Nathan Zavanelli1, Woon-Hong Yeo1,2,3. 1. George W. Woodruff School of Mechanical Engineering, Center for Human-Centric Interfaces and Engineering at the Institute for Electronics and Nanotechnology, Georgia Institute of Technology, Atlanta, Georgia 30332, United States. 2. Wallace H. Coulter Department of Biomedical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States. 3. Parker H. Petit Institute for Bioengineering and Biosciences, Neural Engineering Center, Institute for Materials, Institute for Robotics and Intelligent Machines, Georgia Institute of Technology, Atlanta, Georgia 30332, United States.
Abstract
Stretchable electronics have demonstrated tremendous potential in wearable healthcare, advanced diagnostics, soft robotics, and persistent human-machine interfaces. Still, their applicability is limited by a reliance on low-throughput, high-cost fabrication methods. Traditional MEMS/NEMS metallization and off-contact direct-printing methods are not suitable at scale. In contrast, screen printing is a high-throughput, mature printing method. The recent development of conductive nanomaterial inks that are intrinsically stretchable provides an exciting opportunity for scalable fabrication of stretchable electronics. The design of screen-printed inks is constrained by strict rheological requirements during printing, substrate-ink attraction, and nanomaterial properties that determine dispersibility and percolation threshold. Here, this review provides a concise overview of these key constraints and a recent attempt to meet them. We begin with a description of the fluid dynamics governing screen printing, deduce from these properties the optimal ink rheological properties, and then describe how nanomaterials, solvents, binders, and rheological agents are combined to produce high-performing inks. Although this review emphasizes conductive interconnections, these methods are highly applicable to sensing, insulating, photovoltaic, and semiconducting materials. Finally, we conclude with a discussion on the future opportunities and challenges in screen-printing stretchable electronics and their broader applicability.
Stretchable electronics have demonstrated tremendous potential in wearable healthcare, advanced diagnostics, soft robotics, and persistent human-machine interfaces. Still, their applicability is limited by a reliance on low-throughput, high-cost fabrication methods. Traditional MEMS/NEMS metallization and off-contact direct-printing methods are not suitable at scale. In contrast, screen printing is a high-throughput, mature printing method. The recent development of conductive nanomaterial inks that are intrinsically stretchable provides an exciting opportunity for scalable fabrication of stretchable electronics. The design of screen-printed inks is constrained by strict rheological requirements during printing, substrate-ink attraction, and nanomaterial properties that determine dispersibility and percolation threshold. Here, this review provides a concise overview of these key constraints and a recent attempt to meet them. We begin with a description of the fluid dynamics governing screen printing, deduce from these properties the optimal ink rheological properties, and then describe how nanomaterials, solvents, binders, and rheological agents are combined to produce high-performing inks. Although this review emphasizes conductive interconnections, these methods are highly applicable to sensing, insulating, photovoltaic, and semiconducting materials. Finally, we conclude with a discussion on the future opportunities and challenges in screen-printing stretchable electronics and their broader applicability.
Biological surfaces can stretch and deform. Their mechanics differ
greatly from rigid systems, and this mechanical mismatch causes traditional
electronic systems to interface very poorly with human skin.[1] As a result, wearable healthcare applications
were limited for many years to obtrusive systems that coupled incompletely
with the body.[1] Stretchable electronics,
on the other hand, can integrate with a variety of soft materials,
offering a high degree of control over their material properties.[1] Central to these systems are electrical interconnections
that are highly conductive and maintain their structural integrity
with strain.[2] Traditionally, these interconnects
consist of ultrathin metals with fractal geometries that are fabricated
through established MEMS/NEMS methods.[1] This method offers excellent control over print architecture and
high spatial resolution, but it is expensive and low throughput.[1] In contrast, conductive nanomaterials can be
directly patterned on substrates through noncontact techniques, like
aerosol jet, inkjet, and electrohydrodynamic (EHD) printing, and contact
methods, like gravure, flexographic, and screen printing.[2] However, each of these approaches presents several
challenges.[2] Aerosol jet printing offers
good print resolution and thin material deposition, but it is too
low-throughput for industrial scales.[2] Inkjet
printing is sufficiently scalable, but clogging at the nozzle head
limits the use of large particles and high viscosities are required
in a printable ink.[2] EHD printing overcomes
several of these limitations by pulling inks to the substrate with
electrical forces, allowing the formation of high-resolution traces
through a large nozzle. However, it is limited by a low yield rate
and strict stand-off height requirements.[2] Contact printing methods are a high-throughput and mature alternative,
and among these approaches, screen printing offers the highest control
over pattern deposition, print resolution, and substrate choice.[2,3]Several essential manufacturing requirements must be met to fabricate
stretchable printed circuit boards (PCBs) via screen printing.[4] First, the conductive ink must be printable on
the stretchable target substrate.[1] This
requires the ink’s rheology to be optimized for the complicated
fluid dynamics during screen printing and the surface chemistry at
the ink–mesh and ink–substrate interface suitable to
the printing mechanisms described in section .[5,6] Second, the ink must
be highly conductive and maintain this conductivity with strain up
to 20% for wearable applications.[2] This
requires a solid understanding of the nanomaterial–polymer
matrix interactions that form the material’s percolation threshold.[5−7] Third, the resulting print must be durable through repeated strain
over multiple uses, which is also controlled primarily by the particle
dispersion and matrix composition.[2] Finally,
the print width should be sufficiently thin (<100 μm) and
precisely controlled to allow for reliable and small feature device
fabrication.[1,2] This is a function of the ink
rheology, interface surface chemistry, and screen-printing fabrication
parameters.[6,8]These fundamental requirements are nontrivial to meet, necessitating
the discovery of new nanomaterial–polymer formulations.[2] Although microscale materials have been proposed,
the large, asymmetric particles lead to decreased pseudoplasticity
caused by interparticle attractions and durability concerns due to
fragmentation with cyclic strain.[9] Likewise,
polymer inks, like those formed from PEDOT:PSS, are highly stretchable
and transparent, but they are limited by high sheet resistance.[10] In contrast, recent advancements in the formulation
of nanomaterial inks comprising nanoparticles (NP), nanowires (NW),
or nanotubes (NT) embedded in a stretchable polymer matrix offer an
exciting new approach to screen printing stretchable conductors.[2] Screen-printable stretchable inks may be formulated
by many additional materials (e.g., graphene, graphene oxide, nanographene
platelets, and liquid metals). However, we focus here on NPs, NWs,
and NTs, because they exhibit the most satisfactory mechanics, electrical
behavior, and dispersibility.[2,4,9,11,12] For each of these materials, finely controlling material properties
and interparticle interactions during synthesis, particle dispersion,
and polymer matrix composition allows for the delivery of high printability,
conductivity, reliability, and resolution in a printable ink.[5,7,12]In this review, we summarize nanomaterial approaches to screen
printing stretchable electronics, with a particular focus on the optimization
of nanomaterial properties, polymer matrix composition, particle dispersion,
surface chemistry, and screen-printing manufacturing parameters to
address the key design criteria in fabricating stretchable PCBs. We
begin with an overview of the screen-printing process and fluid mechanics,
which informs our discussion of print parameters and ink rheology
optimization. We then discuss the specific chemical mechanisms employed
in each nanomaterial’s dispersion and the formulation of this
material into a printable ink. We continue with a summary of state-of-the-art
screen-printed nanomaterial interconnects and conclude with commentary
on the future development and critical challenges facing the field.
Screen Printing Fundamentals
Ink Transfer Mechanics
Screen printing
involves the direct contact transfer of ink from a stenciled mesh
to a target substrate, as shown in Figure A.[8] As an ancient
art, screen printing has long been implemented in garment manufacturing
without understanding the scientific principles that govern it.[6,13] In addition, the first analytic models describing the process made
several deceptively intuitive assumptions that proved to be incorrect,
and their poor predictive power further fueled the idea that screen
printing was an art, not a science.[6,13,14] Riemer et al. first implemented the Navier–Stokes
equation in cylindrical polar coordinates simplified for creeping
flows as an analytic model to describe the ink transfer during screen
printing, but they neglected the effects of ink adhesive and cohesive
forces, instead implicitly assuming that ink is injected out of mesh
openings solely by hydrostatic pressure.[13] As a result, the proposed model did not produce realistic flows
or accurately predict thick film depositions.[13] The assumption that ink is forced out of the mesh openings and onto
the substrate via downward force is intuitive but not correct.[14] Instead, Messerschmitt et al. argued that the
ink’s adhesion primarily guides screen printing to the mesh
and substrate and its cohesive forces, and Abbott et al. developed
this qualitative theory into a computational model that could be experimentally
validated.[6,14] They based this model on Messerschmitt’s
three-stage printing mechanism, represented by (a), (b), and (c) in Figure B.[6] In Figure B (a), the ink is flooded into the mesh such that it occupies the
entire open area.[6] In Figure B (b), the mesh is brought
into contact with the substrate via downward force from the substrate.[6] The ink adheres to both the substrate and the
mesh based on the interface free energy for each system.[6] In Figure B (c), the mesh is pulled vertically, and the ink forms filament
structures until its cohesive forces are overcome, leading to a deposition
of ink on the substrate and a percentage remaining in the mesh.[6] This final stage can be divided into four substages
(c-i, ii, iii, iv).[6] First, (c-i) is the adhesion of the ink to the substrate and mesh; second, (c-ii)
is the extension of the ink structure as the mesh
is pulled vertically; third, (c-iii) is the flow of
ink into filament structure; and fourth, (c-iv) is the separation of the two ink structures.[6] These distinct
stages can be captured with high-speed imaging, as shown in Figure C.[7]
Figure 1
Overview of screen printing techniques. (A) Depiction of the ink
transfer process during screen printing from screen to a substrate.
(B) Schematic showing the three stages of screen printing, as proposed
by Abbott et al.[6] (a) Excess fluid on the
mesh after flood stroke. (b) Squeegee forces the screen into contact
with the substrate and fills cavities with ink. (c) (i–iv)
Screen separates from the substrate, and ink is pulled from mesh.
(C) High-speed image and illustration of the final stage involved
in ink transfer (reprinted with permission from J. Coat. Technol.2020, 17, 447–459.[7] Copyright 2020, Springer).
Overview of screen printing techniques. (A) Depiction of the ink
transfer process during screen printing from screen to a substrate.
(B) Schematic showing the three stages of screen printing, as proposed
by Abbott et al.[6] (a) Excess fluid on the
mesh after flood stroke. (b) Squeegee forces the screen into contact
with the substrate and fills cavities with ink. (c) (i–iv)
Screen separates from the substrate, and ink is pulled from mesh.
(C) High-speed image and illustration of the final stage involved
in ink transfer (reprinted with permission from J. Coat. Technol.2020, 17, 447–459.[7] Copyright 2020, Springer).Clearly, any process guided by these steps will be predominantly
influenced by the ink viscosity, cohesive and adhesive forces, pseudoplasticity,
and mesh angle relative to the substrate, not the squeegee pressure
and speed, and these parameters will be discussed in the next section.[6] In their computational model, Abbott et al. divided
the ink volume between the mesh and the substrate into 100 rectangular
sections in two dimensions and calculated the capillary number and
meniscus behavior based on the ink’s rheology, adhesive and
cohesive forces, squeegee speed and pressure, mesh height, angle,
and threads per micron.[6] Numerical integration
yielded the theoretical ink remaining in the mesh, and thus the printed
thickness.[6] Even though this model is two-dimensional
and neglects substrate properties, ink compression, and inertia effects,
it correlated well with experimental results.[6] Although further studies have shown that the complicated variable
interactions make the proper determination of specific parameters
like print height and width challenging, Abbott’s qualitative
assertions have largely formed the basis for subsequent investigations
into print parameter and ink property optimization.[8]
Key Process Parameters and Ink Properties
The deposition height is determined by the percentage of ink remaining
in the mesh during extension and filament separation. The resolution
is guided by the ink–substrate equilibrium contact angle and
ink pseudoplasticity. The print quality is determined primarily by
minimizing filament size, assuming the process is set up correctly
to proceed in the four steps described previously.[5,6,8] This is because large filaments produce
thick circular depositions in the area where they collapse, leading
to an uneven print and reduced resolution.[6] The deposition height has been shown to depend very little on the
squeegee speed and pressure; instead, it is highly dependent on the
mesh geometry and, to a lesser degree, the ink composition and interaction
with the substrate.[5,6,8] This
thickness depends on the substrate’s ability to pull ink from
the mesh, and thus increases approximately linearly with the fraction
of open area in the mesh.[11] It is also
dependent on the ink’s cohesive forces and adhesion to the
substrate.[7,8] Viscosity was not found to impact print
height to a high degree, but increasing ink cohesion (e.g., higher
material loading or polymer composition) and higher substrate–ink
adhesion do.[8] For ultrathin prints, the
height is also dependent on the print resolution, where the equilibrium
contact angle causes the ink to slump down to the side and lower the
print.[5] This slumping is the primary limiting
factor in print resolution, and thus print resolution and height are
inversely related.[8] Therefore, decreasing
the mesh open area increases resolution, but this also impacts the
printability of the ink by increasing adhesive forces, especially
with large material loading.[11] In addition,
the mesh can be chemically treated to control adhesion, the substrate
surface chemistry can be modified to increase the contact angle, the
ink can be made thicker and more viscous, the humidity can be minimized,
and the substrate reduced in temperature.[5,6,8,12] Nanomaterial
screen printing inks are constrained by the demands of printability,
conductivity, and stretchability. Still, the development of ultrathin
(<70 μm, or the resolution limit of microscale flake inks)
screen printing depositions is an area of active research.[4,11] Recent work has focused on improving ink viscosity, viscosity recovery
time, yield stress and ink–substrate adhesion through careful
choice of particle solvent and rheological agents, resulting in print
resolutions down to 22 μm.[4,11,12,15] For instance, dispersion agents
are necessary to prevent particle agglomeration, but they greatly
decrease viscosity, and several solvents, like ethyl cellulose, have
consistently demonstrated promising rheological properties.[12] Finally, print quality depends on a complex
interaction of manufacturing parameters and ink properties, but the
device settings can be easily optimized due to the speed of prototyping.[8] Therefore, printable ink design that also demonstrates
high conductivity with strain and minimum printable resolution form
the central challenge.[12] An ink’s
printability depends primarily on several rheological parameters.[5] Ideal screen-printing inks are pseudoplastic,
meaning they decrease viscosity with shear, but they are neither viscoelastic
nor thixotropic.[6] Pseudoplasticity allows
the ink to flow from the mesh when shear is applied during extension,
then rapidly recover during separation to yield a high-resolution
trace.[6] Pseudoplasticity is controlled
primarily by the choice and concentration of polymer binders and rheological
additives, although particle dispersion, geometry, and loading also
play an essential role.[12] For instance,
hydroxypropyl methyl cellulose (HMC) was found to greatly increase
printability in AgNW inks through both increased pseudoplasticity
and improved dispersion stability due to bonding between hydroxyl
groups and the surface of AgNWs.[4] Similarly,
ethyl cellulose was found to improve pseudoplasticity in low concentrations
compared to Thixatrol in a systematic study and validated in a carbon-based
nanomaterial conductive ink with excellent printability and resolution.[11,12] Beyond pseudoplasticity, viscoelasticity and thixotropicity tend
to reduce print quality and should be minimized.[6] Viscoelastic inks tend to prolong filament formation and
result in uneven or otherwise damaged prints.[5,6,12] Thixotropic inks cause a time delay in the
pseudoplastic viscosity recovery with low strain, resulting in slumping
and poor print quality.[6] Finally, parameters
like viscosity, yield stress, and surface tension tend to be interrelated
because of their dependence on cohesive forces in the ink, but these
parameters have contradictory impacts on printability.[4,6] Therefore, an optimal condition that is low viscosity to permit
fine print resolution, high in yield stress to improve postprint recovery,
and high in surface tension to maximize contact angle is desired.[5,6,12]
Nanomaterial Ink Approaches
Fundamentals
Conductive screen-printing
inks generally consist of three components: conductive nano- or microparticles,
organic binders and rheological agents, and a solvent.[4,5,12] These inks’ formation
depends heavily on the chemical and geometrical properties of the
conductive materials and rheological requirements covered previously.[4,5] In choosing a conductive filler, the tendency to agglomerate, percolation
threshold, and particle size are key design criteria.[9,15] Strong intermolecular forces leading to agglomeration complicate
dispersion, high percolation thresholds require heavy material loading,
limiting printability and stretchability, and large particle sizes
cause complications in fine trace width prints and can lead to fracturing.[9] Generally, the solvent is highly polar and the
filler nonpolar.[12] This allows for an amphiphilic
dispersion agent, like polyvinylpyrrolidone (PVP), to bind to the
filler and create repulsive complexes that disperse throughout the
matrix.[9,12] However, PVP greatly degrades printability
in large concentrations because of its tendency to produce low viscosity
and non-pseudo-plastic rheology.[4] As discussed
previously, the solvent, binder, and rheological agents are crucial
in determining printability, and many potential combinations exist
to impart the proper rheology.[5]
Silver Nanoparticle (AgNP) Inks
Spherical
AgNPs, like those shown in Figure A, have been frequently investigated for screen-printing
applications despite several key material properties that are not
conducive to proper ink design.[9,16,17] First, strong interparticle attractions tend to agglomerate particles,
complicating dispersion.[9,17] Second, despite these
attractive forces, the spherical geometry results in a high percolation
threshold without sintering.[17] Finally,
the AgNPs tend to form gaps when stretched or fracture when sintered.[9] Examples of fracturedAgNP prints after strain
is shown in Figure B, and Figure C depicts
sintered AgNP patterns, which appear as semirigid films.[9,16]
Figure 2
Silver Nanoparticles (AgNPs) for stretchable screen-printed electronics.
(A) SEM images of printed AgNPs (reproduced with permission from J. Mater. Sci. Mater. 2017, 28 (22), 16939–16947.[16] Copyright
2020, Springer). (B) Optical micrograph images of pattern fracturing
after applied strain (reproduced with permission from J. Manuf.
Process. 2014, 120, 216–220.[9] Copyright 2014, Elsevier). (C) AgNPs after sintering
at different temperature for 30 min: (a) without sintering, (b) 220
°C, (c) 240 °C, (d) 260 °C, (e) 280 °C, and (f)
300 °C (reproduced with permission from J. Mater. Sci.
Mater. 2017, 28 (22), 16939–16947.[16] Copyright 2020, Springer). (D) SEM image of
in situ formed AgNPs and photos of their application for a stretchable
screen-printed ECG array (reprinted with permission from ACS
Appl. Mater. Interfaces. 2019, 11, 8567–8575.[18] Copyright 2019,
ACS. photograph courtesy of Wei Guo, copyright 2019).
Silver Nanoparticles (AgNPs) for stretchable screen-printed electronics.
(A) SEM images of printed AgNPs (reproduced with permission from J. Mater. Sci. Mater. 2017, 28 (22), 16939–16947.[16] Copyright
2020, Springer). (B) Optical micrograph images of pattern fracturing
after applied strain (reproduced with permission from J. Manuf.
Process. 2014, 120, 216–220.[9] Copyright 2014, Elsevier). (C) AgNPs after sintering
at different temperature for 30 min: (a) without sintering, (b) 220
°C, (c) 240 °C, (d) 260 °C, (e) 280 °C, and (f)
300 °C (reproduced with permission from J. Mater. Sci.
Mater. 2017, 28 (22), 16939–16947.[16] Copyright 2020, Springer). (D) SEM image of
in situ formed AgNPs and photos of their application for a stretchable
screen-printed ECG array (reprinted with permission from ACS
Appl. Mater. Interfaces. 2019, 11, 8567–8575.[18] Copyright 2019,
ACS. photograph courtesy of Wei Guo, copyright 2019).These material properties present several critical challenges to
be overcome. Because AgNPs are difficult to disperse, mechanisms to
limit PVP concentrations, typically through removal, additional surfactants,
or dissolution in acetone, are required.[9] The high percolation threshold requires substantial material loading,
which further complicates dispersion and limits options to improve
printability.[9,17] Finally, trade-offs exist between
conductivity and reliability with strain when using AgNPs. Despite
these challenges, several groups have achieved promising ink formulations
within the material constraints. For instance, Jung et al. dissolved
AgNPs with high material loading in α-terpineol to yield bulk
conductivity above 3 × 105 S/cm but noted conductivity
degradation beyond 8% strain.[9] On the other
hand, Kim et al. optimized the AgNP dispersion for stretchability
with minimal material loading and sintering, leading to consistent
conductivity up to 38% strain, but only 1.97 Ω/sq bulk conductivity.[9,17] These results are contextualized with the remaining works to be
discussed in Table . AgNPs can also be formed in situ from Ag flake fillers, as shown
in Figure D.[18] These inks have demonstrated high conductivity
(>1 × 105 S/cm) and stretchability (80% strain), but
they are limited in resolution because of large particles, which can
also lead to fracture.[18] Although AgNPs were the first nanomaterial
explored for screen printing conductive inks, these limitations and
trade-offs have ultimately required the investigation of additional
materials when high conductivity, stretchability, and reliability
are required simultaneously.[4]
Table 1
Reported Conductivity and Stretchability
of Screen-Printed Conductors Using Nanomaterials
ref
conductor
substrate
material loading (wt %)
primary solvent
sintering
conductivity
stretchability
(9)
AgNP
PU
73
terpineol
60 min at 150 °C
3.3 × 104 (S/cm)
8%
(16)
AgNP
PI
80
HMC
30 min at 220 °C
1.2 × 105 (S/cm)
(17)
AgNP
PU
75
tetradecane
room temperature
1.97 Ω/sq
∼38%
(4)
AgNW
PUA (transfer from PET)
6.6
HMC
15 min at 150 °C
4.67 × 104 (S/cm)
∼70%
(20)
AgNW
PDMS
2
terpineol
photonic (laser 0.67 ms, 9 W)
1.9 Ω/sq
∼20%
(21)
AgNW
PDMS
70
terpineol
2 h at 80 °C
6.9 × 104 (S/cm)
∼100%
(24)
MWCNT
silicone
7.5
ethanol
room temperature
0.5–1.3 Ω/sq
(25)
Ag/MWCNT
PI
0.6 (CNT)
not mentioned, added SDS
20 min at 120 °C
7.26 μΩ/sq
Silver Nanowire (AgNW) Inks
AgNWs
are particularly attractive as a conductive basis for screen printing
applications because their elongated geometry imparts several key
advantages over spherical NPs.[2,4,20,21] When dispersed in random orientations,
the long particles form highly conductive networks, as shown in Figure A–B, maintaining
contact during strain to a much higher degree than NPs.[4] In addition, NWs are sufficiently thin to allow
for low material loading without fracture or loss of conductivity,
which greatly improves printability and resolution when combined with
optimized solvents and additives.[4,21] Finally, NWs
tend to disperse much more easily than NPs, requiring much fewer stabilizing
additives that degrade printability, like PVP.[4,19] Qibing
et al. were the first to demonstrate the full potential of AgNWs by
designing an ink with high conductivity (4.7 × 105 S/cm), stretchability (100% strain), reliability (cyclic bending,
1000 cycles), and resolution (50 μm).[4] These results were achieved through the use HMC as a dispersion
agent, Zonyl FS-300 as a surface tension modifier, and very low material
loading (6.6%) for optimal pseudo plastic recovery after printing.[4] The process did, however, require the transfer
of printed traces from a flexible poly(ethylene terephthalate) (PET)
substrate to poly(urethane acrylate) (PUA), reducing scalability.[4] Likewise, Cui et al. used a similar transfer
approach with PDMS to design highly conductive circuit interconnects
with 100% stretchability and excellent reliability: an application
in Figure C.[21] Finally, Shamim et al. directly printed AgNWs
on an ultraviolet/ozone (UVO) treated PDMS substrate by utilizing
low material loadings and a 6 wt % ethyl cellulose/PVP–terpineol
ink matrix.[20] The low material loading
resulted in a transparent deposition, but it greatly limited conductivity
(41 Ω/sq) and stretchability (<20%) compared to other works.[4,20] To address these trade-offs, the AgNW deposition was laser sintered
post-print with a 9 W Yb:fiber laser and exposure time of 0.67 ms
to yield AgNW nanowelding, as shown in Figure D.[20] The result
increased conductivity from 41 to 1.9 Ω/sq with no change in
stretchability or reliability. The final nanowelded network is shown
in Figure F.[20] These prints have demonstrated sufficient conductivity,
stretchability, and reliability (1000 rounds cyclic testing) for use
in wearable applications, but no study of high-resolution patterning
was conducted.[20] In addition, it is unknown
whether similar methods can be employed with higher material loadings
to yield conductivities approaching that of intrinsic silver.[20]
Figure 3
Silver nanowires (AgNWs) for stretchable screen-printed electronics.
(A,B) SEM images of screen-printed AgNWs after post-treatment with
low (A) and high (B) magnification (reproduced with permission from Adv. Mater. 2016, 28, 5986–5996.[4] Copyright 2016, Wiley). (C) Functional circuit
composed of stretchable AgNW interconnects on PDMS (reprinted with
permission from J. Semicond. 2018, 39 (1), 015002.[21] Copyright 2018,
IOP Press). (D–F) SEM images depicting (D,E) laser welded AgNWs
with 100 nm scale bars and (F) AgNW network with 10 μm scale
bars (reproduced with permission from npj Flex. Electron. 2019, 3 (13).[20] Copyright 2019, Springer Nature).
Silver nanowires (AgNWs) for stretchable screen-printed electronics.
(A,B) SEM images of screen-printed AgNWs after post-treatment with
low (A) and high (B) magnification (reproduced with permission from Adv. Mater. 2016, 28, 5986–5996.[4] Copyright 2016, Wiley). (C) Functional circuit
composed of stretchable AgNW interconnects on PDMS (reprinted with
permission from J. Semicond. 2018, 39 (1), 015002.[21] Copyright 2018,
IOP Press). (D–F) SEM images depicting (D,E) laser welded AgNWs
with 100 nm scale bars and (F) AgNW network with 10 μm scale
bars (reproduced with permission from npj Flex. Electron. 2019, 3 (13).[20] Copyright 2019, Springer Nature).
Carbon Nanotube (CNT) Inks
CNTs are
a versatile, low-cost material with excellent elastic and conductive
properties, and their high aspect ratio is promising for stretchable
conductor applications; however, CNTs interact strongly through van
der Waals forces and tend to agglomerate into heterogeneous distributions.[22−24] Typically, sufficient dispersions require the addition of anionic
surfactants, like sodium dodecyl sulfate (SDS).[23] SDS is strongly amphiphilic, like PVP, allowing it to bind
to the hydrophobic CNT surfaces and dissolve in water.[23] The negatively charged SDS tails create repulsive
forces, greatly aiding in dispersion.[22]Figure A depicts
the analytically derived interaction potential for 70% SDS coverage
on CNTs, demonstrating a suitable profile for dispersion.[22] The analytic model predicted that dispersion
effectiveness and solution mechanics are very sensitive to SDS coverage
percentage, and this hypothesis has been validated in numerous experiments,
such as the one depicted in Figure B.[23] Stringent dispersion
requirements complicate the design of stretchable, conductive, and
printable inks, but such inks have been reported.[24] Surendran et al. demonstrated a printable multiwalled CNT
(MWCT) ink for screen printing using 9 wt % material loading, 7.5%
SDS–ethanol dispersant loading, and 50 wt % PVP concentration.[24] The solution was mechanically agitated to promote
dispersion. Because of high PVP concentration, viscosity was low,
but the ink was screen-printable on a variety of substrates. No discussion
of the resolution was provided, but it is assumed that low viscosity
would preclude resolutions below 100 μm. Likewise, there is
no discussion of conductivity during strain, but the sheet resistance
with three printing passes was reported as 0.5 Ω/sq.[24] Because proper CNT dispersions are difficult
to design, CNTs are typically employed in sensor applications (beyond
the scope of this review) that take advantage of their remarkable
material properties or as secondary fillers to improve Ag microparticle
inks.[2,22,25] Deng et al.
compared the electrical and mechanical properties of Ag inks with
particle sizes of around 0.2–1 μm before and after the
addition of CNTs.[25] The CNTs formed conductive
bridges between microparticles, as shown in Figure C, that improved conductivity by more than
60% and demonstrated excellent reliability during cyclic bending and
thermal shock.[25] However, this approach
is limited by the difficulty of dispersing CNTs and assembling bridge
structures in a highly printable ink, and no discussion of resolution
is provided.[25] Overall, CNTs are highly
promising materials for screen printing stretchable conductors, but
novel approaches to overcome particle agglomeration require further
investigation.
Figure 4
Carbon nanotubes (CNTs) for stretchable screen-printed electronics.
(A) Mean-density model of surfactant heads for the dispersion of CNTs
with sodium dodecyl sulfate (SDS) with an analytically derived potential
of mean force for SDS coverage of 70% (reproduced with permission
from Appl. Surf. Sci. 2018, 439, 1133–1142.[22] Copyright
2018, Elsevier). (B) SEM images of CNT dispersion with varying concentrations
of SDS and CNTs, reproduced with permission from RSC Adv. 2018, 8 (30), 16444–16454.[23] Copyright 2018, The Royal Chemical Society).
(C) SEM images of printed Ag (a, b) and Ag-CNTs (c, d) before bending
(a, c) and after (b, d) 1000-cycle bending (r = 4
mm), reprinted with permission from J. Mater. Sci. Technol. 2017, 33 (10), 1113–1119.[25] Copyright 2017, Elsevier).
Carbon nanotubes (CNTs) for stretchable screen-printed electronics.
(A) Mean-density model of surfactant heads for the dispersion of CNTs
with sodium dodecyl sulfate (SDS) with an analytically derived potential
of mean force for SDS coverage of 70% (reproduced with permission
from Appl. Surf. Sci. 2018, 439, 1133–1142.[22] Copyright
2018, Elsevier). (B) SEM images of CNT dispersion with varying concentrations
of SDS and CNTs, reproduced with permission from RSC Adv. 2018, 8 (30), 16444–16454.[23] Copyright 2018, The Royal Chemical Society).
(C) SEM images of printed Ag (a, b) and Ag-CNTs (c, d) before bending
(a, c) and after (b, d) 1000-cycle bending (r = 4
mm), reprinted with permission from J. Mater. Sci. Technol. 2017, 33 (10), 1113–1119.[25] Copyright 2017, Elsevier).
Conclusions
Screen printing of nanomaterial conductors presents one possible
mechanism by which tremendous advances in stretchable electronics
can be translated to medical and commercial applications that directly
improve patient outcomes and quality of life.[2] Central to such applications are inks with nanomaterial, solvent,
binder, and rheological agent solutions tailored specifically to screen
printing’s fluid dynamics and maintenance of conductivity with
strain.[5−8] An ink’s effectiveness is primarily limited by the nanomaterial
filler’s properties (e.g., interaction potential and geometry)
that determine dispersibility and conductive network formation. However,
substantial opportunities remain to improve solvent and additive compositions,
especially in the case of CNT inks.[4,5,24] Although AgNPs were the first nanomaterial considered
for screen printing and remain a common filler choice, particle agglomeration
limits dispersion, and high percolation thresholds require high material
loading.[9] AgNWs overcome these challenges
through an elongated geometry that promotes conductive network formation
at low material loadings, allowing for substantial freedom in ink
rheological optimization.[4] In the short
term, further investigations into AgNW ink dispersion techniques,
rheology, and sintering will likely make them the material of choice
for screen-printed stretchable conductors, despite their high cost.[4] CNTs, however, present both the greatest promise
and technical challenges, making them a strong target for future development.[24] Excellent elastic and electrical properties
and cost-effective production make them highly suitable for screen
printing, but powerful interparticle attractions make stable dispersion
difficult.[24] Overall, screen printing is
a promising method for stretchable interconnect fabrication, but substantial
investigations into particle dispersion, ink rheology, pattern mechanics
under strain, and conductive network formation remain before it can
translate stretchable electronics from laboratory to commercial and
medical use.
Authors: Woo Jin Hyun; Sooman Lim; Bok Yeop Ahn; Jennifer A Lewis; C Daniel Frisbie; Lorraine F Francis Journal: ACS Appl Mater Interfaces Date: 2015-06-03 Impact factor: 9.229
Authors: Edyta Niezabitowska; Jessica Smith; Mark R Prestly; Riaz Akhtar; Felix W von Aulock; Yan Lavallée; Hanene Ali-Boucetta; Tom O McDonald Journal: RSC Adv Date: 2018-05-04 Impact factor: 4.036