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2017 Inkjet-Printed Optoelectronics
2017 Inkjet-Printed Optoelectronics
2017 Inkjet-Printed Optoelectronics
Inkjet-printed optoelectronics
Cite this: Nanoscale, 2017, 9, 965 Zhaoyao Zhan,* Jianing An, Yuefan Wei, Van Thai Tran and Hejun Du*
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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
Received 20th October 2016, applications of inkjet printing in optoelectronics fabrication including solar cells, light-emitting diodes, photo-
Accepted 6th December 2016
detectors and transparent electrodes. In each application field, the challenges with the inkjet printing process
DOI: 10.1039/c6nr08220c and the possible solutions are discussed before a few remarks. In the last section, a brief summary on the pro-
www.rsc.org/nanoscale gress of inkjet printing fabrication of optoelectronics and an outlook for future research effort are presented.
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strates, ranging from conventional flat and rigid substrates to by a nozzle in the printhead and can be formed through either
the emerging flexible and even curved ones, paving the way to a continuous or a drop-on-demand (DOD) manner. In the con-
the development of flexible and conformable electronics. tinuous operating process, an ink-supply pump pressurizes the
Among all forms of printing techniques, inkjet printing is a ink and ejects it from the nozzle, generating a stream of liquid
powerful and cost-effective technique for deposition of liquid droplets. In the course of droplet generation, the droplets are
inks with high accuracy, which is not only of great significance selectively charged by the electric voltage applied to the
for graphic applications but also has enormous potential for the nozzle. The charged droplets will be deflected by an electric
direct printing of optoelectronic devices. The peculiar character- voltage on the deflection electrode and separated from the
istics offered by inkjet printing include additive patterning, uncharged ones. After that the charged droplets will reach the
reduced material consumption, maskless and non-contact depo- print substrate, while the uncharged ones which are not used
sition, low cost, and the capability of large-scale manufacturing.1 for printing are caught by the gutter and carried back to the
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The direct writing feature of inkjet printing enables deposition ink tank. The advantage of continuous printing is the high fre-
of numerous thin films with the ease of altering the design from quency of droplet generation and printing. Nowadays,
batch to batch. Moreover, inkjet printing is capable of depositing however, the DOD system is more widely employed because it
a given material in pre-determined sites on a substrate that has has lower system complexity and offers higher controllability
pre-existing patterns, where contamination or damage of pat- and accuracy of droplet displacement.5,6
terns would be induced with other deposition processes. In a DOD system, the ink droplets are jet from the nozzle by
This review highlights recent advancements of inkjet print- pulses generated by a thermal resistor, a piezoelectric transdu-
ing-based fabrication, in terms of active deposition and elec- cer, a thermal buckling or an acoustic wave. A thermal print-
trode deposition, of optoelectronic devices, such as solar cells, head uses a thin film resistive heater to rapidly vaporize a thin
LEDs, photodetectors, and transparent electrodes. The inkjet layer of the ink liquid (within a few microseconds) to form a
printing techniques are able to overcome these challenges fast expanding bubble which pressurizes the ink solution (see
existing in traditional fabrication processes, therefore produ- Fig. 1). The pressure for actuation should approximate the
cing new functionalities and/or boosting the cost-effectiveness saturated vapor pressure of the ink liquid at its superheat
and performance of the existing ones. 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
2. Principles of inkjet printing low costs, however it is confined to vaporizable inks due to the
technology requirement of the bubble formation. The elevated operating
temperature (ca. 300 °C) makes it inappropriate for polymer-
2.1 Droplet formation based printing. The piezoelectric DOD system has been widely
Inkjet printing, based on a drop-by-drop deposition fashion, employed to bypass this limitation. In the piezoelectric print-
has been invented and used for typewriting and recording for head, a piezoceramic transducer is electrically stimulated to
over 50 years. The droplets of ink with low viscosity are ejected induce mechanical actuation according to its resonant modes.
966 | Nanoscale, 2017, 9, 965–993 This journal is © The Royal Society of Chemistry 2017
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Z ¼ ðdργÞ1=2 =τ
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in order to produce patterns with feature sizes of 20–50 µm appear when NPs in the ink accumulate along the perimeter of
and a thickness lower than 1 µm. This coarse resolution is the drying droplet due to inhomogeneous evaporation of the
caused by the combined effects of droplet diameters which are solvents.14 The uneven morphology leads to the formation of
usually larger than ∼10–20 µm and placement errors which are electric defects.
in the range of ±10 µm at the standoff distances of ∼1 mm. In To overcome the coffee-ring effect, the evaporation process
electrohydrodynamic (EHD) printing, which uses electric fields of the solvent has been modified by introducing drying agents,
rather than a resistive heater, piezoelectric transducer or precisely controlling the humidity in the ambient environment
acoustic wave to eject the ink liquid, the droplets are created during the solvent evaporation, or tuning the heating rate.14–17
by a fine jet generated at the apex of the conical ink meniscus In an optimized solvent mixture, the drying agent has a higher
at the tip of the nozzle (see Fig. 2).10 Unlike conventional boiling point (B. P.) and a lower surface tension compared
inkjet printing processes, EHD printing pulls the liquids with the main solvent. During the drying, the main solvent
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rather than pushing them, thus printing of the high viscosity having a lower B. P. and higher surface tension evaporates
ink is not challenging for EHD printing. The advantages of faster at the contact line creating an outward flow, which is
EHD printing include high resolution (submicron), flexibility gradually delayed as the contact line approaches the solvent
in the ink formulation design, and easy jetting without clog- with a larger fraction of the drying agent. Meanwhile, an
ging the nozzle. EHD printing has enormous potential in inward flow (Marangoni flow) will be developed by the surface-
printing of complex and high-resolution features and is tension gradient over the whole droplet. The outward and
opening up new ways toward nanotechnology. Marangoni flows continuously circulate the ink contents
inside the fluidic droplet, producing a uniform assembly of
2.2 Control of pattern morphology and feature size the ink contents. The drying process of a droplet inkjet-
Ink volatility and viscosity are critical parameters of controlling printed with a mixed-solvent ink is schematically shown in
the pattern morphology. Non-uniform films are easily formed Fig. 3, where chlorobenzene (CB) is the main solvent, and
due to the ‘coffee-ring’ effect or central ‘mountaintop’ effect dodecane is the drying agent. Fig. 4 presents the non-uniform
which induces capillary12 or Marangoni13 flows during the and uniform surface profiles of Al2O3 NPs respectively pro-
evaporation of the ink solvents. Coffee-ring edges usually 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.
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greatly improve the final inkjet-printed pattern profile by intro- unfavorable cost. Since the first report of organic solar cells by
ducing the recirculating flow. The heating process is also screen printing,20 this technique has been presenting promise
found to be critical in controlling the coffee-ring effect, since of developing industrially scalable low-cost fabrication pro-
the solvent evaporation is also highly dependent on the cesses. However, the ever growing demand for improved per-
heating process. Gradual heating could effectively restrict the formance has led to an expanding interest in inkjet printing
convection flow during the evaporation in a printed low- which enables printing features with higher resolution, result-
viscosity Ag (Ag) NP ink, causing the lines to become convex ing in lower shadowing losses and reduced manufacturing
with the homogeneously and very densely packed NPs, which costs. In addition, inkjet printing technology allows for the
greatly enhances the electrical conductivity of inkjet-printed deposition of active materials in specific areas of the pre-
Ag lines.17 patterned substrate. The first demonstration of inkjet printing
Apart from the long-standing coffee-ring effect, the mor- of a thin-film library of donor/acceptor systems used in bulk
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phology of printed patterns could also be greatly affected by heterojunction (BHJ) organic solar cells was reported by Marin
many other factors, such as the aerodynamic effect, electro- et al.21 In addition, the morphology studies on inkjet-printed
static interaction of droplets, satellites, and interaction films with atomic force microscopy (AFM) suggested the for-
between the liquid ink and the substrate. It is quite challen- mation of homogeneous structures. Then Steirer et al.22 sys-
ging to print long-distance and continuous lines, with con- tematically investigated the critical parameters for both inkjet
trolled feature sizes and morphology.5 To minimize the feature and ultrasonic spray deposition of poly(3,4-ethylenedioxythio-
size of the printed patterns, it is essential to limit ink spread- phene) polystyrene sulfonate (PEDOT:PSS) thin films on com-
ing on the surface. Changing the surface energy of the sub- mercial indium tin oxide (ITO) for organic photovoltaic device
strate and creating patterned chemical/physical structures on fabrication. Their study showed that the efficiency of organic
the substrate are efficient methods to control the wetting be- solar cells with an inkjet-printed PEDOT:PSS hole conducting
havior of the droplets on the substrate and to increase the layer were comparable with that of solar cells fabricated
printing resolution. The droplets on a non-wetting substrate through the traditional spin-coating process. The drop spacing
tend to partially recede or even completely rebound, while the and the substrate temperature are critical parameters in inkjet
ones on a wetting surface are prone to spread away,18 giving a printing; while for ultrasonic spray coating, the substrate
flat-disk-shaped pattern with a diameter larger than the orig- temperature and the solution flow rate will play critical roles.
inal droplet, resulting in very coarse printed structures. PEDOT:PSS films produced by optimized inkjet printing, ultra-
Although dewetting treatment could to some extent improve sonic spraying and spin coating were compared in a proto-
the pattern resolution, bulges will be formed on lines that are typical BHJ organic solar cell which employs a poly(3-hexylthio-
unstable on substrates with too low surface energy, which phene) and 6,6-phenyl-C61-butric acid-methyl ester (P3HT:
would locally broaden the printed graphics and degrade the PCBM) blend as the absorber. The results revealed that the
continuity of printed features. In addition to surface energy efficiencies of the devices fabricated by the three processes
modification, pre-patterning the surface with varying wetta- were comparable (in detail, the efficiencies were 3.3% 3.5%
bilities or surface topographies in different regions of the and 3.6%, for inkjet printing, spray deposition, and spin
substrate could benefit reducing the spreading of the ink solu- coating respectively). Furthermore, hybrid transparent conduc-
tion. Ultrafine gaps can be created by a self-aligned printing tive films prepared by inkjet printing PEDOT:PSS and other
method that relies on differentiation of wettability.19 Another conductive components have also been demonstrated for
scenario lies in optimizing the ink materials and formulations, replacing the ITO transparent electrodes in organic solar cells,
which not only influence the droplet formation process, but which will be covered in section 3.4.3.
also prescribe the printing resolution and the device perform- It is found that the morphology of inkjet-printed films
ance. The utilization of an ultrafine nozzle is desirable for could be dramatically tuned by using additives, and thus
printing patterns with small feature size if the clogging could affects the properties of organic optoelectronics and the
be avoided by using low viscosity inks with fine NPs. Addition overall performance of the devices. Xia et al.23 fabricated
of special additives into the ink dispersion is also useful for organic solar cells by using a blend of poly(9,9-dioctylfluorene-
tuning the viscosity of the ink and benefiting inkjet printing of co-benzothiadiazole) (F8BT) with poly(9,9′-dioctylfluorene-
high-resolution patterns.18 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-
3. Applications butylphenyl)diphenylamine) (TFB). They compared the devices
with a film produced by either inkjet printing or spin-coating.
3.1 Solar cells It has been discovered that the rapid drying of the small
Solar cells could directly convert solar irradiation into electri- inkjet-printed droplets resulted in a finer phase separation,
cal energy and thus offer the promise to relieve our reliance on producing OLEDs and organic solar cells with even better per-
the long-standing fossil energy resources which have caused formances and a higher efficiency than those prepared by the
serious environmental issues to our home planet. The use of traditional spin coating method. However, a critical issue with
solar cells, however, has not been expanded yet due to the 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 a fine film morphology and also the coffee-ring effect would be
p-xylene. This problem could be possibly alleviated by using a decreased.28
solvent mixture. Hoth et al.24 used a blend of P3HT:PCBM in a Though inkjet printing technology has manifested its versa-
mixed solvent of o-dichlorobenzene and mesitylene to inkjet tility in fabricating active components and/or hole conducting
print organic solar cells on PEDOT:PSS coated ITO, where layers, the development of an ambient environment compati-
Ca : Ag was deposited as the top cathode. They also suggested ble inkjet printing process is highly desirable. Aernouts et al.29
that by optimizing the ink solvent formulation, the morpho- have demonstrated inkjet-printed P3HT:PCBM blend solar
logical and interfacial properties of the printed P3HT:PCBM cells in the ambient environment by utilizing a polymer: fuller-
blend photoactive layer could be significantly improved. For ene blend dissolved in a mixture of the main solvent CB and
example, a mixture of high and low boiling solvents, 68% of the high B. P. solvent tetrahydronaphthalene (THN). They
ortho-dichlorobenzene (ODCB) and 32% of mesitylene could found that a balance between ink viscosity and surface wetting
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print organic solar cells with an intimate morphology in the is critical to a smooth active layer with a small surface rough-
P3HT:PCBM blend, giving a better solar cell performance with ness, producing devices with a PCE of 1.4% under simulated
a larger short-circuit current of 8.4 mA cm−2, an open-circuit AM1.5 conditions. The addition of a high B. P. solvent could
voltage of 0.54 V, a filling factor of 0.64, and a higher power also help to prevent clogging of the nozzle. Recently, Jung and
conversion efficiency (PCE) of 2.9%. While, the device pre- co-workers27 reported the fabrication of all-inkjet-printed,
pared with the inkjet-printed P3HT:PCBM blend with the tetra- air-processable organic solar cells with the structure of
lene solvent shows a much large roughness and a poor distri- PEDOT:PSS/poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-
bution of PCBM in the P3HT domain, thus, outputting a poor thienyl-2′,1′,3′-benzothiadiazole)]:[6,6]-phenyl-C71-butyric acid
performance. More recently, Hoth et al. further improved the methyl ester (PCDTBT:PC70BM)/ZnO/Ag. A high-conductivity
performance of inkjet-printed organic solar cells by using the PEDOT:PSS aqueous dispersion was printed to replace ITO as
combined regioregularity(RR)-96%-P3HT and the ODCB/ the anode. 5 wt% dimethyl sulfoxide (DMSO) and 0.1 wt%
mesitylene solvent mixture to control ink drying and film fluorosurfactant were added into the PEDOT:PSS ink to
formation processes. They have obtained a suitable gelation prepare a highly conductive and uniform film. A PCDTBT:
time, improved the morphology of the P3HT:PCBM layer, and PC70BM (at ratio of 1 : 4) donor/acceptor blend dispersed in a
achieved an impressive PCE of 3.5%.25 Eom et al. reported 5 : 4 : 1 volume mixture of the CB, mesitylene (MT) and chloro-
P3HT:PCBM blend organic solar cells produced with the form (CF) ternary solvent, was then printed onto the PEDOT:
inkjet-printed PEDOT:PSS hole transporting layer, and PSS layer. It was found that the inkjet-printed PCDTBT:
suggested that the addition of a certain amount of the glycerol PC70BM blend layer presented similar morphological pro-
and ethylene glycol butyl ether (EGBE) surfactant into PEDOT: perties (see Fig. 5) and excited state dynamics with its spin-
PSS inks improved the surface morphology and conductivity of coated counterparts. The all-inkjet-printed organic photo-
the PEDOT:PSS hole transporting layer, resulting in enhanced voltaic devices exhibited an average PCE of 2%. A noteworthy
performance of the organic solar cells. Using the optimized advantage in this work was that all the fabrication and
ink formulation of PEDOT:PSS to print the hole transporting measurement processes were performed in air at room temp-
layer and the P3HT:PCBM blend as the photoactive layer, they erature. The performance could be drastically improved to 5%
have achieved a PCE of 3.16% in P3HT:PCBM based BHJ solar by depositing the cathode via evaporation. The effects of addi-
cells.26 tives on the inkjet-printed organic solar cells are summarized
They further demonstrated the organic solar cells fabricated in Table 1.
by inkjet printing both the photoactive P3HT:PCBM layer and Despite its versatile roles in organic solar cell fabrication,
the PEDOT:PSS hole transporting layer, and the results inkjet printing of inorganic solar cells remains a challenge.
suggested that adding high B. P. additives, including 1,8 The suspended particles in inorganic inks have a strong ten-
octanedithiol (ODT), ODCB and chloronaphthalene (Cl-naph), dency to agglomerate, leading to an increase in viscosity and
into the photoactive dispersion in the CB solvent drastically thus clogging of the nozzles. These challenges could be miti-
affected the morphological and optoelectronic properties, and gated or eliminated by designing ink formulations, for
overall solar cell performance. A device printed from an ODT- example, replacing the inorganic NPs in the ink with their dis-
formulated ink exhibited the best overall performance with a solvable precursors could greatly alleviate the ink agglomera-
PCE of 3.71%. Thus, developing a proper formulation of multi- tion and clogging of nozzles. Wang et al.30 have fabricated
component inks to tune the morphological properties of the chalcopyrite CuInxGa1−xSe2 (CIGS) thin film solar cells by
inkjet-printed BHJ solar cells is an essential step for the inkjet inkjet printing CIGS precursors on a molybdenum (Mo) elec-
printing of high performance organic photovoltaics. The trode, followed by selenization of the printed CIGS precursor
inclusion of high B. P. additives enables a controlled drying to form CIGS light absorber layers, and deposition of n typed
and thus allows for sufficient time for film formation of the CdS layers and ZnO window layers, as shown in Fig. 6. They
photoactive layer, thereby improving the crystallinity of the achieved inkjet-printed CIGS solar cells with a short circuit
photoactive polymer. Moreover, the wettability of the P3HT: current, open circuit voltage, filling factor, and total area PCE
PCBM inks on the PEDOT:PSS layer could also be enhanced, of 29.78 mA cm−2, 386 mV, 0.44, and 5.04%, respectively.
thus the produced active layer would have high uniformity and 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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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. 9 (a) Emission spectra of devices with ten drops per pixel (dashed
Fig. 8 (a) Optical images of an inkjet-printed library of CdTe NCs/PVA
curve) and 15 drops per pixel (solid curve); (b) luminance vs. applied
composite layers emitting at different wavelengths. The PVA content in
voltage. Inset: An optical photograph of QD LEDs (243 pixels with a
the solution used for printing was systematically varied from left to right
common cathode) at the operation voltage of 12 V. Reproduced with
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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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and a responsivity of 0.11 A W−1 at a gate voltage of −10 V and Fig. 14g and h. Upon irradiation, drain current raised within
a bias voltage of 1 V. Polymer phototransistors have also been 1 s, however, after light was switched off, drain current did not
achieved by inkjet printing a diketopyrrolopyrrole-thiazolothia- decay to the dark current but stayed at steady level the for at
zole copolymer (PDPPTzBT) as the photoactive layer on a least 104 s, due to the persistent photoconductivity (PPC). The
bottom gate and bottom contact structure.61 The authors first PPC effect could be erased by applying an opposite gate
defined the electrode areas by inkjet printing a pure solvent to voltage.
selectively remove the PMMA photoresist. After electrode depo- Though the organic semiconducting materials are most
sition and lift-off, the channel length could be defined, as commonly utilized to provide a proof-of-concept device fabri-
shown in Fig. 14a–d. With this method, the minimum channel cation feasibility, many inorganic semiconducting materials
width could reach 700 nm. The PDPPTzBT was also deposited are also examined to extend the optical absorption window of
onto the channel area by inkjet printing the ink formulation of photodetectors. Inorganic nanomaterials include NPs,56,58
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photodetectors, especially for UV light detection. Indium comparable with that of other devices fabricated by the con-
doped zinc oxide (IZO) films and TiO2 NWs, both exhibiting a ventional techniques, including vacuum deposition and spin-
photoresponse in the UV region, have showcased this possi- coating. The versatility of this technique has been clearly
bility. IZO-based phototransistor fabricated by inkjet printing demonstrated by the reported studies where varied materials,
showed a current on/off ratio of four orders in magnitude, and structures and patterns were used after a systematic optimiz-
the rise and decay times of 5 ms and 10 ms respectively.85 ation of the ink.59 Further effort toward large-scale application
Chen et al.86 demonstrated inkjet printing of high-perform- of this technique lies in improvement in fabrication yield,
ance TiO2 NW based UV photodetectors. They first printed a resolution, and device performance.
commercial Ag NW suspension in isopropanol (IPA) onto flex-
ible and transparent polyethylene terephthalate (PET) sub- 3.4 Transparent electrodes
strates to form the electrode patterns, then another layer of From section 3.1 to section 3.3, we have discussed the recent
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TiO2 NWs was also inkjet-printed onto the electrode patterns advances in inkjet printing of solar cells, LEDs and also photo-
to fabricate a UV photodetector with >80% visible transmit- detectors. However, apart from the photoactive layer, the trans-
tance. The printed UV photodetectors presented high an on/ parent electrodes (TEs) are also essential elements in various
off ratio of 2000 and also fairly a low dark current of 10−12– optoelectronic devices. In the past decade, the demand for
10−14 A. Under a 2 V bias voltage, the detectors responded to transparent conductive electrodes has been persistently
UV illumination with rise and decay times of 0.4 s and 0.1 s soaring due to the increasingly expanding market of various
respectively. A summary of performance of inkjet-printed daily electronics ranging from touch screen displays to solar
photodetectors is shown in Table 3. cells, and there is no doubt that the market will continue spur-
The above examples confirm the great potential of applying ring in the foreseeable future.2 A general requirement in the
the inkjet printing technique in the photodetector fabrication sheet resistance of TEs is in the range of 10–103 Ω sq−1 at a
process, which allows for the production of a performance transparency of ≥90%, which is also application specific.
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A sheet resistance of 400–1000 Ω sq−1 is adequate for many However, there is always a trade-off between the high conduc-
applications in touch screens, and of 10–50 Ω sq−1 is already tivity and low optical absorption of the film.
suitable for OLEDs and solar cell applications.87,88 Currently, The solvent properties are one the most essential factors
the commercially used TEs in most optoelectronic devices are determining the final film properties. The inclusion of a high
made of ITO, which is usually prepared by vacuum deposition. B.P. solvent to control the wetting behavior, surface tension,
However, there are serious issues related to the use of such evaporation and drying of droplets on the substrate is a widely
ITO-based TEs in terms of sustainable development due to adopted strategy to design the feature of the printed patterns.
both technical and economic restrictions. First, the price of Ummartyotin et al.99 demonstrated PEDOT:PSS films de-
the element indium is becoming more expensive because of its posited by inkjet printing an aqueous dispersion of PEDOT:
ever increasing consumption and scarcity. Second, the ITO PSS NPs. By optimizing the particle size, the surface tension,
deposition process needs to be conducted in a high vacuum at and the viscosity of the ink, PEDOT:PSS films were successfully
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high temperatures, and usually wastes a large part of the ITO inkjet-printed on flexible cellulous substrates, whilst retaining
source. Furthermore, the brittleness and the high temperature its transparency feature and enhanced the electrical conduc-
process could not be compatible with flexible, and stretchable tivity. Eom et al.26,28 have also systematically investigated
requirements of current optoelectronic devices.89 Inkjet print- inkjet printing of PEDOT:PSS layers, and found that the mor-
ing enabled by a solution process will provide an effective phology and conductivity of the inkjet-printed PEDOT:PSS
alternative to the traditional ITO technology. The expanding films could be well improved by adding high B. P. solvents
class of inks for printing TEs includes conductive organic poly- such as glycerol and the ethylene glycol butyl ether surfactant.
mers, transparent conducting oxides (TCOs), metal NW net- Natori et al.100 found that the conductivity of printed films
works, graphene, and CNTs. In the next section we will briefly also depended on the substrates, for example the conductivity
present TEs fabricated by inkjet printing these nanomaterials of PEDOT:PSS layers printed on PET is different from that of
and their hybrids. the film on polyester. The most significant improvement in
3.4.1 Conductive organic polymer inks. The conductive sheet resistance was realized by printing PEDOT:PSS onto poly-
organic polymers are one of the indispensable components in ester with a small addition of glycerol in the ink. The decrease
current organic optoelectronics. The solution-processibility in the sheet resistance was attributed to the decreased rough-
enables us to build flexible optoelectronics in a large-scale, ness of the substrate and the surfactant glycerol which reduces
cost-effective manner. Several conducting polymers, such as the solution’s surface tension and leads to smoother films.
polypyrrole, polyaniline and PEDOT have been well studied The inkjet-printed PEDOT:PSS films were also explored as
and widely used in optoelectronics. Taking PEDOT as an TEs for various kinds of optoelectronics. The chemical doping
example, its application potential lies in its important pro- of PEDOT:PSS was proven to be an effective method for inkjet
perties such as excellent electrical conductivity, optoelectronic printing the PEDOT:PSS films with high transparency and con-
properties, and thermally stability (up to 230 °C). However, its ductivity simultaneously, toward fabrication of ITO-free opto-
solubility problem has hampered the fabrication involved with electronic devices.101–104 Ma et al.104 fabricated transparent
inkjet printing. This could be overcome by mixing it with a and flexible touch sensors based on inkjet-printed PEDOT:PSS
water-dispersible polystyrene-sulfonate (PSS), by charge-balan- films as TEs and inkjet-printed poly(methylsiloxane) as a
cing counterion doping polymerization, which yields water-dis- dielectric layer. Yoshioka et al.40 have demonstrated the prepa-
persible PEDOT:PSS.90 By appropriate modification, PEDOT: ration of PEDOT:PSS films with area-specific conductivity by
PSS films could possess very good conductivity comparable selectively inkjet printing a hydrogen peroxide ink and varying
with most widely used ITO films while having enough optical the oxidation state of PEDOT:PSS. Jung et al.27 have demon-
transparency, and thus it is a competitive candidate to replace strated that inkjet-printed PEDOT:PSS films could be directly
ITO in optoelectronics.91–93 The formulated PEDOT:PSS used as both hole conducting layers and the anode for organic
aqueous dispersion is very stable in water and has excellent photovoltaic solar cells. They deposited the PEDOT:PSS films
versatility to be deposited into films by various kinds of pro- directly on glass by inkjet printing the ink of the high-conduc-
cesses,94 including spin coating,95,96 spray coating,93 and tivity PEDOT:PSS aqueous suspension as the anode. The
inkjet printing.26,27 inclusion of 5 wt% DMSO and 0.1% fluorosurfactant into the
As a matter of fact, Ballarin et al.97 have found that there ink benefits high conductivity and uniform morphology. By
was no obvious distinction in the surface morphology and printing PEDOT:PSS/PCDTBT:PC70BM/ZnO/Ag layers in
electrochemical characteristics between continuous PEDOT: sequence, the organic solar gave a PCE of 2%; by replacing the
PSS films fabricated by inkjet printing and by spin-coating, inkjet-printed Ag cathode with evaporated Ag, the PCE was
indicating that inkjet-printed PEDOT:PSS films could be an drastically improved to 5%. The interesting observation is that
efficient and clean alternative. The thickness of the PEDOT: the solar cells with an inkjet-printed PEDOT:PSS anode
PSS films increased linearly with the increase of the coating showed comparable performance with those based on ITO
layers. Kwon et al.98 proposed that the resistance of the TEs. Chou et al.105 have reported inkjet printing of PEDOT:PSS
printed PEDOT:PSS films decreased for thicker films, which TEs for OLED with high performance. They found that the
could be attributed to the increased hopping paths for charge addition of the IPA solvent to the aqueous ink could effectively
carrier transport when the thickness of the film increased. 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 Among all solution synthetic processes, hot injection has been
be comparable with that of devices fabricated by spin-coating, intensively studied for the synthesis of colloidal NCs in recent
and the sheet resistance of the inkjet-printed films was years. In a typical hot injection synthesis process, a chemical
decreased 10-fold in magnitude, comparing with that prepared reaction will happen between the injected source and the
by the spin-coating technique. Micro-Raman spectroscopic mother solution and NCs will form in a localized environment.
characterization suggested that the improved electric pro- This method has been successfully employed to synthesize
perties were ascribed to a longer effective conjugation length AZO111 and ITO112 NCs with simultaneous control of their size
of PEDOT chains in inkjet-printed PEDOT:PSS films. and doping level. Uniform NC films of up to the centimeter
3.4.2 Metal oxide inks. TCOs are a family of metal–oxide scale have been assembled from these NCs and presented
materials bearing both optical transparency and electrical con- impressive electrical conductivity (356 Ω sq−1) and optical
ductivity, and have been widely used as TEs in various current transparency (93% in visible spectra range) after appropriate
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daily electronics. A typical TCO group includes the most widely thermal treatment. Ito et al.113 proposed a high-yield hot-injec-
used ITO, FTO, and also aluminum-doped zinc oxide (AZO). tion synthetic process that was able to produced crystalline,
Most scientific studies and current industrial applications monodisperse TCO NCs at a temperature lower than the
mainly involve the vacuum deposition processes, which cause decomposition temperature of the source. A rapid esterifica-
a lot of practical technical issues in applications and also tion reaction was initiated by slowly injecting the metal oleate
bring about the cost and environmental concerns. Inkjet print- complex into oleyl alcohol at 230 °C. This protocol can be used
ing of metal oxides will provide a greener, more efficient, and to synthesize different types of NCs, including ITO, iron oxide
more cost-effective alternative to the current mainstream and ZnO and so on.
vacuum technology. The hot inject synthetic process has two disadvantages.
The ink used for inkjet printing of TCO TEs could be either First, the ability to scale up the process is limited by the small
TCO precursors or synthesized TCO NCs. The synthesis of TCO dose adopted to promote high-quality doping. Second, the
NCs through solution phase processes is a promising strategy doping quality is strongly dependent on the injection para-
for the deposition of TCO films. A typical example of the metal meters and the dopant. The optimization of these parameters
oxide ink which one could come out easily should be the ITO for the preparation of other NCs is highly time-consuming,
ink, because it has been widely used in current optoelectronic thus greatly hindering the scaling up of the production of
devices. The implementation of inkjet printing enables us to various NC inks for industrial applications.
precisely control the position and amount of ITO ink drops, To overcome the limitation of the hot injection method,
which would greatly reduce the material consumption. Kim Song et al.114 developed a general one-pot process for the
et al.106–108 demonstrated the fabrication of ITO TEs for cost- preparation of various kinds of TCO NCs, which could be
efficient organic solar cells by inkjet printing ITO NPs. After readily scaled up to a production of 10 g per pot. The syn-
performing a rapid thermal annealing at 450 °C, they directly thesized TCO NCs (Fig. 17) have good crystallinity, uniform
obtained patterned ITO electrodes with an average transmit- morphology, narrow size distribution, and well-controlled
tance higher than 80% and a sheet resistance of around 200 doping level. The final colloids could sustain good dispersion
Ω sq−1 without using a traditional photolithography process. capability over 1 year and hence could be used as inks to print
Another strategy implemented to reduce the consumption of high-performance TE films. The resulted TCO NC based TEs
the scarce element indium was doping the indium oxide with showed high performance in solution-based devices. Gaspera
other elements.89,109 The transparent zinc- and tin-co-doped et al.115 reported a non-injection synthetic process for the pro-
indium oxide (IZTO) electrode with a sheet resistance of as low duction of monodispersed ZnO-based NCs with Al, Ga, or In
as 20.6 Ω sq−1 and an optical transmittance of up to 81.29% dopants. The synthetic method is highly reproducible and
was obtained by applying rapid thermal annealing on the permits dopant/Zn atomic ratios of over 15%. Another advan-
inkjet-printed IZTO TEs in a nitrogen/oxygen mixture atmo- tage of this method is that the synthesis could be even per-
sphere.109 Titanium (Ti)110 was also used to dope In2O3, after formed at a precursor concentration greater than 0.2 M with
an optimized rapid thermal annealing process, the inkjet- reaction yields higher than 90%. The resulting colloidal dis-
printed Ti-doped In2O3 (ITiO) film showed a sheet resistance persions present good electric conductivity after being
of 37.41 Ω sq−1 and an optical transmittance of 85.40%. These assembled into films and excellent transparency in the visible
results suggested that the degree of interconnection of the spectral range. Luo et al.116 also presented the fabrication of
ITiO NPs critically affects the sheet resistance, optical transpar- high quality TEs by wet-chemical deposition of antimony
ency, and surface morphology of the final ITiO electrode. doped tin oxide (ATO) NCs. They also found that OLED fabri-
The solution synthesis enables one to control the size, mor- cated on ATO NC-based TEs exhibited a performance compar-
phology, and composition of the TCO NCs simultaneously. able to that of commercial ITO-based devices. These above
Other advantages related to the use of TCO NC inks in the mentioned advances indicate the potential of solution pro-
inkjet printing technique include the compatibility with flex- cesses for production of high-quality metal oxide NC colloidal
ible and stretchable substrates, and the simple and straight- inks for ink-jet printing of next-generation TEs. However, the
forward deposition manner. A lot of efforts have been made to as-printed TEs are not suitable for various optoelectronic
synthesize TCO NC inks in solution over the past few years.89 devices. UV treatment could effectively remove the organic
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inkjet printing of the Ag NW ink onto a polymer substrate. tively high sheet resistance (97% at a sheet resistance of
They found that the dilution of the ink suspension and 20 Ω sq−1) have been demonstrated by changing the printing
addition of diethylene glycol (DEG) could improve the print- parameters.
ability of the Ag NW ink. The optimized NW concentration was The coffee-ring effect is normally considered as a negative
0.85 mg ml−1 and the IPA : DEG volumetric ratio was factor in inkjet printing. However, by appropriately designing
0.85 : 0.15, for the best printing performance with stable the coffee-ring pattern, it also helps to form excellent TEs.
droplet generation and movement. The solvent evaporation Layani et al.138 demonstrated that the coffee-ring effect could
during and after deposition is also critical to form a high- be used to inkjet print transparent conductive patterns. The
performance TE film. The intermediate drying step during a TEs were achieved by forming a 2D array of interconnected Ag
print session in a vacuum at a pressure of 0.1 mPa and temp- NP rings. The interconnected Ag patterns were fabricated by
erature of 110 °C for 30 min to slowly evaporate the solvent is inkjet printing the Ag NP ink (0.5 wt%, ∼20 nm Ag NPs) on
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critical to obtain a conductive Ag NW network. Lu et al.137 plastic substrates. The width and height of the rim of the indi-
demonstrated an inkjet-printed AgNW film as a top electrode vidual rings are less than 10 µm and 300 nm respectively. The
for semitransparent organic solar cells. They found that the diameter of the ‘hole’ surrounded by the rim is about 150 µm;
addition of ethylene glycol into the Ag NW ethanol dispersion thus the whole array of the interconnected rings is highly
was very critical to prevent nozzle clogging. The optical and transparent. The rims of the rings consist of self-assembled,
electrical measurement results showed that the sheet resist- closely packed Ag NPs, making the individual rings and the
ance of the printed Ag NW decreased dramatically from 2190 whole ring array highly conductive. The whole interconnected
Ω sq−1 to 26.4 Ω sq−1 with the increase of printing times from ring array presented a high transparency of 95% and a low
3 to 9, whereas the average transparency of the printed Ag NW sheet resistance of ∼4 Ω sq−1, which were better than those of
films over a 400–800 nm wavelength just decreases slightly traditional ITO TEs. Another strategy to form TEs based on
from 95% to 83%. Note that the 7-time-printed Ag NW layer metal NPs is by printing metal grids with both good optical
has an average sheet resistance of 44.9 Ω sq−1 and an average transmittance and electrical conductivity.
transparency of 86.4%, which are close to that of the widely The current issues with the inkjet printing of metal-based
used ITO electrodes. TEs include the clogging of the printer nozzle due to the high
Metal NP dispersions are ideal inks for inkjet printing of tendency of precipitation of metal contents in the ink, the
conductive traces. Ag NPs were commonly used for electrode rough surface of the printed TEs and also the instabilities in
printing in a wide range of electronic devices.59,88,138–140 the ambient environment. The clogging problem could be alle-
Layani et al.141 also demonstrated inkjet printing of Ag grid viated by proper design of the ink formulation,137 passivation
TEs from the Ag NP ink on transparent plastic substrates. The on the printed surface will help to reduce the surface rough-
inkjet-printed TEs showed a low sheet resistance (1–5 Ω sq−1) ness,144 and the stabilities could be readily improved by
at a high transparency of 83% in the range of 400–800 nm, encapsulation.145–147
which could be superior to those of many TEs used in opto- 3.4.4 CNT based ink. CNTs are composed of one-atom-
electronics. The light reflection on the wide metal grid is the thick sheets of carbon with a hexagonal structure in a cylindri-
main cause for the reduction in the transparency of the metal cal-hollow-wall configuration. There are single-walled CNTs
grid TEs. Shrinking the width of the metal grid line was (SWCNTs) and multi-walled CNTs (MWCNTs), and their length
believed to be an effective method to reduce the light reflec- could range from less than a micrometer to centi-
tion on the metal grid. Jang et al.142 have fabricated invisible meters.70,71,148 For SWCNTs, the electronic properties are
Ag-grid (less than 10 µm) by EHD inkjet printing of Ag NP determined by their chiral structures, one third of them are
inks. As one expected, the improvement in the electrical con- conducting, and two thirds of them are semiconducting. The
ductivity of the TEs was at the cost of the optical transparency intrinsic electrical resistivity was found to be around 10−6
as the Ag-grid pitch decreased. After annealing at 200 °C under Ω cm for individual SWCNT and 3 × 10−5 Ω cm for single
near-infrared, the EHD inkjet-printed 150 µm Ag-grid pitch MWCNT.87,149 Because of their excellent electrical properties,
TEs presented a sheet resistance of 4.87 Ω sq−1 and a transmit- solution processability, mechanical flexibility, and potential
tance of 81.75%. Schneider et al.143 have employed EHD inkjet for low-cost and large-scale production, thin films made of
printing to print Au and Ag grids with line widths from 80 to randomly distributed CNTs were extremely promising for the
500 nm with Au and Ag NP inks. The high-resolution was fabrication of flexible TEs.
achieved with the help of the high resolution NanoDrip print- The printing of CNTs has several advantages, such as low
ing mode. This EHD inkjet printing process demonstrated the material consumption, low equipment costs, high throughput,
capability of printing high-aspect-ratio structures (nanowalls and additive fabrication. CNT inks for high-quality TE printing
or NWs) with a high resolution, significantly decreasing the can be prepared by combining the CNT dispersions with suit-
sheet resistance while maintaining the high-level optical trans- able additives, depending on the required printing method.
parency. The EHD inkjet printing also provided flexibility in The dispersion medium could be water or organic solvents,
designing the application specific TEs, for example, both low and the concentration of CNTs is in a wide range from
sheet resistance with a relatively low transparency (8 Ω sq−1 at 0.01–10 mg ml−1. Concentration limitation is very essential for
a transmittance of 94%) and high transmittance with a rela- 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 ent back electrode was fabricated by rod coating of MWCNT
less critical compared to screen printing. Despite their high films, and the counter electrode was fabricated by inkjet print-
hydrophobicity and tendency to aggregate, CNTs can be dis- ing MWCNT films on transparent flexible substrates. The elec-
persed well in many solvents by proper surface chemical modi- troluminescent device gave an intense emission after applying
fication or with the help of solubilizing additives, including a bias between the two printed MWCNT electrodes.154
surfactants, cellulose derivatives, and conducting polymers, Similar to the case of inkjet printing of Ag TEs from the Ag
and thus can then be used as inks for printing. Chemical NP ink,138 the coffee-ring effect is also not always a bad thing.
modifications of the CNTs with functional groups favor the Lee et al.161 reported the fabrication of circular rings by inkjet
interactions between CNTs and the dispersing medium. The printing the water-based SWCNT ink. Most of the SWCNT con-
major issue related to organic solvents without using disper- tents concentrated at the rims due to the coffee-ring effect.
sing agents is the low CNT concentration limit, which is lower They found that weak oxidants such as UV/ozone could also be
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than 0.1 g L−1.2 The advantages of water-based CNT inks able to create oxygen-containing groups on SWCNTs and to
include the high concentration limit and also high safety enhance the dispersion stability of the SWCNTs in a water-
during the printing process. To obtain stable aqueous disper- based solvent. The TEs were achieved by inkjet printing the
sions of CNTs, various kinds of surfactants such as Triton interconnected or stacked rings; a sheet resistance of 870
X-100,150,151 sodium dodecylbenzene sulfonate (SDS),150,152 Ω sq−1 and an optical transparency of 80% (at 550 nm) were
and CTAB,153 were widely used to stabilize the CNT content. achieved in the TEs after 40 prints. Shimoni et al.157 have also
When a surfactant is added into a water-based CNT ink, with inkjet-printed transparent conductive patterns, and arrays of
the help of hydrophobic tails, the surfactant molecules are interconnected CNT circular rings on flexible substrates by
attached onto the surface of each CNT, which create a barrier using the coffee-ring effect. Direct fabrication of these rings
around the perimeter of the CNT to physically mitigate the van was realized by inkjet printing an aqueous-CNT dispersion,
der Waals forces between the CNTs in close proximity. In which concentrated and self-assembled at the rims of the pat-
addition, because of the hydrophilic heads in capping surfac- terns. The electrical performance of the printed CNT films
tants on CNTs, there is a repulsive chemical force between could be much improved by post-printing treatment with hot
CNTs which also helps to stabilize the CNT dispersion. nitric acid, after which a sheet resistance of 156 Ω sq−1 and an
Azoubel et al.154 reported a MWCNT ink with a good inkjet optical transmittance of 81% at 600 nm was achieved. This
printing performance at a concentration of 10 mg ml−1, dis- makes CNT-based TEs very competitive for various electronic
persed in water with a 0.5 wt% polymeric dispersant, and applications, as demonstrated in electroluminescent devices
0.1 wt% of the wetting agent. The printing of CNTs has been (Fig. 18).
well summarized recently by several groups,155,156 here we will Although CNT inkjet printing is relatively new, it has been
only focus on the inkjet printing of CNTs for TE applications. demonstrated to be very promising for printing mechanically
Generally, for SWCNT-based TE films, the sheet resistance flexible and chemically stable TEs. However, there still exist a
and optical transmittance are typically in the range of 60–870 few issues including high sheet resistance, low transparency,
Ω sq−1 and 70–90% respectively, depending on the SWCNT and large roughness. Only after overcoming these issues,
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 Fig. 18 (a) Mechanical profilometer result of a printed CNT ring with a
300 nm thickness. (b) The corresponding optical profilometer result of
70% after 30 prints, they could also print higher transparency
the CNT ring. (c) Optical image of printed CNT rings forming a transpar-
patterns (∼90%) with however a much higher sheet resistance ent conductive film. (d) A flexible electroluminescent device prepared by
of ∼10 kΩ sq−1. An electroluminescent device with two printed the printed CNT rings. Reproduced with permission from ref. 157,
CNT electrodes was also demonstrated recently. The transpar- Copyright 2014, Royal Society of Chemistry.
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inkjet printing could become a mature method for CNT depo- graphene based thin films with the ink composed of liquid
sition. The high roughness could be well negated by deposit- phase exfoliated few-layer graphene nanosheets in the organic
ing another layer of transparent conductive materials, for solvent N-methylpyrrolidone (NMP). The merit of this process
example deposition of PEDOT onto the inkjet-printed CNT relies on the high quality of the resultant graphene flakes, due
films could effectively smooth the surface.144 Other post-print- to the oxidization-free process. They used the graphene ink to
ing chemical treatments could also improve the conductivity inkjet print graphene thin film transistors with a mobility of
of CNT films through various mechanisms, including remov- up to ∼95 cm2 V−1 s−1, and also transparent and conductive
ing the organic residues on CNTs and improving the CNT– patterns with an optical transparency of up to 80% and a sheet
CNT contact, or doping the CNT films.144,162,163 resistance of 30 kΩ sq−1. It was found that the wettability of
3.4.5 Graphene based ink. Graphene is a 2D material con- the substrate to the ink is quite critical to the final feature of
sisting of sp2 hybridized carbon atoms with a honey-comb the printed graphene patterns, the silane groups in the mole-
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lattice.164 Due to its unique structure and superior physical, cular structure of hexamethyldisilazane (HMDS) could
chemical, electronic, and optical properties, graphene has promote the adhesion of metallic particles to the substrate.
been paid plenty of attention since its first exfoliation from Similarly, HMDS may also improve the adhesion between gra-
graphite in 2004.72,73,164–170 Graphene possesses exceptional phene flakes and the substrate, thus promoting the assembly
in-plane conductivity and low sheet resistance even though it of graphene flakes into a regular network. However the ink
only has a single atomic layer. Light absorption by a defect- based on graphene flakes dispersed in organic solvents always
free graphene is estimated to be 2.3% while its sheet resistance suffers from low concentration or toxicity. A high printing
could be as low as 60 Ω sq−1. Recent progress in the prepa- efficiency requires high stability and also a high concentration
ration and characterization of graphene suggest it as one of of the graphene dispersion-based ink. Li et al.181 developed an
best candidates for TE fabrication through solution processes. ink formulation based on graphene flake dispersion in non-
Liquid dispersions of graphene nanosheets could be very toxic terpineol for inkjet printing of graphene patterns. The
promising for deposition by solution processes, including spin graphene ink was prepared by first exfoliating graphite flakes
coating, roll-to-roll processing, and inkjet printing. Bulk graph- in DMF, and exchanging DMF with terpineol to distil due to
ite powder can be exfoliated into single graphene nanosheets the large difference between their boiling points. The gra-
or few-layer graphene flakes, which depends on the exfoliation phene content could be greatly concentrated after solvent
method. The chemical exfoliation of graphite flakes in solvents exchange and distillation. To prevent graphene sheet aggrega-
is the most promising process for large-scale production of tion during DMF evaporation, a certain amount of polymer
graphene and solution-phase processing of a graphene (ethyl cellulose) was added into the graphene/DMF suspension
ink.171–173 as a stabilizer. Finally, the stabilizer can be effectively removed
The first demonstration of inkjet printing of graphene was through a post-printing annealing at 300–400 °C in air for 1 h.
conducted by Huang et al.174 who studied inkjet printing of a After polymer stabilization, graphene/terpineol dispersions
series of graphene-based inks. Under optimized conditions, could reach a concentration of around 1 mg ml−1 and remain
high-quality graphic patterns could be fabricated by inkjet stable for at least several weeks. The resultant inkjet-printed
printing water-soluble single-layered or few-layered GO-based film showed a sheet resistance down to 30 kΩ sq−1 and an
inks on various kinds of flexible substrates, ranging from approximate 80% transmittance at a wavelength of 550 nm.
paper, PET to PI. After thermal reduction, the printed gra- The key factor of controlling the concentration of the gra-
phene-based patterns showed a high electrical conductivity phene dispersion is to prevent the graphene flake from aggre-
which increased with the number of printed layers. More gating. The graphene flakes dispersed in an organic solvent
importantly, these printed patterns retained the same conduc- could be dramatically concentrated by using a specific stabil-
tivity over several bending cycles, indicating their application izer, and the conductivity of the inkjet-printed graphene pat-
potential in flexible TEs. Then Kong et al.175 inkjet-printed gra- terns could also be improved by post-printing annealing.
phene TEs on flexible substrates with GO dispersion in water, A concentrated graphene ink was obtained by liquid exfolia-
and then reduced GO with infrared light at 200 °C for only tion of graphite powders in an environmentally benign solvent
10 min. By optimizing the distance between the adjacent dro- ethanol with ethyl cellulose (EC) as a stabilizer. Subsequently,
plets and the printing layers, the final reduced GO TEs gave a the obtained graphene/EC powders were re-dispersed in a
sheet resistance as low as 0.3 MΩ sq−1 at an optical transpar- mixture with a cyclohexanone : terpineol ratio of 85 : 15, and the
ency of 86%. graphene concentration could be as high as 3.4 mg ml−1.182
One disadvantage of printing the aqueous graphene ink is During solvent evaporation, the polymeric stabilizer EC encap-
that a reduction process (either thermal treatment or chemical sulates the graphene flakes, and thus proper post-printing
reduction) is needed to restore the conductivity of the gra- annealing is needed to restore the electrical conductivity of the
phene sheet,176–179 which is undesirable for many appli- printed graphene films. After a thermal annealing at 250 °C
cations. Few-layer graphene flakes produced by the liquid-exfo- for 30 min, the treated graphene films presented a resistivity
liation method could restore the electrical conductivity of gra- of 4 mΩ cm and a uniform morphology, good compatibility
phene to a large extent and thus present promising application with flexible substrates and also excellent tolerance to
potential in TEs. Torrisi et al.180 reported inkjet printing of 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 light reflection of Ag grids, but is still comparable to the 87%
obtained by shear-exfoliation of graphite powers in the organic transmittance of the pure ITO films. Combinations of Ag grids
solvent NMP with most of the graphene flakes being ∼4 layers with conductive organic films also provide a more effective
thick and 160 nm in diameter. The graphene ink could be well charge collection, due to the filling effect of the conductive
inkjet-printed on various substrates. After 10 prints and a organic matrix. Murali et al.186 developed Ag grid/PEDOT:PSS
thermal annealing at ∼350 °C for 150 min, graphene TEs with TEs by inkjet printing both PEDOT:PSS and Ag NP inks. At an
a sheet resistance of 260 Ω sq−1 and a transparency of 86% Ag grid pitch size of 1 mm, the Ag grid/PEDOT:PSS hybrid TEs
were readily achieved. had a sheet resistance of 10.3 Ω sq−1 and an optical transmit-
The current low performance of inkjet-printed graphene tance of 73% which represented a ∼10% reduction in optical
TEs limits their application in many optoelectronics, such as transmittance compared to that of inkjet-printed Ag-grid free
LEDs, and solar cells; the fabrication of TEs with low sheet PEDOT:PSS films. The organic solar cells based on these
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resistance and high transmittance remains a critical challenge. hybrid TEs could be comparable with those using ITO. Kahng
Recent progress indicate that inkjet printing of hybrid films et al.187 described the fabrication of hybrid TEs based on
could possibly provide an alternative solution to the issues inkjet-printed Ag grids and CVD grown graphene films, and
with single-component inks. demonstrated their application in organic solar cells. It was
3.4.6 Hybrid inks. Though countless demonstrations of found that the graphene/Ag grid TEs showed a better perform-
inkjet printing of TEs have been reported, and significant pro- ance compared with the Ag grid. The enhancement was attrib-
gress has been made in terms of cost and scalability of the pro- uted to the void filling effect of graphene films on Ag grid elec-
duction, and performance of TEs currently, the performance trodes that have a large void area of ∼2 × 2 mm2 per each
of inkjet-printed TEs has not matched the requirements of square grid pattern. CNTs have also been incorporated into Ag
practically commercial applications. For example, the sheet NW films to enhance the charge transport by providing extra
resistance of the inkjet-printed TCO NC films is not optimal local electron transport pathways between the adjacent Ag
for optoelectronics. The large surface roughness of the metal NWs composing the backbone electrode of Ag NW mesh.188
NW films also applies some limits to optoelectronic device The implementation of this multiscale hierarchical approach,
fabrication. The tube–tube junctions within the CNT bundle which combines the advantages of materials of different
may block the inter-tube charge transport thus increasing the dimensions and of their properties, provides efficient pathways
resistivity of the CNT films. Graphene films also face a similar for electron transport, demonstrating a novel strategy for
dilemma, GO films need high temperature or harsh chemical designing highly stretchable and conductive TEs.
processing to restore the electrical conductivity, the liquid- As we know, the big change with the graphene- and CNT-
exfoliated graphene nanosheets have lower defects, but are based TE technology mainly lies in the fact that it is difficult
smaller in size, degrading the charge transport capability in to achieve good conductivity and high transparency simul-
the printed films. For Ag grids, the large void area tends to fall taneously. For CNT-based electrodes, the tube-to-tube junc-
short in charge collection, the Ag NW films also presents a tion resistance mainly contributes the large sheet resistance
high NW-to-NW junction resistance. Recent progress indicate of the CNT films. As for the graphene based TEs, neverthe-
that inkjet printing of hybrid films could possibly provide an less, because the size of graphene needs to be limited in a
alternative solution to the issues with the development of safe range which is smaller than 1/20 of the diameter of a
transparent conducting technologies. small nozzle, thus the charges need to hop between small
For example, the inkjet-printed Ag grids have excellent elec- graphene sheets, which increases the electrical resistance.180
trical conductivity and transparency, but fall short in rough- Recently, some researchers have shown that some metal NPs
ness and charge collection efficiency. The combination of Ag have the capability to improve the conductivity of carbon
grids with conductive films will be beneficial to alleviate these nanomaterials. Li et al.189 demonstrated that a layer of fine
issues. Jeong et al.184 have proposed a strategy to improve the Au NPs could significantly improve the electrical conductivity
conductivity of the inkjet-printed ITO films by inserting an Ag of CNT fibers, and the Au NPs not only increased the carrier
grid pattern between the inkjet-printed ITO layers, forming density in CNTs, but also facilitated the charge transport
ITO/Ag grid/ITO hybrid TEs. At an Ag grid pitch size of 3 mm, between the CNTs. Ag nanostructures with different mor-
the hybrid electrode presented an impressive sheet resistance phologies have also been included into the graphene
of 2.86 Ω sq−1 with an optical transmittance of 74.06%, and a nanosheets to improve their conductivity though the mechan-
figure of merit of 17.35 × 10−3 Ω−1. Hwang et al.185 also ism is still unclear.123,190–192 Li et al.192 presented a method
implemented a similar scenario to reduce the sheet resistance to assemble Ag nanotriangle platelets (Ag NTP) and Ag poly-
of inkjet-printed ITO TEs by patterning the Ag grid between hedral NPs onto GO to form the ink formulations. After
two ITO layers. With an Ag-grid separation distance of 2 mm, reduction, the inkjet-printed Ag NTP-rGO pattern displays a
the Ag-grid embedded ITO films gave a sheet resistance lower low sheet resistance of 170 Ω sq−1 with a transmittance of
than 3.4 Ω sq−1 after proper post-print annealing. By inserting 90.2%, demonstrating a significant improvement in the per-
the Ag-grid, the electrical properties of the Ag-grid/ITO hybrid formance of graphene-based TEs. Table 4 summarizes the
film (2 mm Ag grid pitch) were significantly improved while performance of various TEs fabricated by inkjet printing
the optical transmittance slightly reduced to 82% due to the techniques.
986 | Nanoscale, 2017, 9, 965–993 This journal is © The Royal Society of Chemistry 2017
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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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Concerns with TEs prepared with inkjet printing metal- mittance of ∼90% in visible light, demonstrating the merits
based inks include the stability due to oxidation, since Cu and comparable to ITO and Ag NW TEs. In addition, the 2D gra-
Ag are easily oxidized in humid or acidic environments. In phene were also expected to tightly hold metal NWs to
addition, NW-to-NW junction resistance is the main cause to enhance the charge transport between the metal NWs and
the high electrical resistance in transparent metal NW films. create a smooth film surface.195 Liang et al.196 demonstrated
2D graphene nanosheets are transparent, conductive, and the preparation of TEs based on an Ag NW percolation
hydrophilic, and also gas impermeable, and are thus suitable network modified with GO nanosheets. The GO nanosheets
as a coating and a protective layer for metal NW-based TEs.147 wrapped around Ag NWs and soldered the Ag NW junctions
As shown in Fig. 19a, the optical transmittance of Ag NW and thus dramatically reduced the inter-NW junction resist-
based and Ag NW-rGO based TEs almost have no significant ance without heat treatment or mechanical pressing. The GO-
change with the exposure time; however, the sheet resistance wrapped Ag NW network had a sheet resistance of 14 Ω sq−1
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of Ag NW TEs increased by more than 2.5 times when it is with 88% transparency at a wavelength of 550 nm, indicating
exposed to 70% RH at 70 °C for 8 days; but the sheet resistance the promising application in most fully flexible optoelectronic
of Ag NW-rGO TE films only increased by 50% under the same devices. Thus the inclusion of graphene into metal NW-based
exposure conditions, as displayed in Fig. 19b. Both the Ag electrodes opens a new way to produce large-area, flexible,
NWs and Ag NW-rGO are quite transparent, indicating that the highly conductive and transparent metal NW/graphene TEs.
rGO could not only greatly improve the resistance of Ag NW to Though the examples listed here were not prepared by inkjet
thermal oxidation but also retain the high transparency of the printing, the same strategies could also work well for inkjet-
TE. Lee et al.193 have described hybrid TEs based on graphene printed metal-based TEs.
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 4. Outlook
against electric breakdown and oxidation, and also impressive
mechanical flexibility and stretchability. Dou et al.194 reported In this review, we have attempted to provide a summary of the
a solution-based approach to wrap the surface of ultrathin Cu applications of the inkjet printing technique in optoelectronics
NWs with GO nanosheets. The solution process offers possi- fabrication. The material deposition processes for opto-
bility for inkjet printing. After deposition, high-quality Cu-rGO electronic device fabrication including solar cells, LEDs,
core–shell NW-based transparent conductive electrodes could photodetectors TEs, etc. currently involve the use of solution
be obtained by reducing the GO through a mild thermal processes (such as spin-coating, spray-coating, doctor blading,
annealing. The core–shell NW structures enabled the pro- and screen printing) or vacuum deposition approaches. In
duction of high-performance, low-cost Cu NW based TEs some cases, inkjet printing which has traditionally been used
which could maintain stability over 200 days in air and have a in the graphical and publishing industries has recently been
sheet resistance of ∼28 Ω sq−1, and a haze of ∼2% at a trans- 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
Fig. 19 (a) Transmittance of TE made of Ag NW and Ag NWs-rGO as a advance further development in this very exciting field.
function of time. (b) Sheet resistance of TE made of Ag NW and Ag NW-
Significant progress has been achieved in recent work to allevi-
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
ate such drawbacks on film quality and device performance, as
Ag-rGO film. Reproduced with permission from ref. 147, Copyright shown in the application examples. Given the impressive
2012, American Chemical Society. recent progress and versatile nature of inkjet printing, we
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