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Inkjet-printed optoelectronics
Cite this: Nanoscale, 2017, 9, 965 Zhaoyao Zhan,* Jianing An, Yuefan Wei, Van Thai Tran and Hejun Du*
Published on 07 December 2016. Downloaded by Cinvestav IPN on 07/04/2017 22:22:23.

Received 20th October 2016,
Accepted 6th December 2016
DOI: 10.1039/c6nr08220c
www.rsc.org/nanoscale
Inkjet printing is a powerful and cost-effective technique for deposition of liquid inks with high accuracy,
which is not only of great significance for graphic applications but also has enormous potential for the direct
printing of optoelectronic devices. This review highlights a comprehensive overview of the progress that has
been made in optoelectronics fabrication by the inkjet printing technique. The first part briefly covers the
droplet-generation process in the nozzles of printheads and the physical properties affecting droplet for-
mation and the profiles of the printed patterns. The second section outlines the recent activities related to
applications of inkjet printing in optoelectronics fabrication including solar cells, light-emitting diodes, photo-
detectors and transparent electrodes. In each application field, the challenges with the inkjet printing process
and the possible solutions are discussed before a few remarks. In the last section, a brief summary on the pro-
gress of inkjet printing fabrication of optoelectronics and an outlook for future research effort are presented.

1. Introduction ible electronics for integration, and also adapted to low-temp-

The fast-expanding market of optoelectronic devices, including
photodetectors, light emitting diodes (LEDs), photovoltaics,
and displays, calls for innovative production of nanostructures
from optoelectronic materials in a low-cost, high-throughput,
and large-scale fashion.1,2 The candidates of optoelectronic
materials should be, ideally, compatible with silicon and flex-
School of Mechanical and Aerospace Engineering, Nanyang Technological University,
50 Nanyang Ave, 639798, Singapore. E-mail: zhanhit@hotmail.com,
mhdu@ntu.edu.sg
erature solution processing.3
The solution-processable materials fall into diverse cate-
gories including soluble semiconducting polymers or their
precursor molecules, colloids, and organic or inorganic nano-
particles (NPs).4 The inorganic NPs show a relatively high
stability in the ambient environment. Owing to the tunability
of the formulations and rheology and thereby of designing
inks for variant printing techniques and applications, the solu-
tion-processable materials could readily lend themselves to
printing. The low-temperature nature of the printing process
allows for the fabrication of devices on various types of sub-

Dr Zhaoyao Zhan received his Dr Jianing An received her

B.E. and M.E. degrees in materials B.E. from the Harbin Institute
science and engineering from the of Technology, China in
Harbin Institute of Technology in 2009 and her Ph.D. from
2006 and 2008, respectively, and Nanyang Technological University,
his Ph.D. degree from Nanyang Singapore in 2014. She has been
Technological University (NTU) working as a postdoctoral
in 2013. During 2014–2016, he research fellow at Nanyang
had worked as a postdoctoral Technological University since
researcher at the Chalmers 2014. Her research focuses on fs
University of Technology, laser-based 3D printing of micro/
Sweden. Now he is working as a nanostructures for electrical and
Zhaoyao Zhan research fellow at NTU, Jianing An optical applications.
Singapore. He has co-authored
one book chapter, and published more than 40 technical papers
with citations close to 600 and a H-index of 14. His current
research interests include carbon nanomaterials (carbon nano-
tubes, graphene), printed electronics and sensors.

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strates, ranging from conventional flat and rigid substrates to
the emerging flexible and even curved ones, paving the way to
the development of flexible and conformable electronics.
Among all forms of printing techniques, inkjet printing is a
powerful and cost-effective technique for deposition of liquid
inks with high accuracy, which is not only of great significance
for graphic applications but also has enormous potential for the
direct printing of optoelectronic devices. The peculiar character-
istics offered by inkjet printing include additive patterning,
reduced material consumption, maskless and non-contact depo-
sition, low cost, and the capability of large-scale manufacturing.1
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The direct writing feature of inkjet printing enables deposition
of numerous thin films with the ease of altering the design from
batch to batch. Moreover, inkjet printing is capable of depositing
a given material in pre-determined sites on a substrate that has
pre-existing patterns, where contamination or damage of pat-
terns would be induced with other deposition processes.
This review highlights recent advancements of inkjet print-
ing-based fabrication, in terms of active deposition and elec-
trode deposition, of optoelectronic devices, such as solar cells,
LEDs, photodetectors, and transparent electrodes. The inkjet
printing techniques are able to overcome these challenges
existing in traditional fabrication processes, therefore produ-
cing new functionalities and/or boosting the cost-effectiveness
and performance of the existing ones.
2. Principles of inkjet printing
technology
2.1 Droplet formation
Inkjet printing, based on a drop-by-drop deposition fashion,
has been invented and used for typewriting and recording for
over 50 years. The droplets of ink with low viscosity are ejected
Dr Yuefan Wei is a research
fellow in the School of
Mechanical and Aerospace
Engineering of Nanyang
Technological University. She
received both her B.E. and M.E.
in Materials Science and
Engineering from Tianjin
University in 2006 and 2008,
respectively. She obtained her
PhD degree from Nanyang
Technological University in
Yuefan Wei 2013. Her research interest and
expertise are fabrication, physics
and characterization of photovoltaic materials and devices, chemi-
cal vapor deposition and hydrothermal synthesis of nano-
structured materials, three dimensional (3D) printing technology,
energy conversion and storage, photoelectrochemical cells, and
self-cleaning technology.
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by a nozzle in the printhead and can be formed through either
a continuous or a drop-on-demand (DOD) manner. In the con-
tinuous operating process, an ink-supply pump pressurizes the
ink and ejects it from the nozzle, generating a stream of liquid
droplets. In the course of droplet generation, the droplets are
selectively charged by the electric voltage applied to the
nozzle. The charged droplets will be deflected by an electric
voltage on the deflection electrode and separated from the
uncharged ones. After that the charged droplets will reach the
print substrate, while the uncharged ones which are not used
for printing are caught by the gutter and carried back to the
ink tank. The advantage of continuous printing is the high fre-
quency of droplet generation and printing. Nowadays,
however, the DOD system is more widely employed because it
has lower system complexity and offers higher controllability
and accuracy of droplet displacement.5,6
In a DOD system, the ink droplets are jet from the nozzle by
pulses generated by a thermal resistor, a piezoelectric transdu-
cer, a thermal buckling or an acoustic wave. A thermal print-
head uses a thin film resistive heater to rapidly vaporize a thin
layer of the ink liquid (within a few microseconds) to form a
fast expanding bubble which pressurizes the ink solution (see
Fig. 1). The pressure for actuation should approximate the
saturated vapor pressure of the ink liquid at its superheat
limit. Consequently, the pressurized droplet in the nozzle will
be ejected from the nozzle, as schematically illustrated in
Fig. 1. Thermal DOD technology features simple design and
low costs, however it is confined to vaporizable inks due to the
requirement of the bubble formation. The elevated operating
temperature (ca. 300 °C) makes it inappropriate for polymer-
based printing. The piezoelectric DOD system has been widely
employed to bypass this limitation. In the piezoelectric print-
head, a piezoceramic transducer is electrically stimulated to
induce mechanical actuation according to its resonant modes.
Mr Van-Thai Tran received his
Bachelor’s degree from the
Faculty of Mechanical
Engineering, Ho Chi Minh
University of Technology,
Vietnam in 2014. Since August
2014 he has been pursuing his
Ph.D. study in the School of
Mechanical and Aerospace
Engineering, Nanyang Techno-
logical University, Singapore
under the supervision of Prof.
Van Thai Tran Du Hejun and Dr Yang Hongyi
(SIMTech, Singapore). His
research interests include additive manufacturing and functional
material applications, with a particular focus in the field of zinc
oxide and MEMS devices.
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Fig. 1 Droplet formation process in a thermal and piezoelectric inkjet
nozzle.
The mechanical pulse of the piezoelectric membrane propa-
gates into the nozzle, pressurizing the ink solution, and eject-
ing one droplet from the nozzle (as shown in Fig. 1). Thus, the
volume and final velocity of a droplet also rely on the driving
voltage on the transducer. In practice, a printhead usually inte-
grates a big and dense nozzle array containing a large number
of separate nozzles to promote the printing production.
The formation of ink jets starts from ejection and stretch-
ing of the liquid, followed by detachment of the liquid from
the nozzle, contraction of the liquid ligament, breakup of the
liquid ligament into main drops and satellites, and finally
merging of the main drops and satellites.5 The control of drop
generation and subsequent flight of the jetted inks requires
profound studies into the liquid properties at high shear rates,
stretching and contraction of fluid ligaments, drop generation
Dr Hejun Du is currently an
associate professor in the School
of Mechanical and Aerospace
Engineering, Nanyang Techno-
logical University, Singapore. He
obtained both B.E. and M.E.
from the Nanjing University of
Aeronautics and Astronautics,
China, and his PhD from
Imperial College, UK. His
research interests include (1)
numerical and computational
Hejun Du methods for engineering
applications; (2) MEMS and
microfluidics; (3) smart materials and their engineering
applications. He has published over 200 international refereed
journal papers, more than 100 conference papers and a few
invited book chapters. His journal papers were cited over 4000
times in the SCI with a H-index of 36.
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and flight, as well as the aerodynamic and electrostatic inter-
actions of the fluid drops in flight. In the flight, smaller satel-
lite drops would also be created slightly after the drop for-
mation, which recombine with the primary drops after a few
periods. Although satellite formation is quite common during
the droplet formation, it could be minimized or even elimi-
nated by judiciously selecting the printing parameters.5
Generally, the formation of droplet is affected by the ink’s
fluid properties. Fromm7 introduced a dimensionless number
Z to categorize the fluid properties and to analyze the mech-
anics of drop formation in printheads:
Z ¼ ðdργÞ1=2 =τ
where ρ, γ and τ are the density, surface tension and viscosity
of the ink, respectively, and d is a characteristic length, which
is the nozzle diameter in the case of DOD printheads. By refin-
ing the prediction of Fromm, Reis et al.8 proposed that the ink
droplet could be formed when Z ranges from 1 to 10 after
studying alumina wax suspensions with a range of concen-
trations. The lower limit of the Z number is determined by the
viscosity dissipating the pressure pulse, while the creation of
satellites rather than a single droplet is the determinant of its
upper limit. Furthermore, when Z is in the range of 1 < Z < 14,
the droplet volume rises with the increase of Z, which is in
accordance with Fromm’s prediction. However, in practice,
systems with Z numbers much larger than 10 are also printa-
ble if the satellites recombine with the primary droplet in few
periods. Schubert et al.9 found that various solvents that have
low viscosities in the range of 0.4 to 2 mPa s and surface
tensions in the range of 23 to 73 mN m−1 are also printable
although their calculated Z numbers are in the range of 21 to
91. The vapor pressure of the solvents was found to be the
crucial factor of the printability. For solvents with vapor press-
ures higher than approximately 100 mmHg, the printed dro-
plets are unstable or even no droplets could be produced.
The non-contact nature of inkjet printing allows for the
deposition of nanomaterial inks on a wide range of substrates
including polymers, oxides, metals, and biomaterials. Another
advantage of inkjet printing is the feasibility of printing arbi-
trary patterns over a large working area. In addition, the use of
nanomaterials in the dispersion overcomes the solubility limit-
ations of the inks, resulting in higher stability of the printing
process. However, some precautions should be taken to
prevent precipitation or aggregation of dispersion-based nano-
materials in the ink for long-term printing, because the pre-
cipitation or aggregation of the ink contents is the main con-
tribution to clogging of the nozzle, leading to the ‘first drop
problem’. The pre-printing cleaning, capping or stirring of the
ink will be beneficial to alleviate the ‘first-drop problem’
effect.
Generally, for DOD printheads, the ink viscosity must be
within the range of 1–30 mPa s. Because the piezoelectric
transducer and resistive heater only generate limited power,
printing high-viscosity materials is difficult for conventional
inkjet printing. Usually, several picoliters of the ink are ejected
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in order to produce patterns with feature sizes of 20–50 µm
and a thickness lower than 1 µm. This coarse resolution is
caused by the combined effects of droplet diameters which are
usually larger than ∼10–20 µm and placement errors which are
in the range of ±10 µm at the standoff distances of ∼1 mm. In
electrohydrodynamic (EHD) printing, which uses electric fields
rather than a resistive heater, piezoelectric transducer or
acoustic wave to eject the ink liquid, the droplets are created
by a fine jet generated at the apex of the conical ink meniscus
at the tip of the nozzle (see Fig. 2).10 Unlike conventional
inkjet printing processes, EHD printing pulls the liquids
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rather than pushing them, thus printing of the high viscosity
ink is not challenging for EHD printing. The advantages of
EHD printing include high resolution (submicron), flexibility
in the ink formulation design, and easy jetting without clog-
ging the nozzle. EHD printing has enormous potential in
printing of complex and high-resolution features and is
opening up new ways toward nanotechnology.
2.2 Control of pattern morphology and feature size
Ink volatility and viscosity are critical parameters of controlling
the pattern morphology. Non-uniform films are easily formed
due to the ‘coffee-ring’ effect or central ‘mountaintop’ effect
which induces capillary12 or Marangoni13 flows during the
evaporation of the ink solvents. Coffee-ring edges usually
Fig. 2 Structure of nozzles and schematic illustration of a high-resolu-
tion EHD printer. (a) SEM images of a glass microcapillary nozzle (2 µm
internal diameter). The entire outer surface of the nozzle and its inner
surface near the tip are coated with functionalized gold. The tip region
is shown in the magnified images on the right panel. (b) Configuration of
the nozzle and the substrate for printing. The ink droplet was ejected
from the nozzle to a moving substrate to produce the line patterns. (c)
Setup of an inkjet printer. The gold-coated nozzle was connected to a
grounded electrode under the substrate by a power supply. Reproduced
with permission from ref. 10, Copyright 2007, Nature Publishing Group.
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appear when NPs in the ink accumulate along the perimeter of
the drying droplet due to inhomogeneous evaporation of the
solvents.14 The uneven morphology leads to the formation of
electric defects.
To overcome the coffee-ring effect, the evaporation process
of the solvent has been modified by introducing drying agents,
precisely controlling the humidity in the ambient environment
during the solvent evaporation, or tuning the heating rate.14–17
In an optimized solvent mixture, the drying agent has a higher
boiling point (B. P.) and a lower surface tension compared
with the main solvent. During the drying, the main solvent
having a lower B. P. and higher surface tension evaporates
faster at the contact line creating an outward flow, which is
gradually delayed as the contact line approaches the solvent
with a larger fraction of the drying agent. Meanwhile, an
inward flow (Marangoni flow) will be developed by the surface-
tension gradient over the whole droplet. The outward and
Marangoni flows continuously circulate the ink contents
inside the fluidic droplet, producing a uniform assembly of
the ink contents. The drying process of a droplet inkjet-
printed with a mixed-solvent ink is schematically shown in
Fig. 3, where chlorobenzene (CB) is the main solvent, and
dodecane is the drying agent. Fig. 4 presents the non-uniform
and uniform surface profiles of Al2O3 NPs respectively pro-
duced by a water single-solvent ink and a dimethylformamide
(DMF)/water mixed-solvent ink.14 The addition of DMF could
Fig. 3 The process of droplet drying after inkjet printing with a mixed-
solvent ink. Reproduced with permission from ref. 11, Copyright 2008,
John Wiley and Sons.
Fig. 4 SEM images and the corresponding height profiles of an Al2O3
ink droplet. The Al2O3 NPs were produced with the ink of: (a) water
single-solvent and (b) DMF/water mixed-solvent. Reproduced with per-
mission from ref. 14, Copyright 2011, Elsevier.
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greatly improve the final inkjet-printed pattern profile by intro-
ducing the recirculating flow. The heating process is also
found to be critical in controlling the coffee-ring effect, since
the solvent evaporation is also highly dependent on the
heating process. Gradual heating could effectively restrict the
convection flow during the evaporation in a printed low-
viscosity Ag (Ag) NP ink, causing the lines to become convex
with the homogeneously and very densely packed NPs, which
greatly enhances the electrical conductivity of inkjet-printed
Ag lines.17
Apart from the long-standing coffee-ring effect, the mor-
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phology of printed patterns could also be greatly affected by
many other factors, such as the aerodynamic effect, electro-
static interaction of droplets, satellites, and interaction
between the liquid ink and the substrate. It is quite challen-
ging to print long-distance and continuous lines, with con-
trolled feature sizes and morphology.5 To minimize the feature
size of the printed patterns, it is essential to limit ink spread-
ing on the surface. Changing the surface energy of the sub-
strate and creating patterned chemical/physical structures on
the substrate are efficient methods to control the wetting be-
havior of the droplets on the substrate and to increase the
printing resolution. The droplets on a non-wetting substrate
tend to partially recede or even completely rebound, while the
ones on a wetting surface are prone to spread away,18 giving a
flat-disk-shaped pattern with a diameter larger than the orig-
inal droplet, resulting in very coarse printed structures.
Although dewetting treatment could to some extent improve
the pattern resolution, bulges will be formed on lines that are
unstable on substrates with too low surface energy, which
would locally broaden the printed graphics and degrade the
continuity of printed features. In addition to surface energy
modification, pre-patterning the surface with varying wetta-
bilities or surface topographies in different regions of the
substrate could benefit reducing the spreading of the ink solu-
tion. Ultrafine gaps can be created by a self-aligned printing
method that relies on differentiation of wettability.19 Another
scenario lies in optimizing the ink materials and formulations,
which not only influence the droplet formation process, but
also prescribe the printing resolution and the device perform-
ance. The utilization of an ultrafine nozzle is desirable for
printing patterns with small feature size if the clogging could
be avoided by using low viscosity inks with fine NPs. Addition
of special additives into the ink dispersion is also useful for
tuning the viscosity of the ink and benefiting inkjet printing of
high-resolution patterns.18
3. Applications
3.1 Solar cells
Solar cells could directly convert solar irradiation into electri-
cal energy and thus offer the promise to relieve our reliance on
the long-standing fossil energy resources which have caused
serious environmental issues to our home planet. The use of
solar cells, however, has not been expanded yet due to the
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unfavorable cost. Since the first report of organic solar cells by
screen printing,20 this technique has been presenting promise
of developing industrially scalable low-cost fabrication pro-
cesses. However, the ever growing demand for improved per-
formance has led to an expanding interest in inkjet printing
which enables printing features with higher resolution, result-
ing in lower shadowing losses and reduced manufacturing
costs. In addition, inkjet printing technology allows for the
deposition of active materials in specific areas of the pre-
patterned substrate. The first demonstration of inkjet printing
of a thin-film library of donor/acceptor systems used in bulk
heterojunction (BHJ) organic solar cells was reported by Marin
et al.21 In addition, the morphology studies on inkjet-printed
films with atomic force microscopy (AFM) suggested the for-
mation of homogeneous structures. Then Steirer et al.22 sys-
tematically investigated the critical parameters for both inkjet
and ultrasonic spray deposition of poly(3,4-ethylenedioxythio-
phene) polystyrene sulfonate (PEDOT:PSS) thin films on com-
mercial indium tin oxide (ITO) for organic photovoltaic device
fabrication. Their study showed that the efficiency of organic
solar cells with an inkjet-printed PEDOT:PSS hole conducting
layer were comparable with that of solar cells fabricated
through the traditional spin-coating process. The drop spacing
and the substrate temperature are critical parameters in inkjet
printing; while for ultrasonic spray coating, the substrate
temperature and the solution flow rate will play critical roles.
PEDOT:PSS films produced by optimized inkjet printing, ultra-
sonic spraying and spin coating were compared in a proto-
typical BHJ organic solar cell which employs a poly(3-hexylthio-
phene) and 6,6-phenyl-C61-butric acid-methyl ester (P3HT:
PCBM) blend as the absorber. The results revealed that the
efficiencies of the devices fabricated by the three processes
were comparable (in detail, the efficiencies were 3.3% 3.5%
and 3.6%, for inkjet printing, spray deposition, and spin
coating respectively). Furthermore, hybrid transparent conduc-
tive films prepared by inkjet printing PEDOT:PSS and other
conductive components have also been demonstrated for
replacing the ITO transparent electrodes in organic solar cells,
which will be covered in section 3.4.3.
It is found that the morphology of inkjet-printed films
could be dramatically tuned by using additives, and thus
affects the properties of organic optoelectronics and the
overall performance of the devices. Xia et al.23 fabricated
organic solar cells by using a blend of poly(9,9-dioctylfluorene-
co-benzothiadiazole) (F8BT) with poly(9,9′-dioctylfluorene-
co-bis-N,N′-(4-butylphenyl)-bis-N,N′-phenyl-1,4 phenylene-
diamine) (PFB), and organic light emitting diodes (OLEDs) by
using a blend of F8BT with poly(9,9-di-octylfluorene-co-N-(4-
butylphenyl)diphenylamine) (TFB). They compared the devices
with a film produced by either inkjet printing or spin-coating.
It has been discovered that the rapid drying of the small
inkjet-printed droplets resulted in a finer phase separation,
producing OLEDs and organic solar cells with even better per-
formances and a higher efficiency than those prepared by the
traditional spin coating method. However, a critical issue with
the films produced by inkjet printing is the non-uniformity in
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thickness, which may be due to the use of only a single solvent
p-xylene. This problem could be possibly alleviated by using a
solvent mixture. Hoth et al.24 used a blend of P3HT:PCBM in a
mixed solvent of o-dichlorobenzene and mesitylene to inkjet
print organic solar cells on PEDOT:PSS coated ITO, where
Ca : Ag was deposited as the top cathode. They also suggested
that by optimizing the ink solvent formulation, the morpho-
logical and interfacial properties of the printed P3HT:PCBM
blend photoactive layer could be significantly improved. For
example, a mixture of high and low boiling solvents, 68% of
ortho-dichlorobenzene (ODCB) and 32% of mesitylene could
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print organic solar cells with an intimate morphology in the
P3HT:PCBM blend, giving a better solar cell performance with
a larger short-circuit current of 8.4 mA cm−2, an open-circuit
voltage of 0.54 V, a filling factor of 0.64, and a higher power
conversion efficiency (PCE) of 2.9%. While, the device pre-
pared with the inkjet-printed P3HT:PCBM blend with the tetra-
lene solvent shows a much large roughness and a poor distri-
bution of PCBM in the P3HT domain, thus, outputting a poor
performance. More recently, Hoth et al. further improved the
performance of inkjet-printed organic solar cells by using the
combined regioregularity(RR)-96%-P3HT and the ODCB/
mesitylene solvent mixture to control ink drying and film
formation processes. They have obtained a suitable gelation
time, improved the morphology of the P3HT:PCBM layer, and
achieved an impressive PCE of 3.5%.25 Eom et al. reported
P3HT:PCBM blend organic solar cells produced with the
inkjet-printed PEDOT:PSS hole transporting layer, and
suggested that the addition of a certain amount of the glycerol
and ethylene glycol butyl ether (EGBE) surfactant into PEDOT:
PSS inks improved the surface morphology and conductivity of
the PEDOT:PSS hole transporting layer, resulting in enhanced
performance of the organic solar cells. Using the optimized
ink formulation of PEDOT:PSS to print the hole transporting
layer and the P3HT:PCBM blend as the photoactive layer, they
have achieved a PCE of 3.16% in P3HT:PCBM based BHJ solar
cells.26
They further demonstrated the organic solar cells fabricated
by inkjet printing both the photoactive P3HT:PCBM layer and
the PEDOT:PSS hole transporting layer, and the results
suggested that adding high B. P. additives, including 1,8
octanedithiol (ODT), ODCB and chloronaphthalene (Cl-naph),
into the photoactive dispersion in the CB solvent drastically
affected the morphological and optoelectronic properties, and
overall solar cell performance. A device printed from an ODT-
formulated ink exhibited the best overall performance with a
PCE of 3.71%. Thus, developing a proper formulation of multi-
component inks to tune the morphological properties of the
inkjet-printed BHJ solar cells is an essential step for the inkjet
printing of high performance organic photovoltaics. The
inclusion of high B. P. additives enables a controlled drying
and thus allows for sufficient time for film formation of the
photoactive layer, thereby improving the crystallinity of the
photoactive polymer. Moreover, the wettability of the P3HT:
PCBM inks on the PEDOT:PSS layer could also be enhanced,
thus the produced active layer would have high uniformity and
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a fine film morphology and also the coffee-ring effect would be
decreased.28
Though inkjet printing technology has manifested its versa-
tility in fabricating active components and/or hole conducting
layers, the development of an ambient environment compati-
ble inkjet printing process is highly desirable. Aernouts et al.29
have demonstrated inkjet-printed P3HT:PCBM blend solar
cells in the ambient environment by utilizing a polymer: fuller-
ene blend dissolved in a mixture of the main solvent CB and
the high B. P. solvent tetrahydronaphthalene (THN). They
found that a balance between ink viscosity and surface wetting
is critical to a smooth active layer with a small surface rough-
ness, producing devices with a PCE of 1.4% under simulated
AM1.5 conditions. The addition of a high B. P. solvent could
also help to prevent clogging of the nozzle. Recently, Jung and
co-workers27 reported the fabrication of all-inkjet-printed,
air-processable organic solar cells with the structure of
PEDOT:PSS/poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-
thienyl-2′,1′,3′-benzothiadiazole)]:[6,6]-phenyl-C71-butyric acid
methyl ester (PCDTBT:PC70BM)/ZnO/Ag. A high-conductivity
PEDOT:PSS aqueous dispersion was printed to replace ITO as
the anode. 5 wt% dimethyl sulfoxide (DMSO) and 0.1 wt%
fluorosurfactant were added into the PEDOT:PSS ink to
prepare a highly conductive and uniform film. A PCDTBT:
PC70BM (at ratio of 1 : 4) donor/acceptor blend dispersed in a
5 : 4 : 1 volume mixture of the CB, mesitylene (MT) and chloro-
form (CF) ternary solvent, was then printed onto the PEDOT:
PSS layer. It was found that the inkjet-printed PCDTBT:
PC70BM blend layer presented similar morphological pro-
perties (see Fig. 5) and excited state dynamics with its spin-
coated counterparts. The all-inkjet-printed organic photo-
voltaic devices exhibited an average PCE of 2%. A noteworthy
advantage in this work was that all the fabrication and
measurement processes were performed in air at room temp-
erature. The performance could be drastically improved to 5%
by depositing the cathode via evaporation. The effects of addi-
tives on the inkjet-printed organic solar cells are summarized
in Table 1.
Despite its versatile roles in organic solar cell fabrication,
inkjet printing of inorganic solar cells remains a challenge.
The suspended particles in inorganic inks have a strong ten-
dency to agglomerate, leading to an increase in viscosity and
thus clogging of the nozzles. These challenges could be miti-
gated or eliminated by designing ink formulations, for
example, replacing the inorganic NPs in the ink with their dis-
solvable precursors could greatly alleviate the ink agglomera-
tion and clogging of nozzles. Wang et al.30 have fabricated
chalcopyrite CuInxGa1−xSe2 (CIGS) thin film solar cells by
inkjet printing CIGS precursors on a molybdenum (Mo) elec-
trode, followed by selenization of the printed CIGS precursor
to form CIGS light absorber layers, and deposition of n typed
CdS layers and ZnO window layers, as shown in Fig. 6. They
achieved inkjet-printed CIGS solar cells with a short circuit
current, open circuit voltage, filling factor, and total area PCE
of 29.78 mA cm−2, 386 mV, 0.44, and 5.04%, respectively.
Pi et al. have also demonstrated inkjet printing the silicon
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Fig. 6 (a) Fabrication steps of CIGS solar cells. (b) Top view of a real
device. (c) I–V characteristics of the CIGS solar cell. Reproduced with
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permission from ref. 30, Copyright 2011, Elsevier.

application of the inkjet printing technique in solar cell

Fig. 5 (a) Schematic structure of an all-inkjet-printed, air-processable
organic solar cell and (b) energy level alignment of each component. All
the four layers are produced by a single nozzle inkjet printer and all pro-
cesses have been conducted in the ambient environment. The AFM
images of inkjet-printed PCDTBT:PC70BM films (c) spin-coated from
100% CB; (d) spin-coated from a solvent mixture of 50% CB, 40% MT
and 10% CF; and (e) inkjet printing from a solvent mixture of 50% CB,
40% MT and 10% CF. Reproduced with permission from ref. 27,
Copyright 2014, John Wiley and Sons.
quantum dots (Si-QD) ink onto polycrystalline Si solar cells,
and found that the PCE of polycrystalline Si solar cells could
be improved by 2% (from 17.2% to 17.5%), which was attribu-
ted to both the down-shifting absorption band from the UV
zone (<400 nm) to a long wavelength around 773 nm, and also
the absorption enhancement by porous Si-QD films on the
solar cell surface.31 The successful demonstration of
inkjet printing of inorganic layers will significantly extend the
fabrication.
In the past decade, hybrid organic–inorganic perovskite
solar cells have emerged as a competitive solution for solar
energy harvesting, with the PCE boosting from the initial 2.2%
to over 20%.33,34 It has been revealed that the ideal photo-
voltaic properties of the perovskite materials (CH3NH3PbI3 and
CH3NH3PbI3−xClx), including appropriate and tunable direct
band gaps, high mobilities of electrons and holes,35 high
absorption coefficients, excellent (balanced) carrier transport
diffusion lengths (100 to 1000 nm),36 and high defect toler-
ance, contributed to the upsurge of the PCE. Furthermore, the
perovskite materials are solution-processable, low-cost, and
suitable for inkjet printing. Wei et al. have demonstrated
inkjet printing perovskite solar cells with a planar structure
where a nanocarbon layer with a precisely controlled pattern
and interface was utilized as the hole-extraction layer, as
shown in Fig. 7a–e.32 They found that the CH3NH3PbI3 photo-
active layer could be readily inkjet-printed and converted by
the formulating ink precursor (nanocarbon and CH3NH3I) for
in situ transformation of the PbI2 layer. After printing, an inter-
penetrating seamless interface could be instantly constructed
between the CH3NH3PbI3 active layer and the carbon hole-
extraction electrode, which remarkably reduced the charge
recombination, as shown in Fig. 7c, e and f. The final device
structure of the TiO2/CH3NH3PbI3/C solar cells is displayed in
Fig. 7f. The energy level diagram in Fig. 7g indicates the

Table 1 Effects of additives on performance of inkjet-printed organic solar cells

Printed materials Solvents Additives Performance and reasons

PEDOT:PSS 22
Diluted with 75% DI water — PCE = 3.3%, comparable with that of spin-coated devices.
F8BT:PFB23 p-Xylene — PCE ∼ 2% at a wavelength of 380 nm, which is higher than spin-coated
devices, due to finer phase separation.
P3HT:PCBM24,25 ODCB/mesitylene — PCE = 2.9%–3.5% The solvent mixture controlled ink drying and
Tetralene PCE = 1.29% improved the film morphology.
PCDTBT:PC70BM 27
ODCB/mesitylene — PCE = 4% The addition of chloroform leads to a
Chloroform PCE = 5% homogeneous active layer.
PEDOT:PSS26 Tetralene — PCE = 2.09% The additives improved the surface morphology
Glycerol/EGBE PCE = 3.16% and conductivity of the PEDOT:PSS hole
transporting layer.
P3HT:PCBM28 Chlorobenzene — PCE = 1.97% The additives improved the film morphology, light
ODT PCE = 3.71% absorption and reduced recombination losses.

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Fig. 7 (a) Fabrication flowchart for inkjet printing the C/CH3NH3PbI3
planar perovskite solar cells. For comparison, another fabrication strat-
egy was also demonstrated in a separate step 3 and 4 to convert PbI2
into CH3NH3PbI3; (b) SEM image (cross-section view) of the TiO2
compact layer deposited by TiCl4 treatment. (c) SEM image (cross-
section view) of the multiple spin-coated TiO2/PbI2 thin film. (d, e)
Cross-sectional SEM images and the corresponding schematic illus-
tration of inkjet-printed TiO2/CH3NH3PbI3/C solar cells from the C ink
(d) and the C + CH3NH3I ink (e); (f ) a basic configuration; (g) energy
level diagram; (h) J–V characteristics; (i) the wavelength-dependent
IPCE profiles of the solar cells respectively fabricated from the C ink and
the C + CH3NH3I ink. Reproduced with permission from ref. 32,
Copyright 2014, John Wiley and Sons.
charge transfer and transport processes in the solar cells.
When the solar cell is under light excitation, electron–hole
pairs are generated in the CH3NH3PbI3 layer, and then elec-
trons and holes will transfer to the conduction band and the
valence band of CH3NH3PbI3, respectively. Due to the proper
energy level alignment, the electron will be injected from the
conduction band (∼3.86 eV) of CH3NH3PbI3 to the conduction
band of TiO2 (∼4.00 eV), and finally collected by the fluorine-
doped tin oxide (FTO) glass. Meanwhile, the holes are accepted
by the nanocarbon layer through the C/CH3NH3PbI3 interface
from the valence band of CH3NH3PbI3 to C, as shown in
Fig. 7g. Consequently, a considerably higher PCE up to 11.60%
was produced by the perovskite solar cell, as displayed in
Fig. 7h and i. This method demonstrates a major step towards
fabricating highly efficient perovskite solar cells in a low-cost,
large-scale, metal-electrode-free manner.
The above examples indicated that inkjet printing is a cost-
effective processing candidate for the incorporation of photo-
voltaic devices into electronic applications or production of
photovoltaic modules. Though the present performance of
inkjet-printed devices could not fulfill the requirement of com-
mercial applications, the progress made thus far is promising.
3.2 Light emitting diodes
As emerging optoelectronic devices, LEDs could emit light
with high luminous efficacy and brightness. Intensive studies
have been carried out for employing semiconductor colloidal
nanocrystals (NCs) and organic semiconductors as consti-
tutional components in LEDs, including the color filter, the
emitting layer, and the hole-transport layer.1,38 The process of
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optimizing LED device structures usually needs adjustment of
different layer thicknesses and determination of optimal
device designs. Repeated device fabrication and measurement
procedures are in turn required for the optimization, which
normally consume a lot of time and materials.1 Inkjet print-
ing, which is based on a direct writing process and avoids the
use of any mask, is thus a suitable technique for combinatorial
studies of various devices.39,40
Tekin et al.41 utilized the inkjet printing technique to study
the effects of various side chains and film thicknesses on
the emission properties of six different poly( phenylene-
ethynylene)/poly( p-phenylene vinylene) (PPE/PPV)-based
π-conjugated polymers. Thanks to the inkjet printing tech-
nique, they could examine the influences of various para-
meters (side chain and film thickness) in a parallel manner.
The results suggested that the emission wavelength of the
printed polymers was strongly dependent on inter-chain inter-
actions which are stronger for thicker films and varied with
side chains. In addition, the emission color could be signifi-
cantly changed by annealing by increasing the aggregation of
polymer chains.
Photoluminescence (PL) of inkjet-printed CdTe NPs was
demonstrated by the same group.37 An aqueous mixture of sur-
factant stabilized CdTe NPs with 1 wt% polyvinyl alcohol (PVA)
and varied concentrations of ethylene glycol (0–20 vol%) was
inkjet-printed on both ITO and glass. They observed that the
coffee-ring formation was drastically suppressed with 2 vol%
of glycol, while films with a lower roughness were only pro-
duced when PVA was included in the mixture, demonstrating
the key role of the solvent mixture in controlling the mor-
phology of the final films. The PL results demonstrated that
strong emission would come out when CdTe NPs were
embedded in the PVA matrix. But when poly(diallyldimethyl-
ammonium chloride) (PDDA) was used as the matrix, the emis-
sion of CdTe NPs was weakened. The enhancement in the PL
intensity of the films where the CdTe NPs were embedded in
PVA was attributed to the increase of the inter-particle space,
preventing the inter-particle interaction that results in self-
quenching of the PL (Fig. 8a). In the films printed from the
mixture of large particles (3.5 nm) and small particles
(2.6 nm), the gradual decrease of the emission intensity of the
small particles (green-emitting), and the gradual increase of
the PL intensity from the larger particles (red-emitting) were
observed, indicating the Förster resonant energy transfer
process where the energy transfers from the smaller donor
NPs to the larger accepter NPs, as shown in Fig. 8b. This
method in principle can be used for practical LED fabrication,
considerably reducing the process and environmental fluctu-
ations and uncertainties in sequential processing of varied
device configurations.
Inkjet printing was also employed to prepare OLEDs based
on small molecules which were commonly prepared through
vacuum processes. Jung et al.42 demonstrated that fabrication
of OLEDs by inkjet printing 5 wt% tris(2-phenylpyridine)
iridium(III) (Ir( ppy)3) doped in the 4,4′-bis(carbazol-9-yl)bi-
phenyl (CBP) ink as the light emitting material on a 40 nm-thick
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Fig. 8 (a) Optical images of an inkjet-printed library of CdTe NCs/PVA
composite layers emitting at different wavelengths. The PVA content in
the solution used for printing was systematically varied from left to right
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panels in each row: from 0 to 1.4 wt% with an increment step of
0.2 wt%. The corresponding molar ratios of PVA/CdTe NCs in the films
are from 0 (0/1.6 × 10−8) to 21.9 with an increment step of 3.12. (b)
Photograph of an inkjet-printed library containing mixed green-and red-
emitting CdTe NCs (top). The corresponding PL spectra (bottom).
Reproduced with permission from ref. 37, Copyright 2006, John Wiley
and Sons.
4,4′,4″-tris(carbazol-9-yl)triphenylamine (TCTA) hole transport-
ing layer. The OLEDs exhibited high performance with high
power and the external quantum efficiencies (EQEs) of
29.9 lm W−1 and 11.7% respectively.
Haverinen et al.43 have reported bright LEDs from inkjet-
printed CdSe/ZnS quantum dots (QDs) sandwiched between a
hole transporting polymer and a 1,3,5-tris(2-N-phenylbenzimid-
azolyl (TPBi)) electron transport layer. Octadecylamine stabil-
ized CdSe/ZnS QDs were dissolved in CB and inkjet-printed in
air onto the cross-linked poly(N,N′-bis(4-butylphenyl)-N,N′-bis
( phenyl)benzidine) ( poly-TPD) layer. Subsequently the printed
structure was covered by 20 nm of the TPBi electron transport
layer and also a LiF/Al cathode through vacuum deposition.
The LEDs showed an EQE and a brightness of 0.19% and
381 cd m−2 (at 15.9 V), respectively. Furthermore, inkjet print-
ing of CdSe/ZnS QDs also extended its display applications by
printing devices on a pre-patterned substrate with a quarter
video graphics array. The structure of the device was designed
as glass/ITO/poly-TPD/printed QDs/TPBi/LiF/Al, with 243
pixels under common cathode. The operational voltages which
were defined at a brightness of 1 cd m−2 of devices for 10
drops per pixel are 6 V and for 15 drops per pixel are 10.6 V.
The maximum brightness of 150 cd m−2 can be obtained at
around 12 V and 16 V for the device with 10 and 15 drops per
pixel, respectively (Fig. 9). This study also demonstrated that
control of the emitted color could be simply achieved by opti-
mizing the number of printed drops per pixel. Wood et al.44
reported a planar, full-color alternative current driven-electro-
luminescence display comprising inkjet-printed luminescent
CdSe/ZnS QD thin films which first absorb blue electrolumine-
scence from a phosphor layer consisting of ZnS : Cu powders
and then emit photons at a longer wavelength characteristic of
the CdSe/ZnS QD band gap. They inkjet-printed the CdSe/ZnS
QDs and polyisobutylene (PIB) ink on ITO to form the red–
green–blue emission layers and coated the phosphor layer on
the top of the QD–PIB composite layer. It was also found that
the coffee-ring effect could be suppressed by optimizing the
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Fig. 9 (a) Emission spectra of devices with ten drops per pixel (dashed
curve) and 15 drops per pixel (solid curve); (b) luminance vs. applied
voltage. Inset: An optical photograph of QD LEDs (243 pixels with a
common cathode) at the operation voltage of 12 V. Reproduced with
permission from ref. 43, Copyright 2009, AIP Publishing LLC.
ratio of octane to hexane in the solvent mixture. The control
over luminance and color is critical for specific display appli-
cations and it could be tuned by optimizing the thickness of
the QD–polymer composite layer.
Singh et al.45 fabricated OLEDs by inkjet printing a polymer
ink which comprises poly(9-vinylcarbazole) (PVK) as a hole
transporting polymer and 2-4-biphenylyl-5-4-tertbutyl-phenyl-
1,3,4-oxadiazole (PBD) as an electron transporting polymer. Ir-
based phosphorescent macromolecules anchored on a poly-
hedral oligomeric silsesquioxane (Ir@POSS) molecule were
also added in the ink as a luminescent dye. The device demon-
strated a peak luminance of more than 6000 cd m−2 with a
relatively low turn-on voltage of 6.8 V (defined at a luminance
of 5 cd m−2), and a quantum efficiency of 1.4%. However, it
was indicated that the interface roughness (resulting from the
coffee-ring effect) of the printed layers significantly determines
the device performance. They further boosted the peak lumi-
nance to 10 000 cd m−2 with peak quantum efficiencies of
around 2.5%.46 Lee et al.47 developed an inkjet printing
technology for realization of multilayer printing (both light
emitting layer and hole transporting layer) by controlling the
wetting conditions and aligning the multilayer visually. They
have successfully fabricated an OLED and demonstrated the
basic working of OLEDs by sequentially inkjet printing a hole
injection layer with the PEDOT:PSS ink and a light emitting
layer using the poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-
vinylene] (MEH-PPV) ink, although the device could not meet
the requirement of commercialization in terms of the bright-
ness and the operating voltage.
Due to good compatibility between the solution process
and the direct patterning method, the inkjet printing method
has been developed for OLED multicolor displays. Yang et al.48
demonstrated the first polymer light emitting logo by inkjet
printing, wherein the light emitting area was defined by the
printed PEDOT film. Then the inkjet-printed logo was covered
by a spin-coated electroluminescent polymer MEH-PPV
(serving as buffer layer) to seal the pin-holes. Afterwards they
extended the inkjet printing technique to fabricate multicolor
OLED displays with controlled patterning of red–green–blue
multicolor organic light emitting pixels.49 They used the blue-
emission PVK as the buffer layer ( prepared by spin-coating),
while the inkjet-printed dopants, 4-dicyanomethylene-2-
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methyl-6-( p-dimethylaminostyril)-4H-pyran (DCM) and tris
(4-methyl-8-quinolinolato)Al(III)(Almq3), were printed on the
top of the PVK buffer layer. By employing the buffer layer
(blue-emission PVK) as the hole transport layer, multicolor
OLEDs were fabricated, where the orange-red emission was
obtained from the PVK/DCM bilayer structure and green–blue
emission was obtained from the PVK/ALmq3 bilayer structure.
However, the device performance of the inkjet-printed OLEDs
could not compete with that of the OLEDs fabricated by the
thermal sublimation process. Kobayashi et al.50 demonstrated
an OLED display by inkjet printing the light emitting polymer
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PPV for a green emitter and PPV with Rhodamine 101(R-PPV)
for a red emitter. Subsequently, poly(di-octyl fluorine) (F8) was
spin-coated on the top of the PPV layer operating as an elec-
tron-transferring layer or a blue emitter. The device was driven
by a thin film transistor (TFT) substrate and displayed a multi-
color image using the TFT-LED display. The display panel was
about 2-inch large with a pixel size of 11 × 82 µm2 and a line
pitch of 52 µm. The brightness of the display was about
30 cd m−2, consuming 0.7 W of power.
Inkjet printing of real full-color LED display with high
resolution is a stride toward commercial applications. Gohda
et al.51 have demonstrated a 3.6-inch, 202-ppi full-color
AMPLED display using the inkjet printing technique. They
printed three organic layers, a hole transport layer, an inter-
layer and an emission layer with a 7 picoliter inkjet printhead
on a continuous grain-Si active-matrix backplane, as shown in
Fig. 10a. High resolution was achieved by utilizing a smaller
printhead and also appropriate surface treatment of the sub-
strate. The ink formulation is also crucial to control the
surface roughness of the printed organic layer, determining
the final performance of the OLED display. By judiciously opti-
mizing the printing process and ink formulation, they have
achieved very high resolution (202-ppi) display using the inkjet
printing technique (Fig. 10b). Chen et al.52 also reported an
inkjet-printed 65-inch OLED panel with 34 ppi. The panel was
prepared by inkjet printing solution-processable organic
materials for the hole injection layer (HIL), the hole transport-
ing layer (HTL) and the emitting layers (EML) for multiple
colors (red, green and blue) on the TFT backplane (Fig. 11a). It
was discovered that fine-tuning the dry rate in a vacuum after
printing benefits the production of uniform pixels, as shown
in Fig. 11b. They further successfully demonstrated a 200-ppi
OLED panel fabricated by the inkjet printing technique.53
Fig. 10 (a) A cross sectional scratch showing the schematic structure
of an inkjet-printed full-color AMPLED display; (b) an example of the
picture of a high-resolution display. Reproduced with permission from
ref. 51, Copyright 2006, John Wiley and Sons.
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Fig. 11 (a) Schematic diagram of the inkjet-printed OLED structure; (b)
light-on image of the 65-inch OLED display panel; (c) the pixel design
for the 200-ppi resolution panel. (a–b) are reproduced with permission
from ref. 52, Copyright 2014, John Wiley and Sons. (c) is reproduced
with permission from ref. 53, Copyright 2015, John Wiley and Sons.
They found that the resolution of the printed pattern was
determined by the machine accuracy and the drop displace-
ment accuracy. By optimizing the bank angle and width, the
droplet displacement accuracy could be improved, further
enhancing the resolution of the printed patterns. Another
important factor affecting the resolution is the ink volume
which determines the droplet diameter and the final accuracy
of the patterns, as displayed in Fig. 11c.
The resolution could be further improved by optimizing the
design of the pixel pattern. In addition, EHD printing which
could generate droplets smaller than the nozzle aperture will
provide a solution to printing of LEDs for high-resolution
display. Kim et al.54 demonstrated high-resolution printing of
QDs layers with a precisely controlled thickness and lateral
resolution down to submicron meter as active layers in QD
LEDs with EHD inkjet printing. The ink composes QDs (CdSe/
CdZnSeS green or CdSe/CdS/ZnS red core/shell QDs) dispersed
in organic solvents. By applying a bias voltage between a sub-
strate and a metal-coated glass capillary, the ink flow could be
pulled through the fine opening (e.g., 5 µm) at the end of the
nozzle. The AFM characterization results suggested that the
profile of the printed patterns could be precisely controlled
with height resolution in tens of nm and lateral resolution in
sub-µm. The QD layer thickness is a crucial factor determining
the performance of a QD LED. Arbitrary patterning of QD
layers could be realized by the simultaneously programmed
movement of the substrate and control of the voltage. The
final green QD LEDs consisting of ITO/PEDOT:PSS/TFB/
printed CdSe/CdZnSeS QDs/ZnO/Al showed the maximum
luminance and an EQE of 36 000 cd m−2 and 2.5%, respect-
ively. The maximum luminance and EQE of ITO/PEDOT:PSS/
TFB/printed CdSe/CdS/ZnS QDs/ZnO/Al red QD LED are 11 250
cd m−2 and 2.6%, respectively, as shown in Fig. 12. The EHD
inkjet printing of organic small-molecule OLEDs with a pixel
width as small as 5 µm has also been demonstrated recently.55
EHD inkjet printing of small-molecule emission layers with a
flawless surface and a uniform morphology results in the
highly-efficient and reliable operation of OLEDs surpassing
those OLEDs fabricated by conventional inkjet printing
technology. It is believed that the ability to print high-resolu-
tion small-molecule OLEDs represents the substantial poten-
tial of EHD inkjet printing for high-definition and low-cost dis-
plays in future.
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Table 2 Performance of inkjet-printed LEDs

LED or display
Printed ink structure Performance
49
DCM:Almq3 ITO/PEDOT/PVK/ Luminance is around
DCM:Almq3/Ca 25 cd m−2, EQE is
0.05%, which is lower
than that of devices
fabricated by thermal
evaporation, due to
the presence of the
residual moisture and
oxygen.
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CdSe/ZnS QDs43 ITO/poly-TPD/printed EQE of 0.19%,

QDs/TPBi (20 nm)/ brightness of 381
LiF (1.5 nm)/ cd m−2 at 15.9 V.
Al (180 nm)
PVK:PBD:Ir@POSS45 ITO/PEDOT:PSS/PVK: Peak luminance is
PBD:Ir@POSS/BCP/ 6000–10 000 cd m−2,
LiF/Al EQE of 1.4%–2.5%,
which is lower than
that of spin-coated
devices, due to the
coffee-ring effect.
CBP:Ir(ppy)342 ITO/TCTA (40 nm)/ EQE is 11.7%, power
CBP:Ir(ppy)3 (20 nm)/ efficiency is 29.9 lm
BCP (10 nm)/Alq3 W−1, comparable
(40 nm)/LiF (1 nm)/Al with that of devices
(100 nm) fabricated by vacuum
deposition.
PPV, R-PPV50 ITO/PEDOT/PPV/F8/ The luminance of the
cathode(blue) 2 inch display was
ITO/PEDOT/R-PPV/ about 30 cd m−2, con-
F8/cathode(green) suming 0.7 W power.
ITO/PEDOT/F8/
cathode(red)
PEDOT–PSS, ITO/PEDOT:PSS Luminance is
interlayer (IL) and (60 nm)/IL (10 nm)/ 200 cd m−2; EQE is
light emitting layer LEP (80 nm)/Ba/Al 4% at the window.
Fig. 12 QD LEDs fabricated by EHD inkjet printing of homogeneous (LEP)51 The addition of high
QD arrays (a, b) schematic illustration and photographic description of boiling point solvents
QD LEDs. (c, d) Electroluminescence images of green and red QD LEDs. results in the flat
surface flatness and
The stage speeds for green and red QDs were 50 μm s−1 and 30 μm s−1,
smooth resultant film
respectively. (e, f ) Plots of current density–voltage ( J–V), luminance– Hole injection layer ITO/HIL/HTL/EML Luminance is
voltage (L–V) and EQE of green QD LEDs. (g, h) Plots of J–V, L–V, and (HIL), the hole (red:green:blue)/ 200 cd m−2.
EQE of red QD LEDs. Reproduced with permission from ref. 54, transporting layer ETL/Al
Copyright 2015, American Chemical Society. (HTL) and the
emitting layers (EML)
for multiple colors
(red, green and
The performance of inkjet-printed LEDs is summarized in blue)52,53
Table 2. The application examples present the promise offered CdSe/CdZnSeS QDs ITO/PEDOT:PSS/ CdSe/CdZnSeS QDs:
and CdSe/CdS/ZnS TFB/printed QDs/ luminance and EQE
by inkjet printing technology for LED fabrication for signage QDs54 ZnO/Al are 36 000 cd m−2
and personalized electronics. The inkjet printing fabrication and 2.5%; CdSe/CdS/
of LEDs has obvious advantages in reducing material costs, ZnS QDs: luminance
and EQE are 11 250
increasing the production speed, flexibility, precision and the cd m−2 and 2.6%.
scale-up ability. However there are still challenges, such as
contamination and parasitic current paths, which are being
addressed through ongoing research in the architecture of
LED devices. As the technology becomes more widely available
and refined, we could expect its impact on industrial coatings, research, to military applications, and thus attracting plenty of
smart surfaces and lighting. attention.56–58 The consideration in designing a photodetector
is application-specific, depending on the sensitivity to light
intensity, on the spectral response and also on the response
3.3 Photodetectors speed. The photodetectors could also be categorized into
Photodetection is extremely important for a wide spectrum of photodiodes and photoconductors based on their operation
applications ranging from environmental and biological mechanisms. Photodetectors have demonstrated their strong

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impact on current technology in our daily life.59 In this
section, we will highlight the photodetectors realized by inkjet
printing process.
The most commonly used donor–acceptor layer in organic
photodetectors is the P3HT and PCBM blend, because of the
extensive investigations already conducted on organic BHJ
solar cells. Lilliu et al.62 demonstrated organic photodiodes
fabricated by inkjet printing the photoactive BHJ and/or the
hole conducting layer. The device structure featured a stack of
glass/ITO/PEDOT:PSS as the bottom electrode, an inkjet-
printed P3HT:PCBM blend as the photoactive layer, and evapo-
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rated Ca and Ag as the cathode. They also compared the per-
formance of devices with spin-coated and inkjet-printed
PEDOT:PSS hole transporting layers. The device with the spin-
coated hole transporting layer produced a responsivity of 0.32
A W−1, corresponding to 63% peak EQE, and an inkjet-printed
one showed a comparable responsivity of 0.27 A W−1 and an
EQE of 62%. Wojciechowski et al.63 demonstrated miniatur-
ized highly sensitive biosensors with an inkjet printing
organic photodiode based on the P3HT:PCBM blend photo-
active layer and the PEDOT:PSS hole transporting layer. The
photodetector showed a responsivity of 0.25 A W−1 at 532 nm.
The miniaturized biosensor system including a disposable
glass slide and the organic photodiode could detect
Staphylococcal enterotoxin B with sensitivity as high as 0.5 ng
mL−1, which is better than the typical ELISA-based laboratory
tests and comparable to sensitivity of the biosensors using
CCD- and PMT-based detection.
A fully inkjet-printed organic photodetector was reported by
Lavery et al.64 They printed Ag NPs as the cathode, a ∼1 µm
thick blend of PFB and F8BT as the active layer and PEDOT:
PSS as the top electrode. A fluorosurfactant was introduced to
the PEDOT:PSS ink to improve the wettability so that PEDOT:
PSS could also be directly inkjet-printed on the photoactive
blend with good uniformity. The photodetector worked at a
high luminance (∼100–400 × 103 lux) and showed an EQE peak
of 5.9% at 400 nm with a dark current density of 1 nA cm−2 at
1 V reverse bias. The poor uniformity of the inkjet-printed
layer was the main cause to short-circuit or current leakage,
considering the small thickness of the photoactive layer pre-
pared by inkjet printing. Azzellino et al.60 have succeeded in
inkjet printing of an organic photodiode based on the P3HT:
PCBM blend photoactive layer and the PEDOT:PSS hole trans-
porting layer with much enhanced performance and reprodu-
cibility by improving the morphology of the photoactive layer
and the hole conducting layer, as shown in Fig. 13a and b. The
excellent control obtained in the printing process results in a
high production yield and reproducibility. An average thick-
ness of about 120 nm and a coffee-ring free profile photoactive
P3HT:PCBM blend could be obtained by mixing 1,2-dichloro-
benzene and mesitylene solvents to make use of the
Marangoni effect, alleviating the coffee-ring effect. Inkjet print-
ing of a small volume of the ink and proper post-treatment
could contribute to the high performance of the inkjet-printed
organic photodetector. The photodetector showed a responsiv-
ity of 0.39 A W−1 at 525 nm at a reverse applied bias voltage of
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Fig. 13 (a) Schematic description of an inkjet-printed photodetector.
An Ag stripe was used for electrical contact to the PEDOT:PSS layer in
order to minimize resistive losses; (b) optical image of a device: the
dashed square, which is the overlap between the vertical Ag stripe and
the horizontal PEDOT:PSS stripe defines the device area; (c) dark current
and photocurrent (incident power density 3 mW cm−2) of the photo-
detector. (d) EQE spectrum (squares) measured at a bias of 0.9 V (inci-
dent power density: 10 mW cm−2) and a normalized active layer absor-
bance (black solid line). Reproduced with permission from ref. 60,
Copyright 2013, John Wiley and Sons.
0.9 V, the EQE higher than 60% in a wide range with a wave-
length of up to 600 nm, and with a peak of 83% at 525 nm
(Fig. 13c–d).
Apart from the polythiophene based organic light absorb-
ing semiconductor, Pace et al.65 demonstrated the possibility
of inkjet printing active blends comprising fullerenes and
small conjugated molecules. A blend based on a narrow band
gap conjugated molecule 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo
[3,2-b:4,5-b′] dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-
bithiophen]-5-yl)benzo[c][1,2,5]) thiadiazole (T1) and fullerene
PCBM as the photoactive layer, where a small amount of P3HT
was added into the blend to improve the printability of fuller-
enes and a small conjugated molecule ink on flexible poly-
ethylene naphthalate (PEN) substrates. A poly(9,9-bis(3′-(N,N-
dimethylamino)propyl)-2,7-fluorene)-(alt-2,7-(9,9-dioctylfluorene))
(PFN) was inserted between the bottom electrode and the
active material as an interlayer to decrease the electrode work
function difference and enhance its wettability. The spectral
response was extended up to 750 nm, owing to the narrow
band gap small conjugated molecules. In addition, an all-
organic, semi-transparent device could be fabricated fully by
the inkjet printing method by replacing the Ag bottom elec-
trode with a printed PEDOT:PSS/PFN electrode. The EQEs were
measured to be 30% and 60% at ∼550 nm for the ternary
blend and a P3HT:PCBM one in the semitransparent configur-
ation respectively. Kim et al.66 fabricated organic phototransis-
tors with a suspended top-source and drain contact structures
by inkjet printing a 6,13-bis(triisopropylsilylethynyl) pentacene
(TIPS pentacene) film as the photoactive material. Under a
steady-state white light intensity of 9–13 mW cm−2, the photo-
transistor outputs a photocurrent to dark current ratio over 106
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and a responsivity of 0.11 A W−1 at a gate voltage of −10 V and
a bias voltage of 1 V. Polymer phototransistors have also been
achieved by inkjet printing a diketopyrrolopyrrole-thiazolothia-
zole copolymer (PDPPTzBT) as the photoactive layer on a
bottom gate and bottom contact structure.61 The authors first
defined the electrode areas by inkjet printing a pure solvent to
selectively remove the PMMA photoresist. After electrode depo-
sition and lift-off, the channel length could be defined, as
shown in Fig. 14a–d. With this method, the minimum channel
width could reach 700 nm. The PDPPTzBT was also deposited
onto the channel area by inkjet printing the ink formulation of
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PDPPTzBT in a mixed solvent of dichlorobenzene/toluene (v/v
= 95/5), followed by thermal annealing in a glove box filled
with nitrogen at 120 °C for 5 min (Fig. 14e and f ). The final
devices showed a very high responsivity (106 A W−1) under
weak illumination at a wavelength of 650 nm, as displayed in
Fig. 14 (a) A layer of PMMA resist (3 nm thick) is spin-coated on a silica
substrate. (b) Organic solvents were inkjet-printed on PMMA to define
the source and drain electrodes. (c) Subsequent deposition of the Ti
adhesion layer and Au electrodes. (d) Lift-off of PMMA by ultrasonic
cleaning. (e) AFM image of the PDPPTzBT film inkjet-printed across the
channel region (L = 0.7 µm). (f ) The corresponding phase image of the
inkjet-printed film. (g) Transfer characteristics of the transistor in the
dark and under illumination. (h) Current response of a device to on/off
illumination. Reproduced with permission from ref. 61, Copyright 2014,
John Wiley and Sons.
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Fig. 14g and h. Upon irradiation, drain current raised within
1 s, however, after light was switched off, drain current did not
decay to the dark current but stayed at steady level the for at
least 104 s, due to the persistent photoconductivity (PPC). The
PPC effect could be erased by applying an opposite gate
voltage.
Though the organic semiconducting materials are most
commonly utilized to provide a proof-of-concept device fabri-
cation feasibility, many inorganic semiconducting materials
are also examined to extend the optical absorption window of
photodetectors. Inorganic nanomaterials include NPs,56,58
nanowires (NWs),19,28,67–69 nanotubes,70,71 2D
56,72–75
nanomaterials in which nanoscale phenomena such as
plasmonic effects and quantum confinement76–78 play a
crucial role. Nanostructured materials greatly benefit from the
quantum size effect, wherein the band gap and optoelectronic
property of the material are highly size-dependent. The solu-
tion process also enables the inkjet printing of these inorganic
NP inks into the photoactive layer of the photodetector. For
example, Börberl et al.4 fabricated a highly sensitive photo-
detector by inkjet printing the HgTe NPs/CB ink on interdigi-
tated Ti/Au electrodes, they achieved the maximum specific
detectivity of 3.2 × 1010 cm Hz1/2 W−1 under 1 nW of illumina-
tion at 1.4 µm. A six-layer device presented a sensitivity of
65 mA W−1 at 10 V. In addition, the photoresponse behavior of
HgTe NP photodetectors could be well tuned by taking advan-
tage of the size-dependent quantum effect. By changing the
NP size, the responsivity spectrum could be well modulated,
allowing the extension of the spectral response up to 3 μm.
Various NP layers were printed to optimize the film thickness
to absorb sufficient light (Fig. 15). The inorganic NPs such as
CdSe NPs could also been inkjet-printed onto flexible sub-
strates with an office inkjet printer.79
Due to excellent electronic and optical properties, graphene
(G) has been widely investigated as an electrical contact and a
photoactive layer; besides, the solution processibility of gra-
phene oxide (GO) enables fabrication of graphene-based
photodetectors by full inkjet printing technology. Manga et al.
formulated an ionic solution ink by mixing titanium(IV) bis
(ammonium lactate) dihydroxide (TBA) and GO nanosheets,
and printed the ink on coplanar graphene-based electrodes,
producing a fully inkjet-printed photodetector.80 This ink
needs a suitable viscosity to allow for inkjet printing, improv-
ing the solubility of GO in ethanol based solutions and the
rapid hydrolysis of titanate by using aqueous solutions. Finally
the devices were reduced in hydrazine vapor overnight and
then heated in a vacuum to obtain reduced GO (rGO) electro-
des and TiO2-G hybrid films. The final device output showed a
peak EQE of 85% and a specific detectivity of 2.33 × 1012 cm
Hz1/2 W−1 at around 325 nm. The spectral response of the
detector was up to a wavelength of 750 nm but detectivity
quickly decreased to 9.4 × 1011 cm Hz1/2 W−1 in the visible
spectrum range (Fig. 16).
In addition to the dissoluble GO, other carbon based
materials have also been printed to function as an electrode in
fully inkjet-printed photodetectors with inorganic active layers.
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Fig. 15 (a) Optical image of the interdigitated electrodes overlapped by
an array of printed NP stripes. (b) I–V-curves of a photodetector with
6 printed layers in the dark and under illumination with 1 µW and 42 µW.
(c) Sensitivity spectra of devices with 1, 2, 4, and 6 printed layers, bias
voltage was 10 V. (d) Plots of the normalized photocurrent spectra of
another two HgTe NP samples with a larger NP size (HgTePD2: 4 nm,
HgTePD3: 6 nm). Reproduced with permission from ref. 4, Copyright
2007, John Wiley and Sons.
An example is demonstrated by Finn et al.81 who inkjet-
printed a planar photoconductor with an ink composed of
liquid-exfoliated MoS2 nanosheets as the photoactive layer and
liquid-exfoliated graphene as the interdigital electrodes. The
fabrication process could be carried out at a lower temperature
(below 70 °C) on a commercial flexible substrate, and the
current of the printed photodetector increases by a factor of 10
when exposed to an illumination of 640 mW cm−2 at a wave-
length of 532 nm. A mixture of carbon nanotubes (CNT) and
semiconducting NPs was inkjet-printed as a hybrid photo-
active layer of a hybrid photodetector.82 CNTs were deposited
via inkjet printing, while NPs were coated by dip-coating dis-
persion of CdTe NPs onto the printed substrates. When the
light is switched on, the change in drain–source voltage was
examined while keeping the source–drain current at a constant
value of 1 mA. The ratio between voltage change and incident
power was around 20 mV W−1 and 15 mV W−1 for phototran-
sistors with and without CdTe NPs respectively. Gohier et al.83
demonstrated the fabrication of infrared photodetectors by
inkjet printing CNT films on flexible pre-patterned Ag electro-
des (deposited by inkjet printing Ag NPs on polyimide (PI) sub-
strates). The photosensor showed a significant resistance drop
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Fig. 16 A two-terminal photodetector produced by inkjet printing with
graphene films as electrodes and TiO2-G hybrid thin films as the chan-
nels. (a) I–V characteristics of a photodetector measured in darkness
and under white light illumination. Inset: Schematic diagram of the
inkjet-printed graphene-TiO2 photodetector. (b) Photoconductive gain
for varying concentrations of graphene in the composite under ambient
conditions. (c) Detectivity vs. wavelength, with a −5 V bias voltage. (d)
Photocurrent under different levels of light illumination. (e)
Photocurrent response time of a photodetector under 100 mW cm−2
white light illumination. (f ) Plot showing the rise time and fall time of
100 ms. Reproduced with permission from ref. 80, Copyright 2010,
John Wiley and Sons.
of −0.35% within 10 s under illumination of the 850 nm laser
beam with a power density of 0.5 mW mm−2 at 0.2 V bias. The
initial resistance can then be fully recovered when the laser
was turned off after the same time period. The response of the
CNT based infrared photosensor was attributed a bolometric
effect. Later on, Li et al.84 also demonstrated MoS2 photo-
detectors by inkjet printing dispersion of liquid-exfoliated
MoS2 nanosheets in terpineol as the photoactive layer, while
inkjet printing the Ag NPs dispersion as electrodes. Upon inci-
dent illumination, the current rises fast, followed by a slow
decay, forming the upward peaks. On turning off the incident
light, the carrier generation rate decreases rapidly and thus
carrier recombination dominates, resulting in a rapid decay in
current. Gradually, the thermal release of the trapped carriers
contributes to a slow current rise to the original dark current
level. This forms the downward valleys.
Apart from the above mentioned solution-processable in-
organic NPs and 2D nanomaterials, various light sensitive
metal oxides also have strong competitiveness in inkjet printable
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photodetectors, especially for UV light detection. Indium
doped zinc oxide (IZO) films and TiO2 NWs, both exhibiting a
photoresponse in the UV region, have showcased this possi-
bility. IZO-based phototransistor fabricated by inkjet printing
showed a current on/off ratio of four orders in magnitude, and
the rise and decay times of 5 ms and 10 ms respectively.85
Chen et al.86 demonstrated inkjet printing of high-perform-
ance TiO2 NW based UV photodetectors. They first printed a
commercial Ag NW suspension in isopropanol (IPA) onto flex-
ible and transparent polyethylene terephthalate (PET) sub-
strates to form the electrode patterns, then another layer of
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comparable with that of other devices fabricated by the con-
ventional techniques, including vacuum deposition and spin-
coating. The versatility of this technique has been clearly
demonstrated by the reported studies where varied materials,
structures and patterns were used after a systematic optimiz-
ation of the ink.59 Further effort toward large-scale application
of this technique lies in improvement in fabrication yield,
resolution, and device performance.
3.4 Transparent electrodes
From section 3.1 to section 3.3, we have discussed the recent

TiO2 NWs was also inkjet-printed onto the electrode patterns
to fabricate a UV photodetector with >80% visible transmit-
tance. The printed UV photodetectors presented high an on/
off ratio of 2000 and also fairly a low dark current of 10−12–
10−14 A. Under a 2 V bias voltage, the detectors responded to
UV illumination with rise and decay times of 0.4 s and 0.1 s
respectively. A summary of performance of inkjet-printed
photodetectors is shown in Table 3.
The above examples confirm the great potential of applying
the inkjet printing technique in the photodetector fabrication
process, which allows for the production of a performance
advances in inkjet printing of solar cells, LEDs and also photo-
detectors. However, apart from the photoactive layer, the trans-
parent electrodes (TEs) are also essential elements in various
optoelectronic devices. In the past decade, the demand for
transparent conductive electrodes has been persistently
soaring due to the increasingly expanding market of various
daily electronics ranging from touch screen displays to solar
cells, and there is no doubt that the market will continue spur-
ring in the foreseeable future.2 A general requirement in the
sheet resistance of TEs is in the range of 10–103 Ω sq−1 at a
transparency of ≥90%, which is also application specific.

Table 3 Performance of inkjet-printed photodetectors

Printed ink Device structure Performance

62
P3HT:PCBM and PEDOT:PSS ITO/PEDOT:PSS/P3HT:PCBM/Ca/Ag
P3HT:PCBM and PEDOT:PSS63 ITO/PEDOT:PSS/P3HT:PCBM/Al
PFB:F8BT and PEDOT:PSS PEDOT:PSS/PFB:F8BT/Ag
P3HT:PCBM and PEDOT:PSS60 PEN/Ag/P3HT:PCBM/PEDOT:PSS/Ag
T1:P3HT:PC70BM65 PEN/PEDOT:PSS/PFN/T1:P3HT:
PC70BM/PEDOT:PSS
TIPS pentacene66 Au/TIPS pentacene/Au
phototransistor with ITO/PVP as
back gate
PDPPTzBT61 Au/PDPPTzBT/Au short channel
phototransistor with SiO2/Si as back
gate
Mixture of zinc acetate dehydrate indium Au/IZO/Au, IZO-based
acetate, and 2-ethanolamine in phototransistor with SiO2/Si as back
isopropanol85 gate.
HgTe NPs4 Au/HgTe Nps/Au
TBA:GO80 Graphene/TBA:GO/graphene
coplanar TiO2:GO hybrid
photodetectors
Liquid-exfoliated MoS2 and graphene81 Graphene/TBA:GO/graphene
coplanar photodetector
CNT films83 Ag/CNT/Ag photodetector
TiO2 NWs and Ag NWs86 Ag/TiO2 NWs/Ag photodetector
Inkjet PEDOT:PSS device: responsivity and EQE are 0.27
A W−1 and 62% at −5 V, which are comparable with that of
devices with spin-coated PEDOT:PSS.
Responsivity and EQE are 0.25 A W−1 and 50%–60% at
532 nm.
EQE is 5.9% at 400 nm with a dark current density of
1 nA cm−2 at 1 V reverse bias.
Responsivity is 0.39 A W−1 at 525 nm at a reverse bias of
0.9 V, the EQE is in the range of 60%–83%.
EQE was measured to be 30%.
Photocurrent to dark current ratio is higher than 106 and the
responsivity is 0.11 A W−1 at a gate voltage of −10 V and a
bias voltage of 1 V
Responsivity is up to 106 A W−1
The device is effectively turned on in about 5 ms and turned
off in 10 ms. The photosensitivity is about four orders of
magnitude in the depletion region, 10 times higher than that
in the accumulation region.
The maximum specific detectivity of 3.2 × 1010 cm Hz1/2 W−1
under 1 nW of illumination at 1.4 µm, responsivity is up to
65 mA W−1 at 10 V.
Peak EQE was 85% and specific detectivity was 2.33 × 1012
cm Hz1/2 W−1 at around 325 nm.
Current increased by a factor of 10 when exposed to
illumination of a 532 nm laser with an intensity of
640 mW cm−2.
Resistance dropped to −0.35% within 10 s under
illumination of the 850 nm laser beam with a power density
of 0.5 mW mm−2 at 0.2 V bias.
The on/off ratio is up to 2000 and the low dark current is
around 10−12–10−14 A. Under a 2 V bias, the detectors
responded to UV light with rise and decay times of 0.4 s and
0.1 s respectively.

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A sheet resistance of 400–1000 Ω sq−1 is adequate for many
applications in touch screens, and of 10–50 Ω sq−1 is already
suitable for OLEDs and solar cell applications.87,88 Currently,
the commercially used TEs in most optoelectronic devices are
made of ITO, which is usually prepared by vacuum deposition.
However, there are serious issues related to the use of such
ITO-based TEs in terms of sustainable development due to
both technical and economic restrictions. First, the price of
the element indium is becoming more expensive because of its
ever increasing consumption and scarcity. Second, the ITO
deposition process needs to be conducted in a high vacuum at
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high temperatures, and usually wastes a large part of the ITO
source. Furthermore, the brittleness and the high temperature
process could not be compatible with flexible, and stretchable
requirements of current optoelectronic devices.89 Inkjet print-
ing enabled by a solution process will provide an effective
alternative to the traditional ITO technology. The expanding
class of inks for printing TEs includes conductive organic poly-
mers, transparent conducting oxides (TCOs), metal NW net-
works, graphene, and CNTs. In the next section we will briefly
present TEs fabricated by inkjet printing these nanomaterials
and their hybrids.
3.4.1 Conductive organic polymer inks. The conductive
organic polymers are one of the indispensable components in
current organic optoelectronics. The solution-processibility
enables us to build flexible optoelectronics in a large-scale,
cost-effective manner. Several conducting polymers, such as
polypyrrole, polyaniline and PEDOT have been well studied
and widely used in optoelectronics. Taking PEDOT as an
example, its application potential lies in its important pro-
perties such as excellent electrical conductivity, optoelectronic
properties, and thermally stability (up to 230 °C). However, its
solubility problem has hampered the fabrication involved with
inkjet printing. This could be overcome by mixing it with a
water-dispersible polystyrene-sulfonate (PSS), by charge-balan-
cing counterion doping polymerization, which yields water-dis-
persible PEDOT:PSS.90 By appropriate modification, PEDOT:
PSS films could possess very good conductivity comparable
with most widely used ITO films while having enough optical
transparency, and thus it is a competitive candidate to replace
ITO in optoelectronics.91–93 The formulated PEDOT:PSS
aqueous dispersion is very stable in water and has excellent
versatility to be deposited into films by various kinds of pro-
cesses,94 including spin coating,95,96 spray coating,93 and
inkjet printing.26,27
As a matter of fact, Ballarin et al.97 have found that there
was no obvious distinction in the surface morphology and
electrochemical characteristics between continuous PEDOT:
PSS films fabricated by inkjet printing and by spin-coating,
indicating that inkjet-printed PEDOT:PSS films could be an
efficient and clean alternative. The thickness of the PEDOT:
PSS films increased linearly with the increase of the coating
layers. Kwon et al.98 proposed that the resistance of the
printed PEDOT:PSS films decreased for thicker films, which
could be attributed to the increased hopping paths for charge
carrier transport when the thickness of the film increased.
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However, there is always a trade-off between the high conduc-
tivity and low optical absorption of the film.
The solvent properties are one the most essential factors
determining the final film properties. The inclusion of a high
B.P. solvent to control the wetting behavior, surface tension,
evaporation and drying of droplets on the substrate is a widely
adopted strategy to design the feature of the printed patterns.
Ummartyotin et al.99 demonstrated PEDOT:PSS films de-
posited by inkjet printing an aqueous dispersion of PEDOT:
PSS NPs. By optimizing the particle size, the surface tension,
and the viscosity of the ink, PEDOT:PSS films were successfully
inkjet-printed on flexible cellulous substrates, whilst retaining
its transparency feature and enhanced the electrical conduc-
tivity. Eom et al.26,28 have also systematically investigated
inkjet printing of PEDOT:PSS layers, and found that the mor-
phology and conductivity of the inkjet-printed PEDOT:PSS
films could be well improved by adding high B. P. solvents
such as glycerol and the ethylene glycol butyl ether surfactant.
Natori et al.100 found that the conductivity of printed films
also depended on the substrates, for example the conductivity
of PEDOT:PSS layers printed on PET is different from that of
the film on polyester. The most significant improvement in
sheet resistance was realized by printing PEDOT:PSS onto poly-
ester with a small addition of glycerol in the ink. The decrease
in the sheet resistance was attributed to the decreased rough-
ness of the substrate and the surfactant glycerol which reduces
the solution’s surface tension and leads to smoother films.
The inkjet-printed PEDOT:PSS films were also explored as
TEs for various kinds of optoelectronics. The chemical doping
of PEDOT:PSS was proven to be an effective method for inkjet
printing the PEDOT:PSS films with high transparency and con-
ductivity simultaneously, toward fabrication of ITO-free opto-
electronic devices.101–104 Ma et al.104 fabricated transparent
and flexible touch sensors based on inkjet-printed PEDOT:PSS
films as TEs and inkjet-printed poly(methylsiloxane) as a
dielectric layer. Yoshioka et al.40 have demonstrated the prepa-
ration of PEDOT:PSS films with area-specific conductivity by
selectively inkjet printing a hydrogen peroxide ink and varying
the oxidation state of PEDOT:PSS. Jung et al.27 have demon-
strated that inkjet-printed PEDOT:PSS films could be directly
used as both hole conducting layers and the anode for organic
photovoltaic solar cells. They deposited the PEDOT:PSS films
directly on glass by inkjet printing the ink of the high-conduc-
tivity PEDOT:PSS aqueous suspension as the anode. The
inclusion of 5 wt% DMSO and 0.1% fluorosurfactant into the
ink benefits high conductivity and uniform morphology. By
printing PEDOT:PSS/PCDTBT:PC70BM/ZnO/Ag layers in
sequence, the organic solar gave a PCE of 2%; by replacing the
inkjet-printed Ag cathode with evaporated Ag, the PCE was
drastically improved to 5%. The interesting observation is that
the solar cells with an inkjet-printed PEDOT:PSS anode
showed comparable performance with those based on ITO
TEs. Chou et al.105 have reported inkjet printing of PEDOT:PSS
TEs for OLED with high performance. They found that the
addition of the IPA solvent to the aqueous ink could effectively
adjust the viscosity and surface tension of the ink. They also
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found that the performance of OLEDs of inkjet printing could
be comparable with that of devices fabricated by spin-coating,
and the sheet resistance of the inkjet-printed films was
decreased 10-fold in magnitude, comparing with that prepared
by the spin-coating technique. Micro-Raman spectroscopic
characterization suggested that the improved electric pro-
perties were ascribed to a longer effective conjugation length
of PEDOT chains in inkjet-printed PEDOT:PSS films.
3.4.2 Metal oxide inks. TCOs are a family of metal–oxide
materials bearing both optical transparency and electrical con-
ductivity, and have been widely used as TEs in various current
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daily electronics. A typical TCO group includes the most widely
used ITO, FTO, and also aluminum-doped zinc oxide (AZO).
Most scientific studies and current industrial applications
mainly involve the vacuum deposition processes, which cause
a lot of practical technical issues in applications and also
bring about the cost and environmental concerns. Inkjet print-
ing of metal oxides will provide a greener, more efficient, and
more cost-effective alternative to the current mainstream
vacuum technology.
The ink used for inkjet printing of TCO TEs could be either
TCO precursors or synthesized TCO NCs. The synthesis of TCO
NCs through solution phase processes is a promising strategy
for the deposition of TCO films. A typical example of the metal
oxide ink which one could come out easily should be the ITO
ink, because it has been widely used in current optoelectronic
devices. The implementation of inkjet printing enables us to
precisely control the position and amount of ITO ink drops,
which would greatly reduce the material consumption. Kim
et al.106–108 demonstrated the fabrication of ITO TEs for cost-
efficient organic solar cells by inkjet printing ITO NPs. After
performing a rapid thermal annealing at 450 °C, they directly
obtained patterned ITO electrodes with an average transmit-
tance higher than 80% and a sheet resistance of around 200
Ω sq−1 without using a traditional photolithography process.
Another strategy implemented to reduce the consumption of
the scarce element indium was doping the indium oxide with
other elements.89,109 The transparent zinc- and tin-co-doped
indium oxide (IZTO) electrode with a sheet resistance of as low
as 20.6 Ω sq−1 and an optical transmittance of up to 81.29%
was obtained by applying rapid thermal annealing on the
inkjet-printed IZTO TEs in a nitrogen/oxygen mixture atmo-
sphere.109 Titanium (Ti)110 was also used to dope In2O3, after
an optimized rapid thermal annealing process, the inkjet-
printed Ti-doped In2O3 (ITiO) film showed a sheet resistance
of 37.41 Ω sq−1 and an optical transmittance of 85.40%. These
results suggested that the degree of interconnection of the
ITiO NPs critically affects the sheet resistance, optical transpar-
ency, and surface morphology of the final ITiO electrode.
The solution synthesis enables one to control the size, mor-
phology, and composition of the TCO NCs simultaneously.
Other advantages related to the use of TCO NC inks in the
inkjet printing technique include the compatibility with flex-
ible and stretchable substrates, and the simple and straight-
forward deposition manner. A lot of efforts have been made to
synthesize TCO NC inks in solution over the past few years.89
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Among all solution synthetic processes, hot injection has been
intensively studied for the synthesis of colloidal NCs in recent
years. In a typical hot injection synthesis process, a chemical
reaction will happen between the injected source and the
mother solution and NCs will form in a localized environment.
This method has been successfully employed to synthesize
AZO111 and ITO112 NCs with simultaneous control of their size
and doping level. Uniform NC films of up to the centimeter
scale have been assembled from these NCs and presented
impressive electrical conductivity (356 Ω sq−1) and optical
transparency (93% in visible spectra range) after appropriate
thermal treatment. Ito et al.113 proposed a high-yield hot-injec-
tion synthetic process that was able to produced crystalline,
monodisperse TCO NCs at a temperature lower than the
decomposition temperature of the source. A rapid esterifica-
tion reaction was initiated by slowly injecting the metal oleate
complex into oleyl alcohol at 230 °C. This protocol can be used
to synthesize different types of NCs, including ITO, iron oxide
and ZnO and so on.
The hot inject synthetic process has two disadvantages.
First, the ability to scale up the process is limited by the small
dose adopted to promote high-quality doping. Second, the
doping quality is strongly dependent on the injection para-
meters and the dopant. The optimization of these parameters
for the preparation of other NCs is highly time-consuming,
thus greatly hindering the scaling up of the production of
various NC inks for industrial applications.
To overcome the limitation of the hot injection method,
Song et al.114 developed a general one-pot process for the
preparation of various kinds of TCO NCs, which could be
readily scaled up to a production of 10 g per pot. The syn-
thesized TCO NCs (Fig. 17) have good crystallinity, uniform
morphology, narrow size distribution, and well-controlled
doping level. The final colloids could sustain good dispersion
capability over 1 year and hence could be used as inks to print
high-performance TE films. The resulted TCO NC based TEs
showed high performance in solution-based devices. Gaspera
et al.115 reported a non-injection synthetic process for the pro-
duction of monodispersed ZnO-based NCs with Al, Ga, or In
dopants. The synthetic method is highly reproducible and
permits dopant/Zn atomic ratios of over 15%. Another advan-
tage of this method is that the synthesis could be even per-
formed at a precursor concentration greater than 0.2 M with
reaction yields higher than 90%. The resulting colloidal dis-
persions present good electric conductivity after being
assembled into films and excellent transparency in the visible
spectral range. Luo et al.116 also presented the fabrication of
high quality TEs by wet-chemical deposition of antimony
doped tin oxide (ATO) NCs. They also found that OLED fabri-
cated on ATO NC-based TEs exhibited a performance compar-
able to that of commercial ITO-based devices. These above
mentioned advances indicate the potential of solution pro-
cesses for production of high-quality metal oxide NC colloidal
inks for ink-jet printing of next-generation TEs. However, the
as-printed TEs are not suitable for various optoelectronic
devices. UV treatment could effectively remove the organic
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Fig. 17 Application of the one-spot method for the synthesis of
different types of TCO NC inks. (a, b) TEM images of ZnO NCs. The inset
in (b) is an HRTEM image of an individual ZnO NC; (c) TEM image of
AZO; (d) TEM image of GZO; (e) TEM image of IZO. The inset in (e) is the
SAED pattern of IZO NCs. (f ) STEM image and elemental mappings of
IZO NCs. (g) TEM image of Ga2O3 NCs; (h) TEM image of In2O3 NCs; (i, j)
TEM image of ITO NCs; (k) optical image of ITO NC powders synthesized
on a larger scale. (l) Photograph of 30 ml of ITO NC ink re-dispersed in
toluene. Reproduced with permission from ref. 114, Copyright 2015,
John Wiley and Sons.
compounds in the TCO NC films and shorten the interspacing
between TCO NCs, improving the conductivity of the printed
TCO TEs.117 Short-ligand exchange was also demonstrated to
be a versatile method to increase the conductivity of the NC
films.118 The printed films have a wide spectrum of appli-
cations such as TEs in LEDs, and solar cells without the use of
any conventional lithography processes, thus indicating that
the inkjet printing of TEs is a viable alternative to the vacuum
sputtering of ITO TEs for various solution-processable opto-
electronic applications.
3.4.3 Metal based inks. Recently, considerable efforts have
been made to explore the applications of metal NC inks in
various fields, such as flexible and stretchable electronics,
implantable medical devices, flexible and stretchable displays,
OLEDs, and organic solar cells. Various metal-based inks
including Au NPs/NWs, Ag NPs/NWs119,120 and Cu NPs/
NWs121,122 have been demonstrated as conductive inks.
Impressive advances have been made with the corresponding
flexible and stretchable electrodes.
The Ag NW dispersion is possibly the most widely used
metal-based conductive ink for TE preparation.123 A typical
synthetic method for Ag NWs is by reducing Ag nitrate in the
presence of poly(vinylpyrrolidone) (PVP) in ethylene glycol as
the reaction medium and reductant.124,125 The as-prepared Ag
NWs can be well dispersed into diverse solvents, including
water, ethanol, and IPA, to prepare suspension inks for inkjet
printing of TEs. The sheet resistance and optical transparency
of the resulting films are critically dependent on the thickness
and also the post-deposition treatment. For Ag NW-based TEs,
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the sheet resistance and optical transparency are usually in the
ranges of 1–100 Ω sq−1 and 80–90%,88,120,126–128 respectively,
being comparable with those of ITO films. Because of their
high electrical conductivity and optical transparency, Ag NW-
based TEs serve as good candidates for device integration in
the existing applications. The Ag NW-based TEs were prepared
by drop-casing the Ag NW ink onto a glass substrate followed
by post-deposition annealing at 200 °C for 20 min. The result-
ing TEs presented a sheet resistance in the range of 1–100 Ω
sq−1, which depends on coating density.119 Due to the solution
process and high performance as TEs, the Ag NW networks
have been proved to be a promising alternative to the current
ITO-based TEs for organic solar cells.129,130
Compared with Ag NWs, copper (Cu) NWs are less expen-
sive, because the price of Cu is 100 times lower and the abun-
dance of Cu is 1000 times higher, while, the electrical conduc-
tivity of Cu NWs is almost the same as that of Ag NWs, which
could be good enough for most optoelectronic devices. In this
regard, the utilization of the Cu NW ink for conductive film
preparation has become popular in recent years.131–133 Two
general approaches have been developed for Cu NW synthesis:
ethylenediamine (EDA)-mediated and alkylamine-mediated
synthesis. TEs fabricated with Cu NW inks have shown a sheet
resistance as low as 51 Ω sq−1 at 93% optical transmittance.
However, Cu NW-based conductive films have a serious draw-
back that Cu is less stable in oxygen and moisture ambient
environment than other noble metals. Various strategies have
been proposed to improve the stability of Cu NW films. Wiley
et al.134 proposed that growing a nickel shell-coating on Cu
NWs could effectively improve the oxidation resistance of Cu
NWs. Won et al.135 reported the oxidation-resistant Cu NW
based composite electrodes with high transparency and con-
ductivity. The strategy first involved treating of the Cu NWs
with lactic acid to remove the organic capping layer and the
oxides or hydroxides on the surface of Cu NWs, creating a
direct electrical current transport pathway in the Cu NW
network; subsequently embedding the Cu NWs into the AZO
film to dramatically enhance their stability and resistance to
oxygen and moisture. The resultant Cu NW@AZO composite
TEs exhibited an impressively low sheet resistance (35.9 Ω
sq−1) at an optical transmittance of 83.9% at 550 nm. Song
et al.136 developed a synthetic method to prepare a new
Cu@Cu4Ni NW conductive elastomer composite with ultrahigh
stability. They synthesized Cu NWs with a protective Cu4Ni
alloy shell in situ grown on Cu NW surface through a one-pot
method. The final Cu NWs have highly crystalline alloyed
shells, clear and abrupt interfaces, lengths more than 50 μm,
and smooth surfaces. New elastomers were formed by cladding
the Cu@Cu4Ni NW network with polydimethylsiloxane
(PDMS). The final flexible composite TEs presented a sheet
resistance of 62.4 Ω sq−1 at an optical transparency of 80%
which are superior to those of typical ITO/PET electrodes.
Despite the promising application potential of metal Ag
and Cu NWs, the TE enabled by inkjet printing of either Ag or
Cu NWs have been rarely demonstrated. Very recently, Finn
et al.128 have reported Ag NW networks prepared by direct
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inkjet printing of the Ag NW ink onto a polymer substrate.
They found that the dilution of the ink suspension and
addition of diethylene glycol (DEG) could improve the print-
ability of the Ag NW ink. The optimized NW concentration was
0.85 mg ml−1 and the IPA : DEG volumetric ratio was
0.85 : 0.15, for the best printing performance with stable
droplet generation and movement. The solvent evaporation
during and after deposition is also critical to form a high-
performance TE film. The intermediate drying step during a
print session in a vacuum at a pressure of 0.1 mPa and temp-
erature of 110 °C for 30 min to slowly evaporate the solvent is
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critical to obtain a conductive Ag NW network. Lu et al.137
demonstrated an inkjet-printed AgNW film as a top electrode
for semitransparent organic solar cells. They found that the
addition of ethylene glycol into the Ag NW ethanol dispersion
was very critical to prevent nozzle clogging. The optical and
electrical measurement results showed that the sheet resist-
ance of the printed Ag NW decreased dramatically from 2190
Ω sq−1 to 26.4 Ω sq−1 with the increase of printing times from
3 to 9, whereas the average transparency of the printed Ag NW
films over a 400–800 nm wavelength just decreases slightly
from 95% to 83%. Note that the 7-time-printed Ag NW layer
has an average sheet resistance of 44.9 Ω sq−1 and an average
transparency of 86.4%, which are close to that of the widely
used ITO electrodes.
Metal NP dispersions are ideal inks for inkjet printing of
conductive traces. Ag NPs were commonly used for electrode
printing in a wide range of electronic devices.59,88,138–140
Layani et al.141 also demonstrated inkjet printing of Ag grid
TEs from the Ag NP ink on transparent plastic substrates. The
inkjet-printed TEs showed a low sheet resistance (1–5 Ω sq−1)
at a high transparency of 83% in the range of 400–800 nm,
which could be superior to those of many TEs used in opto-
electronics. The light reflection on the wide metal grid is the
main cause for the reduction in the transparency of the metal
grid TEs. Shrinking the width of the metal grid line was
believed to be an effective method to reduce the light reflec-
tion on the metal grid. Jang et al.142 have fabricated invisible
Ag-grid (less than 10 µm) by EHD inkjet printing of Ag NP
inks. As one expected, the improvement in the electrical con-
ductivity of the TEs was at the cost of the optical transparency
as the Ag-grid pitch decreased. After annealing at 200 °C under
near-infrared, the EHD inkjet-printed 150 µm Ag-grid pitch
TEs presented a sheet resistance of 4.87 Ω sq−1 and a transmit-
tance of 81.75%. Schneider et al.143 have employed EHD inkjet
printing to print Au and Ag grids with line widths from 80 to
500 nm with Au and Ag NP inks. The high-resolution was
achieved with the help of the high resolution NanoDrip print-
ing mode. This EHD inkjet printing process demonstrated the
capability of printing high-aspect-ratio structures (nanowalls
or NWs) with a high resolution, significantly decreasing the
sheet resistance while maintaining the high-level optical trans-
parency. The EHD inkjet printing also provided flexibility in
designing the application specific TEs, for example, both low
sheet resistance with a relatively low transparency (8 Ω sq−1 at
a transmittance of 94%) and high transmittance with a rela-
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tively high sheet resistance (97% at a sheet resistance of
20 Ω sq−1) have been demonstrated by changing the printing
parameters.
The coffee-ring effect is normally considered as a negative
factor in inkjet printing. However, by appropriately designing
the coffee-ring pattern, it also helps to form excellent TEs.
Layani et al.138 demonstrated that the coffee-ring effect could
be used to inkjet print transparent conductive patterns. The
TEs were achieved by forming a 2D array of interconnected Ag
NP rings. The interconnected Ag patterns were fabricated by
inkjet printing the Ag NP ink (0.5 wt%, ∼20 nm Ag NPs) on
plastic substrates. The width and height of the rim of the indi-
vidual rings are less than 10 µm and 300 nm respectively. The
diameter of the ‘hole’ surrounded by the rim is about 150 µm;
thus the whole array of the interconnected rings is highly
transparent. The rims of the rings consist of self-assembled,
closely packed Ag NPs, making the individual rings and the
whole ring array highly conductive. The whole interconnected
ring array presented a high transparency of 95% and a low
sheet resistance of ∼4 Ω sq−1, which were better than those of
traditional ITO TEs. Another strategy to form TEs based on
metal NPs is by printing metal grids with both good optical
transmittance and electrical conductivity.
The current issues with the inkjet printing of metal-based
TEs include the clogging of the printer nozzle due to the high
tendency of precipitation of metal contents in the ink, the
rough surface of the printed TEs and also the instabilities in
the ambient environment. The clogging problem could be alle-
viated by proper design of the ink formulation,137 passivation
on the printed surface will help to reduce the surface rough-
ness,144 and the stabilities could be readily improved by
encapsulation.145–147
3.4.4 CNT based ink. CNTs are composed of one-atom-
thick sheets of carbon with a hexagonal structure in a cylindri-
cal-hollow-wall configuration. There are single-walled CNTs
(SWCNTs) and multi-walled CNTs (MWCNTs), and their length
could range from less than a micrometer to centi-
meters.70,71,148 For SWCNTs, the electronic properties are
determined by their chiral structures, one third of them are
conducting, and two thirds of them are semiconducting. The
intrinsic electrical resistivity was found to be around 10−6
Ω cm for individual SWCNT and 3 × 10−5 Ω cm for single
MWCNT.87,149 Because of their excellent electrical properties,
solution processability, mechanical flexibility, and potential
for low-cost and large-scale production, thin films made of
randomly distributed CNTs were extremely promising for the
fabrication of flexible TEs.
The printing of CNTs has several advantages, such as low
material consumption, low equipment costs, high throughput,
and additive fabrication. CNT inks for high-quality TE printing
can be prepared by combining the CNT dispersions with suit-
able additives, depending on the required printing method.
The dispersion medium could be water or organic solvents,
and the concentration of CNTs is in a wide range from
0.01–10 mg ml−1. Concentration limitation is very essential for
most of the printing methods, which require suitable viscosity
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and surface tensions of the ink (such as inkjet or flexo), but
less critical compared to screen printing. Despite their high
hydrophobicity and tendency to aggregate, CNTs can be dis-
persed well in many solvents by proper surface chemical modi-
fication or with the help of solubilizing additives, including
surfactants, cellulose derivatives, and conducting polymers,
and thus can then be used as inks for printing. Chemical
modifications of the CNTs with functional groups favor the
interactions between CNTs and the dispersing medium. The
major issue related to organic solvents without using disper-
sing agents is the low CNT concentration limit, which is lower
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than 0.1 g L−1.2 The advantages of water-based CNT inks
include the high concentration limit and also high safety
during the printing process. To obtain stable aqueous disper-
sions of CNTs, various kinds of surfactants such as Triton
X-100,150,151 sodium dodecylbenzene sulfonate (SDS),150,152
and CTAB,153 were widely used to stabilize the CNT content.
When a surfactant is added into a water-based CNT ink, with
the help of hydrophobic tails, the surfactant molecules are
attached onto the surface of each CNT, which create a barrier
around the perimeter of the CNT to physically mitigate the van
der Waals forces between the CNTs in close proximity. In
addition, because of the hydrophilic heads in capping surfac-
tants on CNTs, there is a repulsive chemical force between
CNTs which also helps to stabilize the CNT dispersion.
Azoubel et al.154 reported a MWCNT ink with a good inkjet
printing performance at a concentration of 10 mg ml−1, dis-
persed in water with a 0.5 wt% polymeric dispersant, and
0.1 wt% of the wetting agent. The printing of CNTs has been
well summarized recently by several groups,155,156 here we will
only focus on the inkjet printing of CNTs for TE applications.
Generally, for SWCNT-based TE films, the sheet resistance
and optical transmittance are typically in the range of 60–870
Ω sq−1 and 70–90% respectively, depending on the SWCNT
dispersion, the film thickness and the deposition process.
Direct inkjet printing of the CNT ink into patterns was first
demonstrated by Vajtai et al.158 who first chemically modified
the surface of the MWCNT surface using oxidants (HNO3 or
KMnO4) to create oxygen-containing functional groups which
would be beneficial for preparing a stable aqueous MWCNT
ink. Patterns with a sheet resistance of 40 kΩ sq−1 were
achieved by multiple prints. The conductivity of printed
MWCNT-based electrodes could be greatly enhanced by mul-
tiple prints, however, the transparency will degrade accord-
ingly. Some groups even achieved MWCNT-based electrodes
with a sheet resistance less than 1 kΩ sq−1 by printing mul-
tiple layers, the lowest sheet resistance of 78 Ω sq−1 was rea-
lized after a total of 200 prints, as demonstrated by Chen
et al.,159 but the transmittance was only 10%. Mustonen
et al.160 have formulated a composite ink of functionalized
SWCNTs and PEDOT:PSS, and printed composite TEs having a
sheet resistance of 1 kΩ sq−1 and an optical transparency of
70% after 30 prints, they could also print higher transparency
patterns (∼90%) with however a much higher sheet resistance
of ∼10 kΩ sq−1. An electroluminescent device with two printed
CNT electrodes was also demonstrated recently. The transpar-
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ent back electrode was fabricated by rod coating of MWCNT
films, and the counter electrode was fabricated by inkjet print-
ing MWCNT films on transparent flexible substrates. The elec-
troluminescent device gave an intense emission after applying
a bias between the two printed MWCNT electrodes.154
Similar to the case of inkjet printing of Ag TEs from the Ag
NP ink,138 the coffee-ring effect is also not always a bad thing.
Lee et al.161 reported the fabrication of circular rings by inkjet
printing the water-based SWCNT ink. Most of the SWCNT con-
tents concentrated at the rims due to the coffee-ring effect.
They found that weak oxidants such as UV/ozone could also be
able to create oxygen-containing groups on SWCNTs and to
enhance the dispersion stability of the SWCNTs in a water-
based solvent. The TEs were achieved by inkjet printing the
interconnected or stacked rings; a sheet resistance of 870
Ω sq−1 and an optical transparency of 80% (at 550 nm) were
achieved in the TEs after 40 prints. Shimoni et al.157 have also
inkjet-printed transparent conductive patterns, and arrays of
interconnected CNT circular rings on flexible substrates by
using the coffee-ring effect. Direct fabrication of these rings
was realized by inkjet printing an aqueous-CNT dispersion,
which concentrated and self-assembled at the rims of the pat-
terns. The electrical performance of the printed CNT films
could be much improved by post-printing treatment with hot
nitric acid, after which a sheet resistance of 156 Ω sq−1 and an
optical transmittance of 81% at 600 nm was achieved. This
makes CNT-based TEs very competitive for various electronic
applications, as demonstrated in electroluminescent devices
(Fig. 18).
Although CNT inkjet printing is relatively new, it has been
demonstrated to be very promising for printing mechanically
flexible and chemically stable TEs. However, there still exist a
few issues including high sheet resistance, low transparency,
and large roughness. Only after overcoming these issues,
Fig. 18 (a) Mechanical profilometer result of a printed CNT ring with a
300 nm thickness. (b) The corresponding optical profilometer result of
the CNT ring. (c) Optical image of printed CNT rings forming a transpar-
ent conductive film. (d) A flexible electroluminescent device prepared by
the printed CNT rings. Reproduced with permission from ref. 157,
Copyright 2014, Royal Society of Chemistry.
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inkjet printing could become a mature method for CNT depo-
sition. The high roughness could be well negated by deposit-
ing another layer of transparent conductive materials, for
example deposition of PEDOT onto the inkjet-printed CNT
films could effectively smooth the surface.144 Other post-print-
ing chemical treatments could also improve the conductivity
of CNT films through various mechanisms, including remov-
ing the organic residues on CNTs and improving the CNT–
CNT contact, or doping the CNT films.144,162,163
3.4.5 Graphene based ink. Graphene is a 2D material con-
sisting of sp2 hybridized carbon atoms with a honey-comb
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lattice.164 Due to its unique structure and superior physical,
chemical, electronic, and optical properties, graphene has
been paid plenty of attention since its first exfoliation from
graphite in 2004.72,73,164–170 Graphene possesses exceptional
in-plane conductivity and low sheet resistance even though it
only has a single atomic layer. Light absorption by a defect-
free graphene is estimated to be 2.3% while its sheet resistance
could be as low as 60 Ω sq−1. Recent progress in the prepa-
ration and characterization of graphene suggest it as one of
best candidates for TE fabrication through solution processes.
Liquid dispersions of graphene nanosheets could be very
promising for deposition by solution processes, including spin
coating, roll-to-roll processing, and inkjet printing. Bulk graph-
ite powder can be exfoliated into single graphene nanosheets
or few-layer graphene flakes, which depends on the exfoliation
method. The chemical exfoliation of graphite flakes in solvents
is the most promising process for large-scale production of
graphene and solution-phase processing of a graphene
ink.171–173
The first demonstration of inkjet printing of graphene was
conducted by Huang et al.174 who studied inkjet printing of a
series of graphene-based inks. Under optimized conditions,
high-quality graphic patterns could be fabricated by inkjet
printing water-soluble single-layered or few-layered GO-based
inks on various kinds of flexible substrates, ranging from
paper, PET to PI. After thermal reduction, the printed gra-
phene-based patterns showed a high electrical conductivity
which increased with the number of printed layers. More
importantly, these printed patterns retained the same conduc-
tivity over several bending cycles, indicating their application
potential in flexible TEs. Then Kong et al.175 inkjet-printed gra-
phene TEs on flexible substrates with GO dispersion in water,
and then reduced GO with infrared light at 200 °C for only
10 min. By optimizing the distance between the adjacent dro-
plets and the printing layers, the final reduced GO TEs gave a
sheet resistance as low as 0.3 MΩ sq−1 at an optical transpar-
ency of 86%.
One disadvantage of printing the aqueous graphene ink is
that a reduction process (either thermal treatment or chemical
reduction) is needed to restore the conductivity of the gra-
phene sheet,176–179 which is undesirable for many appli-
cations. Few-layer graphene flakes produced by the liquid-exfo-
liation method could restore the electrical conductivity of gra-
phene to a large extent and thus present promising application
potential in TEs. Torrisi et al.180 reported inkjet printing of
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graphene based thin films with the ink composed of liquid
phase exfoliated few-layer graphene nanosheets in the organic
solvent N-methylpyrrolidone (NMP). The merit of this process
relies on the high quality of the resultant graphene flakes, due
to the oxidization-free process. They used the graphene ink to
inkjet print graphene thin film transistors with a mobility of
up to ∼95 cm2 V−1 s−1, and also transparent and conductive
patterns with an optical transparency of up to 80% and a sheet
resistance of 30 kΩ sq−1. It was found that the wettability of
the substrate to the ink is quite critical to the final feature of
the printed graphene patterns, the silane groups in the mole-
cular structure of hexamethyldisilazane (HMDS) could
promote the adhesion of metallic particles to the substrate.
Similarly, HMDS may also improve the adhesion between gra-
phene flakes and the substrate, thus promoting the assembly
of graphene flakes into a regular network. However the ink
based on graphene flakes dispersed in organic solvents always
suffers from low concentration or toxicity. A high printing
efficiency requires high stability and also a high concentration
of the graphene dispersion-based ink. Li et al.181 developed an
ink formulation based on graphene flake dispersion in non-
toxic terpineol for inkjet printing of graphene patterns. The
graphene ink was prepared by first exfoliating graphite flakes
in DMF, and exchanging DMF with terpineol to distil due to
the large difference between their boiling points. The gra-
phene content could be greatly concentrated after solvent
exchange and distillation. To prevent graphene sheet aggrega-
tion during DMF evaporation, a certain amount of polymer
(ethyl cellulose) was added into the graphene/DMF suspension
as a stabilizer. Finally, the stabilizer can be effectively removed
through a post-printing annealing at 300–400 °C in air for 1 h.
After polymer stabilization, graphene/terpineol dispersions
could reach a concentration of around 1 mg ml−1 and remain
stable for at least several weeks. The resultant inkjet-printed
film showed a sheet resistance down to 30 kΩ sq−1 and an
approximate 80% transmittance at a wavelength of 550 nm.
The key factor of controlling the concentration of the gra-
phene dispersion is to prevent the graphene flake from aggre-
gating. The graphene flakes dispersed in an organic solvent
could be dramatically concentrated by using a specific stabil-
izer, and the conductivity of the inkjet-printed graphene pat-
terns could also be improved by post-printing annealing.
A concentrated graphene ink was obtained by liquid exfolia-
tion of graphite powders in an environmentally benign solvent
ethanol with ethyl cellulose (EC) as a stabilizer. Subsequently,
the obtained graphene/EC powders were re-dispersed in a
mixture with a cyclohexanone : terpineol ratio of 85 : 15, and the
graphene concentration could be as high as 3.4 mg ml−1.182
During solvent evaporation, the polymeric stabilizer EC encap-
sulates the graphene flakes, and thus proper post-printing
annealing is needed to restore the electrical conductivity of the
printed graphene films. After a thermal annealing at 250 °C
for 30 min, the treated graphene films presented a resistivity
of 4 mΩ cm and a uniform morphology, good compatibility
with flexible substrates and also excellent tolerance to
bending strains. Majee et al.183 have shown that the a high
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concentration (up to 3.2 mg ml−1) graphene ink could be
obtained by shear-exfoliation of graphite powers in the organic
solvent NMP with most of the graphene flakes being ∼4 layers
thick and 160 nm in diameter. The graphene ink could be well
inkjet-printed on various substrates. After 10 prints and a
thermal annealing at ∼350 °C for 150 min, graphene TEs with
a sheet resistance of 260 Ω sq−1 and a transparency of 86%
were readily achieved.
The current low performance of inkjet-printed graphene
TEs limits their application in many optoelectronics, such as
LEDs, and solar cells; the fabrication of TEs with low sheet
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resistance and high transmittance remains a critical challenge.
Recent progress indicate that inkjet printing of hybrid films
could possibly provide an alternative solution to the issues
with single-component inks.
3.4.6 Hybrid inks. Though countless demonstrations of
inkjet printing of TEs have been reported, and significant pro-
gress has been made in terms of cost and scalability of the pro-
duction, and performance of TEs currently, the performance
of inkjet-printed TEs has not matched the requirements of
practically commercial applications. For example, the sheet
resistance of the inkjet-printed TCO NC films is not optimal
for optoelectronics. The large surface roughness of the metal
NW films also applies some limits to optoelectronic device
fabrication. The tube–tube junctions within the CNT bundle
may block the inter-tube charge transport thus increasing the
resistivity of the CNT films. Graphene films also face a similar
dilemma, GO films need high temperature or harsh chemical
processing to restore the electrical conductivity, the liquid-
exfoliated graphene nanosheets have lower defects, but are
smaller in size, degrading the charge transport capability in
the printed films. For Ag grids, the large void area tends to fall
short in charge collection, the Ag NW films also presents a
high NW-to-NW junction resistance. Recent progress indicate
that inkjet printing of hybrid films could possibly provide an
alternative solution to the issues with the development of
transparent conducting technologies.
For example, the inkjet-printed Ag grids have excellent elec-
trical conductivity and transparency, but fall short in rough-
ness and charge collection efficiency. The combination of Ag
grids with conductive films will be beneficial to alleviate these
issues. Jeong et al.184 have proposed a strategy to improve the
conductivity of the inkjet-printed ITO films by inserting an Ag
grid pattern between the inkjet-printed ITO layers, forming
ITO/Ag grid/ITO hybrid TEs. At an Ag grid pitch size of 3 mm,
the hybrid electrode presented an impressive sheet resistance
of 2.86 Ω sq−1 with an optical transmittance of 74.06%, and a
figure of merit of 17.35 × 10−3 Ω−1. Hwang et al.185 also
implemented a similar scenario to reduce the sheet resistance
of inkjet-printed ITO TEs by patterning the Ag grid between
two ITO layers. With an Ag-grid separation distance of 2 mm,
the Ag-grid embedded ITO films gave a sheet resistance lower
than 3.4 Ω sq−1 after proper post-print annealing. By inserting
the Ag-grid, the electrical properties of the Ag-grid/ITO hybrid
film (2 mm Ag grid pitch) were significantly improved while
the optical transmittance slightly reduced to 82% due to the
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light reflection of Ag grids, but is still comparable to the 87%
transmittance of the pure ITO films. Combinations of Ag grids
with conductive organic films also provide a more effective
charge collection, due to the filling effect of the conductive
organic matrix. Murali et al.186 developed Ag grid/PEDOT:PSS
TEs by inkjet printing both PEDOT:PSS and Ag NP inks. At an
Ag grid pitch size of 1 mm, the Ag grid/PEDOT:PSS hybrid TEs
had a sheet resistance of 10.3 Ω sq−1 and an optical transmit-
tance of 73% which represented a ∼10% reduction in optical
transmittance compared to that of inkjet-printed Ag-grid free
PEDOT:PSS films. The organic solar cells based on these
hybrid TEs could be comparable with those using ITO. Kahng
et al.187 described the fabrication of hybrid TEs based on
inkjet-printed Ag grids and CVD grown graphene films, and
demonstrated their application in organic solar cells. It was
found that the graphene/Ag grid TEs showed a better perform-
ance compared with the Ag grid. The enhancement was attrib-
uted to the void filling effect of graphene films on Ag grid elec-
trodes that have a large void area of ∼2 × 2 mm2 per each
square grid pattern. CNTs have also been incorporated into Ag
NW films to enhance the charge transport by providing extra
local electron transport pathways between the adjacent Ag
NWs composing the backbone electrode of Ag NW mesh.188
The implementation of this multiscale hierarchical approach,
which combines the advantages of materials of different
dimensions and of their properties, provides efficient pathways
for electron transport, demonstrating a novel strategy for
designing highly stretchable and conductive TEs.
As we know, the big change with the graphene- and CNT-
based TE technology mainly lies in the fact that it is difficult
to achieve good conductivity and high transparency simul-
taneously. For CNT-based electrodes, the tube-to-tube junc-
tion resistance mainly contributes the large sheet resistance
of the CNT films. As for the graphene based TEs, neverthe-
less, because the size of graphene needs to be limited in a
safe range which is smaller than 1/20 of the diameter of a
small nozzle, thus the charges need to hop between small
graphene sheets, which increases the electrical resistance.180
Recently, some researchers have shown that some metal NPs
have the capability to improve the conductivity of carbon
nanomaterials. Li et al.189 demonstrated that a layer of fine
Au NPs could significantly improve the electrical conductivity
of CNT fibers, and the Au NPs not only increased the carrier
density in CNTs, but also facilitated the charge transport
between the CNTs. Ag nanostructures with different mor-
phologies have also been included into the graphene
nanosheets to improve their conductivity though the mechan-
ism is still unclear.123,190–192 Li et al.192 presented a method
to assemble Ag nanotriangle platelets (Ag NTP) and Ag poly-
hedral NPs onto GO to form the ink formulations. After
reduction, the inkjet-printed Ag NTP-rGO pattern displays a
low sheet resistance of 170 Ω sq−1 with a transmittance of
90.2%, demonstrating a significant improvement in the per-
formance of graphene-based TEs. Table 4 summarizes the
performance of various TEs fabricated by inkjet printing
techniques.
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Nanoscale Review

Table 4 Performance of inkjet-printed TEs

Printed
materials Solvents Processing conditions or additives Performance
26
PEDOT:PSS Tetralene Glycerol/EGBE The conductivity of PEDOT:PSS increased from 7.82 ×
10−1 to 1.52 × 102 S cm−1 by adding 6 wt% glycerol
and to 1.64 × 102 S cm−1 by adding 0.2 wt% EGBE.
PEDOT:PSS100 Water Glycerol The resistance of printed PEDOT:PSS films decreased
from 4 MΩ m−1 to 0.0134 MΩ m−1 of 10 prints after
being modified by glycerol.
PEDOT:PSS27 Water 5% DMSO and 0.1% fluorosurfactant Additives helped in improving conductivity and
wettability and increasing the solar cell performance.
105
PEDOT:PSS Water IPA Transparency was higher than 90%, resistance of the
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printed film was 290.63 ± 16.99 × 104 Ω m−2 which is

much lower than that of spin-coated films.
ITO NPs106–108 Ethanol or water Rapidly annealed at 450 °C for A transmittance of ∼85% and a sheet resistance of
4 min. ∼200 Ω sq−1.
ITiO NPs110 Ethanol Rapidly annealed at 500 °C for 4 min A sheet resistance of 37.41 Ω sq−1 and an optical
transmittance of 85.40%
IZTO NPs109 Ethanol Rapidly annealed in N2/O2 at 700 °C A sheet resistance of 20.6 Ω sq−1 and an optical trans-
for 5 min. parency of 81%.
Ag NWs128 IPA Addition of 15% DEG into IPA The lowest sheet resistance was observed to be
8 Ω sq−1, transmittance ∼50%.
Ag NWs137 Ethanol Ethylene glycol A sheet resistance of 44.9 Ω sq−1 at a transparency of
86.4%; a sheet resistance of 26.4 Ω sq−1 at a transpar-
ency of 83%.
Ag NPs138 Water Stabilized by poly(acrylic acid) Ag interconnected rings: a transparency of 95% and a
low sheet resistance of ∼4 Ω sq−1.
Ag NPs 141
Water Stabilized by poly(acrylic acid) Ag grids: a sheet resistance of 1–5 Ω sq−1 at a high
sodium salt transparency of 83% in the range of 400–800 nm.
Ag NPs142 Water Annealing at 200 °C under near- Ag girds: a sheet resistance 4.87 Ω sq−1 and a trans-
infrared mittance of 81.75%.
Ag NPs and Au N-tetradecane Annealed at 150 °C for 10 min for Ag A sheet resistance of 8 Ω sq−1 at a transmittance of
NPs143 grids; annealed at 250 °C for 30 min 94%; a sheet resistance of 20 Ω sq−1 at a transmittance
for gold grids of 97%.
ITO NPs and ITO NPs in water; Ag NPs Annealed at 450 °C in N2/O2 for ITO/Ag grid/ITO film: a sheet resistance of 2.86 Ω sq−1
Ag NPs184 in triethylene glycol 4 min with an optical transmittance of 74.06%, and a figure
monoethyl ether of merit of 17.35 × 10−3 Ω−1 at an Ag grid pitch size of
3 mm.
PEDOT:PSS Water and DMF Annealed at 150 °C for 15 min The PEDOT:PSS/Ag grid/PEDOT:PSS has a sheet
and Ag NPs186 resistance of 10.3 Ω sq−1 and an optical transmittance
of 73%.
MWCNT158 Water Surface modification with HNO3 or A sheet resistance of 40 kΩ sq−1 by multiple prints.
KMnO4
SWCNT 159
Water 1 wt% Sodium dodecyl sulfate A sheet resistance 78 Ω sq−1 at a transmittance of
10%.
PEDOT:PSS: Mixture of ethanol and Surface modification of SWCNT A sheet resistance of 1 kΩ sq−1 and an optical trans-
SWCNT160 water parency of 70% after 30 prints; a transparency of
∼90% with however a much higher sheet resistance of
∼10 kΩ sq−1.
SWCNT161 Water Oxidized with UV/ozone SWCNT interconnected rings: a sheet resistance of
870 Ω sq−1 and an optical transparency of 80% (at
550 nm) after 40 prints.
SWCNT157 Water Surfactants: polymeric dispersant SWCNT interconnected rings: a sheet resistance of
SOLSPERSE 46 000 (1.5 wt%) and 156 Ω sq−1 and an optical transmittance of 81% at
wetting agent Byk 348 (0.2 wt%). 600 nm.
Post-treatment: dipping the samples
for 10 min in 70% HNO3 solution
GO174 Water Reduced in Ar/H2 at 400 °C for 3 h Electrical conductivity: 900 S m−1 after 25 prints.
GO175 Water Reduced with infrared light at 200 °C A sheet resistance of 0.3 MΩ sq−1 at an optical trans-
for only 10 min parency of 86%.
Graphene NMP Treated substrate with HDMS to Thin film transistors with the mobility of up to
nanosheets180 improve adhesion ∼95 cm2 V−1 s−1, an optical transparency up to 80%
and a sheet resistance of 30 kΩ sq−1.
Graphene Terpineol Annealed at 300–400 °C in air for 1 h A sheet resistance down to 30 kΩ sq−1 and approxi-
flakes181 mate 80% transmittance at a wavelength of 550 nm.
Graphene NMP Annealed at 350 °C for 150 min A sheet resistance of 260 Ω sq−1 and a transparency of
nanosheets183 86%.
Ag NPs-GO192 Water Reduced by hydrazine at 110 °C in The printed film has a sheet resistance of 170 Ω sq−1
vacuum for 3 h. with a transmittance of 90.2%.

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Review
Concerns with TEs prepared with inkjet printing metal-
based inks include the stability due to oxidation, since Cu and
Ag are easily oxidized in humid or acidic environments. In
addition, NW-to-NW junction resistance is the main cause to
the high electrical resistance in transparent metal NW films.
2D graphene nanosheets are transparent, conductive, and
hydrophilic, and also gas impermeable, and are thus suitable
as a coating and a protective layer for metal NW-based TEs.147
As shown in Fig. 19a, the optical transmittance of Ag NW
based and Ag NW-rGO based TEs almost have no significant
change with the exposure time; however, the sheet resistance
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of Ag NW TEs increased by more than 2.5 times when it is
exposed to 70% RH at 70 °C for 8 days; but the sheet resistance
of Ag NW-rGO TE films only increased by 50% under the same
exposure conditions, as displayed in Fig. 19b. Both the Ag
NWs and Ag NW-rGO are quite transparent, indicating that the
rGO could not only greatly improve the resistance of Ag NW to
thermal oxidation but also retain the high transparency of the
TE. Lee et al.193 have described hybrid TEs based on graphene
and Ag NWs, and their uses as transparent and stretchable
electrodes. These graphene-capped Ag NW hybrid TEs showed
excellent electrical properties (sheet resistance ∼33 Ω sq−1),
high transmittance (∼94% in the visible range), robust stability
against electric breakdown and oxidation, and also impressive
mechanical flexibility and stretchability. Dou et al.194 reported
a solution-based approach to wrap the surface of ultrathin Cu
NWs with GO nanosheets. The solution process offers possi-
bility for inkjet printing. After deposition, high-quality Cu-rGO
core–shell NW-based transparent conductive electrodes could
be obtained by reducing the GO through a mild thermal
annealing. The core–shell NW structures enabled the pro-
duction of high-performance, low-cost Cu NW based TEs
which could maintain stability over 200 days in air and have a
sheet resistance of ∼28 Ω sq−1, and a haze of ∼2% at a trans-
Fig. 19 (a) Transmittance of TE made of Ag NW and Ag NWs-rGO as a
function of time. (b) Sheet resistance of TE made of Ag NW and Ag NW-
rGO as a function of exposed time. (c) Optical images of Ag NW (left)
and Ag NW-rGO (right) based films on glass substrates. (d) SEM image of
Ag-rGO film. Reproduced with permission from ref. 147, Copyright
2012, American Chemical Society.
988 | Nanoscale, 2017, 9, 965–993
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mittance of ∼90% in visible light, demonstrating the merits
comparable to ITO and Ag NW TEs. In addition, the 2D gra-
phene were also expected to tightly hold metal NWs to
enhance the charge transport between the metal NWs and
create a smooth film surface.195 Liang et al.196 demonstrated
the preparation of TEs based on an Ag NW percolation
network modified with GO nanosheets. The GO nanosheets
wrapped around Ag NWs and soldered the Ag NW junctions
and thus dramatically reduced the inter-NW junction resist-
ance without heat treatment or mechanical pressing. The GO-
wrapped Ag NW network had a sheet resistance of 14 Ω sq−1
with 88% transparency at a wavelength of 550 nm, indicating
the promising application in most fully flexible optoelectronic
devices. Thus the inclusion of graphene into metal NW-based
electrodes opens a new way to produce large-area, flexible,
highly conductive and transparent metal NW/graphene TEs.
Though the examples listed here were not prepared by inkjet
printing, the same strategies could also work well for inkjet-
printed metal-based TEs.
4. Outlook
In this review, we have attempted to provide a summary of the
applications of the inkjet printing technique in optoelectronics
fabrication. The material deposition processes for opto-
electronic device fabrication including solar cells, LEDs,
photodetectors TEs, etc. currently involve the use of solution
processes (such as spin-coating, spray-coating, doctor blading,
and screen printing) or vacuum deposition approaches. In
some cases, inkjet printing which has traditionally been used
in the graphical and publishing industries has recently been
employed to deposit one or more layers of devices.
Considering the high cost of lithography steps in industrial
manufacturing and the urgency to minimize the number and
complexity of these steps, inkjet printing provides an attrac-
tive, material-conserving alternative for some applications.
Compared with traditional deposition approaches, inkjet print-
ing has many advantages including processing flexibility, low
cost and low material wastage. In addition, inkjet printing is
also an ideal process for depositing a given material on a sub-
strate with pre-existing patterns and devices that would, other-
wise, be contaminated and/or damaged if another deposition
process was used. Nevertheless, the local nature of inkjet print-
ing also brings up issues that do not exist in traditional depo-
sition processing, such as nozzle clogging, coffee-ring effect,
wetting behavior of the ink on the substrate, the feature mor-
phology, resolution and so on. A better understanding of the
fluidic behavior of the droplet flight and the interactions with
the substrate or previously deposited layers is fundamental to
advance further development in this very exciting field.
Significant progress has been achieved in recent work to allevi-
ate such drawbacks on film quality and device performance, as
shown in the application examples. Given the impressive
recent progress and versatile nature of inkjet printing, we
This journal is © The Royal Society of Chemistry 2017

Nanoscale
anticipate a promising future of this technology in opto-
electronic device fabrication.
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