.2 Low Melting Point Metals and Alloys
Metals and metal alloys possessing very low melting
points, i.e. the so-called fusible alloys, have also been em-
ployed for the deposition of conductive paths [108, 109].
Their deposition can be carried out by extrusion through
suitable nozzles. The choice of the metal is complex. In
fact, only few pure metals display suitable melting points,
e.g. Hg, Pb, Sn, Na, K and some of them, such as alkali
metals are too reactive to be fruitfully employed. On the
other hand, metal systems based on Hg, Pb and Cd are
toxic. In addition, Hg possesses a very high surface ten-
sion, leading to the formation of spherical drops on many
substrates, instead of wetting surfaces.
An interesting alternative is the use of metals such as
Ga, whose surface forms a thin layer of oxide materials
after deposition [95]. Although the relevant oxide dis-
plays a significant electrical resistance, it protects the
pure metal from the contact with the environment.
On the other hand, metal alloying can be suitably
adopted to modify viscosity, reduce melting points or in-
crease conductivity of extruded materials. For instance,
eutectic mixtures, such as Ga-In, display quite low melt-
ing points, low resistivity ( … 29 mW cm) and low viscosity
( … 2.4 mPa s) [110]. Recently, conductive traces patterned
by extrusion of Ga-In (75–25% w/w) alloy, flowing
through a syringe pump, were used as sensitive elements
of elastomer-encapsulated strain gauges [111, 112].
3.3 Conductive Thermoplastic Filaments
Thin filaments composed of thermoplastic polymeric ma-
terials can be extruded by means of suitable heated noz-
zles located at the bottom of the deposition head. The
polymer, after rapid cooling down, forms a solid thin
wire; the subsequent deposition of wires very close to
one another leads to the formation of solid, mechanically
and also, in some cases, chemically resistant 3D struc-
tures. The polymeric material is supplied to the deposi-
tion head by mechanical systems basically consisting of
proper gears pushing filaments based on a thermoplastic
polymer inside a melting chamber located in the deposi-
tion head and connected to the nozzle.
This printing system, called fused deposition modeling
(FDM), was developed in the Ð80s [113] and was widely
adopted for rapid prototyping of mechanical components.
Its diffusion concerns not only academic and industrial
environments but also hobbyists. In recent years, an in-
crease of the diffusion of this deposition method took
place, due to some key patents concerning the relevant
instrumentation, which led to the reduction of its overall
cost, also thanks to the development of open hardware
and software projects (see, e.g., RepRap [114] and Ardui-
no [115] projects for mechanical components, electronics
and software sub-systems).
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FDM offers a number of advantages, it being a low
cost and easy to use technology close enough to maturity
which does not require dedicated laboratories. A large
community supports the development of new hardware
and software solutions, as well as the development of new
materials, so that it is difficult enough to compile an ex-
haustive list of available systems. Scientific literature on
fundamental aspects of this technology is abundant [113].
Actually, a number of critical aspects makes difficult
the deposition of conductive materials, which is an impor-
tant challenge for enabling easy deposition on curved
substrates, with consequent drastic simplification of elec-
trical wiring in a number of devices [116].
Unfortunately, printed parts are so far mainly fabricat-
ed for structural or decorative purposes, while printing of
more advanced functional materials is still at the infancy.
Despite the large number of available polymeric materi-
als, only few of them are commonly employed. The most
widespread adopted polymeric materials are based on
polylactic acid (PLA) and acrylonitrile butadiene styrene
blends (ABS). Although various printable materials for
anti static, dissipative, electromagnetic interference
shielding [117] are known at present, conductivity is too
low for reliable electrical circuits or sensors.
Composite materials based on a thermoplastic polymer,
e.g. PLA, as matrix and dispersed conductive material
were widely employed. As to conductive materials,
a number of carbon or metal particles containing poly-
mers were employed [118, 119]. For instance, a composite
consisting of Polymorph, which is a commercial formula-
tion of polycaprolactone (PCL), and carbon black (CB)
as filler was adopted to prepare thin filaments suitable
for FDM printing. Conductive layers of this material,
termed Carbomorph, were then patterned and adopted to
assemble capacitive devices and piezoresitive sensors
[26].
In some cases, printed parts are thermally treated after
deposition for burning out [120] the organic matrix and
sintering the original metal particles, thus leading to pure
metal layers.
In general, filament formulations are complex enough
and often not publicly available, so that a proper correla-
tion of formulation and printing parameters with the re-
sulting deposited materials is difficult. As a matter of
fact, standardization in the formulations is a challenge
since filaments from different suppliers are nominally
similar but quite different. Moreover, batch-to-batch var-
iations of the properties are quite common. It is impor-
tant to note that the in-house development of new formu-
lations is often tricky, since it is difficult to obtain in labo-
ratory constant density and diameter using simple and
low cost extrusion systems. This notwithstanding, FDM
technology has exciting possibilities and is so rapidly de-
veloping as to suggest that in the near future it will offer
the possibility to produce easily high-tech sensors, without
the need of production facilities.
Electroanalysis 2016, 28, 250 – 264 261
Review
4 Conclusions
The rapid prototyping and production of custom-made el-
ementary conductive tracks or of even more complex sen-
sitive elements by profiting from alternative patterning
techniques is presented in this review.
Methods reported resort to readily available materials
and easily accessible tools and are characterized by sim-
plicity of use, low hardware costs, as well as reduced con-
sumption of chemicals. On the whole, these techniques
enable deposition of conductive patterns over a wide
range of rigid and flexible materials and represent valid
manufacturing strategies for assembling biomedical point-
of-care devices, sensors for food safety or quality control
and systems for security applications, such as explosives
and drugs detection.
Moreover, the portability of writing tools and the rapid
growing of open-source building-up softwares and proj-
ects, make these approaches ideal candidates to the use
also in decentralized regions.
It is worth noting that, even if these methods have
been mostly adopted for assembling simple electrical cir-
cuits, they show potentiality to revolutionize the way of
assembling analytical devices, electrochemical sensors/
biosensors and detectors.
A number of directions can be identified that require
further developments, such as i) combination of writing
tools with simple, easy to use and affordable automatic
systems to achieve fast and precise deposition when mass
production is required; ii) increase of the number and ty-
pology of pencil leads and inks, suitable to refill pen res-
ervoirs, exploiting different combinations of active mate-
rials thus extending the number of possible applications;
iii) simplification and standardization of formulation of
inks, pastes, pencil leads and FDM 3D printer filaments,
as well as of their production processes; iv) planning of
deposition materials suitable for one-step patterning of
conductive tracks without the need of post-deposition
heating steps, thus reducing energy consumption during
fabrication and offering at the same time the possibility
of assembling sensors on different polymeric materials; v)
combination of the fabrication of components of analyti-
cal devices, such as fluidics, valves, connectors, with the
deposition of conductive materials to directly integrate
sensitive elements (electrodes, microelectrodes arrays)
and electronics; vi) achievement of conditions enabling
precise patterning also on structures with different
shapes, because the right combination of geometrical pa-
rameters, such as vertex shapes and aspect ratios, can im-
prove the electron transfer efficiency or surface currents
of 3D microstructures [102].
Acknowledgements
The financial support of Italian Ministry of University
and Research (MIUR) is gratefully acknowledged.
www.electroanalysis.wiley-vch.de Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Received: May 22, 2015
Accepted: July 2, 2015
Published online: July 29, 2015
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