Journal Pre-proofs

Dewetting-driven self-assembly of web-like silver nanowire networked film

for highly transparent conductors

Jin Kim, Sung Min Lee, Jin Seon You, Na Yeon Kim, Sanghyuk Wooh, Suk
Tai Chang

PII: S1226-086X(21)00672-9
DOI: https://doi.org/10.1016/j.jiec.2021.12.011
Reference: JIEC 5865

To appear in: Journal of Industrial and Engineering Chemistry

Received Date: 23 September 2021

Revised Date: 17 November 2021
Accepted Date: 6 December 2021

Please cite this article as: J. Kim, S.M. Lee, J.S. You, N.Y. Kim, S. Wooh, S.T. Chang, Dewetting-driven self-
assembly of web-like silver nanowire networked film for highly transparent conductors, Journal of Industrial and
Engineering Chemistry (2021), doi: https://doi.org/10.1016/j.jiec.2021.12.011

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© 2021 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights re‐
served.
 Dewetting-driven self-assembly of web-like silver nanowire

networked film for highly transparent conductors

Jin Kim†, Sung Min Lee†, Jin Seon You, Na Yeon Kim, Sanghyuk Wooh, and Suk Tai Chang*

School of Chemical Engineering and Materials Science, Chung-Ang University

84 Heukseok-ro, Dongjak-gu, Seoul 06974, Republic of Korea

*E-mail: stchang@cau.ac.kr
†These authors contributed equally to this work.

1
Abstract

Silver nanowire (AgNW) networked films have received much attention as transparent

conducting materials owing to their excellent conductivity, high transmittance, and moderate

cost. In addition, AgNWs can be easily prepared as dispersions in liquids, enabling solution-

based processing. Nevertheless, the fabrication of highly transparent AgNW networked

electrodes remains challenging owing to the high percolation threshold of AgNWs. In this

study, web-like AgNW networked films were fabricated via the dewetting-driven self-

assembly of AgNWs using meniscus-dragging deposition. The dewetting of liquid thin films

containing AgNWs was finely tuned by adjusting the ethylene glycol content of an AgNW–

isopropyl alcohol dispersion and the surface energy of the coating substrate. The obtained

AgNW networked electrodes with self-assembled web-like structures had a significantly lower

percolation threshold (0.26 μg cm-2) than randomly networked AgNW electrodes (2.53 μg cm-
2), resulting in an outstanding combination of sheet resistance and optical transparency (38 Ω

sq-1 at T = 96%). This large scalable one-step coating strategy for metal mesh thin films can

advance the development of next-generation transparent conducting electrodes.

Keywords: silver nanowires, web-like networked film, metal mesh, transparent electrode,

solution process, dewetting-driven self-assembly

2
1. Introduction

Over the past decades, indium tin oxide (ITO) has been widely employed as a transparent

conductive electrode (TCE) in various optoelectronic devices such as solar cells, organic light-

emitting diodes, and touch screens [1,2]. However, the scarcity of ITO has resulted in price

volatility for ITO-based electronics, stimulating research on alternative TCEs [3]. To develop

ITO alternatives, many studies have focused on various conducting materials, including

graphene [4-6], carbon nanotubes [7-9], conducting polymers [10,11], metal meshes [12-16],

and metal nanowires [17-21]. Among these candidates, metal nanowires, especially silver

nanowires (AgNWs), have been highlighted owing to their excellent optoelectrical properties

and moderate cost [22-24]. In addition, AgNWs can be easily dispersed in a liquid phase,

enabling solution-based processing. Typically, AgNW-based TCEs are obtained as randomly

networked AgNW percolated films via various coating methods, such as spray coating [25,26].

Mayer rod coating [27,28], and vacuum filtration [29,30]. Although these deposition methods

produce well-defined AgNW networked TCEs with excellent electrical conductivity, the

fabrication of high-performance AgNW networked electrodes with high transparency remains

challenging.

Because AgNWs are one-dimensional nanomaterials that can only form conducting

pathways by percolation, there is a percolation threshold for the establishment of connections

between AgNWs. In other words, AgNW networked films are not conductive when the surface

concentration of AgNWs is less than the percolation threshold. Accordingly, toward the

fabrication of highly transparent electrodes, extensive efforts have been devoted to overcoming

the geometric limitations of AgNW networked films [24]. In particular, AgNWs with high

aspect ratios have been synthesized to lower the percolation threshold of AgNW networked

films. For example, the polyol method enables the scalable production of AgNWs with aspect

3
ratios higher than 1000 [31-33]. However, although such AgNWs exhibit excellent

conductivity, it becomes increasingly difficult to uniformly distribute AgNWs on a substrate

without damage as the aspect ratio increases. Therefore, the utilization of AgNWs with high

aspect ratios to control the transmittance and sheet resistance has been hindered by a lack of

deposition techniques for AgNW percolated thin films.

An alternative approach for fabricating highly transparent AgNW networked electrodes is

to minimize the junction resistance by introducing organized structures such as grid-structured

AgNW networked films rather than randomly networked films [34]. Randomly networked

AgNW films contain numerous contact junctions between AgNWs, which are highly resistive.

In contrast, organized AgNW structures are mainly composed of less-resistive junctions

between bundled AgNWs; thus, highly conductive AgNW networked films with large open

areas can be obtained [35]. Much effort has been devoted to the fabrication AgNW networked

films with organized structures via solution-grown nanowire network [36], template-based

patterning [37-40], and assembly of aligned AgNWs [17,20,21,35]. Nevertheless, these

methods involve complex processes, such as photolithography, and nonrecyclable templates.

Although the scalable solution-based processing of AgNW networked films with organized

structures has been reported, further attention should be paid to controlling the fabrication of

AgNW structures in the high-transmittance region to obtain high-performance AgNW

networked films [41].

Herein, we demonstrate a novel approach for fabricating a self-assembled web-like

structured AgNW mesh, driven by the dewetting of a liquid thin film. The dewetting of a liquid

thin film containing AgNWs is finely controlled by adjusting the hydrophobicity of coating

substrate and the composition of AgNW suspension, which allows self-assembly of web-like

AgNW mesh without an external energy input. Octadecyltrichlorosilane (OTS) is adopted to

4
adjust the surface properties of the substrate and ethylene glycol (EG) is added to the AgNW–

isopropyl alcohol (IPA) suspension to drive the dewetting of the liquid thin film. The AgNW

networked film is produced via meniscus-dragging deposition (MDD), in which a uniform

liquid thin film is formed on a large substrate area using a small amount of AgNW dispersion.

To validate this fabrication process, the transmittance and sheet resistance of web-like AgNW

networked films are measured and compared with those of randomly networked AgNW films.

Based on the percolation theory, the structure and properties of the web-like AgNW mesh are

also analyzed and correlated with the percolation threshold. In addition, the controllability of

the resistance over a wide transmittance range is investigated by varying the deposition

parameters.

2. Experimental Section

2.1 Preparation of OTS self-assembled monolayer (SAM) on substrate

Piranha-cleaned glass slides were immersed in a mixture of OTS (Sigma-Aldrich) and

anhydrous toluene (99.8%, Alfa Aesar). To adjust the contact angle with the substrate, the

concentration of OTS was varied from 0.00125 to 0.01 vol.% and the deposition time was

varied from 10 to 180 min. To remove loosely bound OTS molecules, the OTS-treated glass

slides were rinsed with toluene, ethanol, acetone, and DI water, followed by sonication (5800,

Branson) for 2 h in toluene. Subsequently, the OTS-treated glass slides were dried under a N2

flow.

2.2 Preparation of AgNW networked films

AgNWs (average diameter of 40 nm, average length of 20 μm, 0.5 wt.% dispersed in IPA)

were purchased from DS Hi-Metal. Using mixtures of the AgNW dispersion and EG (0–10

5
vol.%), AgNW networked films were fabricated by MDD. The deposition plate was set on the

OTS-treated substrate at an angle of 35°. Subsequently, 20 μL of the AgNW dispersion was

injected between the deposition plate and the OTS-treated substrate. The deposition plate was

moved back and forth using a motion controller (AL1-1515-3S, Micro Motion Technology) at

a constant velocity of 1–4 cm s-1. A deposition number (DN) of 1 was defined as a single set

of back and forth motions, and deposition was performed using DN = 3. Subsequently, the as-

prepared AgNW networked films were annealed at 200 °C on a hotplate for 1 h.

2.3 Characterization of AgNW thin films

The contact angles on the OTS-treated substrates were measured using a contact angle

measurement system (Smart Drop, Femtofab). Contact angles were measured at three points

on the substrate and the average value was reported. Optical images of the AgNW films were

obtained using an Olympus BX-51 optical microscope coupled with a high-resolution ProRes

CF Scan digital charge-coupled device camera (Jenoptik) and analyzed using ImageJ software.

Field-emission scanning electron microscopy (FE-SEM) images of the AgNW networks were

obtained using a Carl Zeiss Sigma field-emission scanning electron microscope at an

accelerating voltage of 5 kV and a working distance of 5.1 mm. The absorbance and

transmittance of solutions and AgNW films were measured using a UV-vis-NIR

spectrophotometer (V-670, Jasco). The electrical properties of the AgNW films were

characterized using the four-point probe technique with a digital multimeter (34450A,

Keysight).

3. Results and Discussion

The details of the dewetting-driven self-assembly of web-like AgNW films are illustrated

in Fig. 1. First, to control the dewetting of the liquid thin film containing AgNWs, EG was

6
added to the AgNW–IPA suspension. Because IPA is a highly volatile solvent with a low

surface tension, little dewetting occurred before IPA evaporation. The EG contact angle with

the substrate was finely tuned by adjusting the OTS deposition conditions (Fig. S1).

Subsequently, a liquid thin film containing AgNWs was formed by MDD of the AgNW

suspension trapped between the coating plate and the substrate. The nonuniform evaporation

of IPA in the liquid thin film induced Marangoni flow, which prevented the AgNWs from

sticking to the substrate. Simultaneously, as IPA evaporated, the AgNW-containing liquid film

became sufficiently thin to generate dewetting holes. As the dewetting holes propagated, a

AgNW pattern formed along the dewetting pattern of the EG-rich liquid thin film. Finally, a

web-like AgNW film was obtained after annealing to remove the EG and PVP capping layer.

Fig. 2 shows optical images (corresponding to Movie S1) of a liquid thin film containing

AgNWs during evaporation. As shown in Fig. 2a, the AgNWs were initially well dispersed in

the liquid thin film and slightly orientated along the coating direction owing to the shear stress

exerted by the coating plate [17]. As evaporation progressed (~20 s, Fig. 2b), some of the

AgNWs settled on the substrate and became entangled with each other (29.6 s, Fig. 2c). With

further IPA evaporation, the liquid thin film ruptured and dewetting began, generating

dewetting holes. As the dewetting of the liquid film progressed, the AgNWs were aligned along

the dewetting pattern, creating a web-like network of AgNWs (~30.5 s, Fig. 2d). The

corresponding FE-SEM images in Fig. 2g and 2h show the well-defined structure of the web-

like AgNWs fabricated by dewetting-driven self-assembly.

As revealed by Fig. 2 and Movie S1, the propagation of the dewetting holes played a key

role in the formation of web-like AgNW networked films. There are two important

considerations for the formation of dewetting holes in liquid thin films; ⅰ) after IPA evaporation,

the EG-rich thin film should be thin enough to generate holes during the dewetting process,

7
and ⅱ) the dewetting velocity should be high enough so that dewetting is complete before

sedimentation of the AgNWs. The free energy for the formation of a dewetting hole in an

evaporating liquid thin film can be expressed as the difference between the free energy of the

liquid thin film (Gthin) and that of the liquid thin film with a dewetting hole (Ghole) [42]. Gthin

and Ghole can be written as:

𝐺𝑡ℎ𝑖𝑛 = 𝐴(𝑙0𝜌𝐿𝛥𝜇 + 𝜎𝑆𝐿 + 𝜎𝐿𝑉) (1)

𝐺ℎ𝑜𝑙𝑒 = (𝐴 ― 𝜋𝑥2)[𝑙0𝜌𝐿𝛥𝜇 + 𝜎𝑆𝐿 + 𝜎𝐿𝑉] +𝜋𝑥2𝜎𝑆𝑉 + 2𝜋𝑥𝑙0𝜎𝐿𝑉 (2)

where A is the surface area of the liquid thin film, 𝑙0 is the thickness of the liquid thin film,

𝜌𝐿 is the density of the liquid, 𝛥𝜇 is the chemical potential difference between the liquid and

the vapor, 𝑥 is the radius of the dewetting hole, and 𝜎 is the surface tension between solid

(V), liquid (L) and vapor (V). Considering Young’s equation (𝜎𝑆𝑉 = 𝜎𝑆𝐿 + 𝜎𝐿𝑉 ∙ cos 𝜃, where

𝜃 is the contact angle between the substrate and the liquid), the difference in free energy (∆G)

can be written as:

∆𝐺 = 𝐺ℎ𝑜𝑙𝑒 ― 𝐺𝑡ℎ𝑖𝑛 = ―𝜋𝑥2[𝑙0𝜌𝐿𝛥𝜇 + 𝜎𝐿𝑉(1 ― 𝑐𝑜𝑠 𝜃)] + 2𝜋𝑥𝑙0𝜎𝐿𝑉 (3)

∂∆𝐺
The critical hole radius (𝑥𝑐) and free energy (∆𝐺𝑐), corresponding to ∂x = 0, can be

expressed as:

𝜋𝑙20𝜎2𝐿𝑉 𝑙0𝜎𝐿𝑉
∆𝐺𝑐 = [𝑙0𝜌𝐿𝛥𝜇 + 𝜎𝐿𝑉(1 ― 𝑐𝑜𝑠 𝜃)] 𝑤ℎ𝑒𝑟𝑒 𝑥 = [𝑙0𝜌𝐿𝛥𝜇 + 𝜎𝐿𝑉(1 ― 𝑐𝑜𝑠 𝜃)] (4)

Therefore, in thicker liquid film and lower contact angle, the energy barrier for hole formation

is increased, resulting in shrinkage of the EG-rich liquid film rather than forming dewetting

holes.

Second, if the dewetting velocity is too low, all the AgNWs will settle on the substrate as

the liquid thin film evaporates instead of being arranged along the dewetting pattern. As shown

in Movie S1, AgNW sedimentation commenced immediately upon the spreading of the AgNW

8
dispersion by MDD. In addition, after the AgNWs settled on the substrate, their positions were

not affected by the dewetting flux of the liquid thin film. The dewetting velocity of a liquid

thin film is expressed by [43]

𝑉𝑑𝑒𝑤𝑒𝑡 = ( )𝜃
𝜅𝜎
𝜇𝑙𝑜𝑤
3
(5)

where 𝜅 is the fluid property constant, 𝜎 is the surface tension, 𝜇𝑙𝑜𝑤 is the viscosity at a low

shear rate, and 𝜃 is the contact angle between the liquid and the substrate. Thus, the contact

angle between the liquid and the substrate must be relatively large to develop a sufficient

dewetting velocity for the alignment of the AgNWs along the dewetting pattern before

sedimentation.

Based on the above thermodynamic treatments, two important parameters should be

considered: the thickness of the liquid thin film and the contact angle between the liquid and

the substrate. Therefore, the effects of the liquid film thickness and the contact angle with the

substrate were investigated, as summarized in Fig. 3. To adjust the thickness of the liquid thin

film before dewetting, the EG concentration was varied from 0 to 10 vol.%. As the EG

concentration increased, the thickness of the EG-rich liquid thin film remaining after IPA

evaporation increased because EG is nonvolatile at room temperature. The dewetting velocity

was varied by adjusting the contact angle between the substrate and EG using various SAM

layer deposition conditions (Fig. S1). Based on the measured EG contact angle (CAEG) or water

contact angle (CAW), the OTS-treated substrates were classified into five groups: CAEG = 55°–

60°, 65°–70°, 70°–75°, 75°–80°, and 85°–90°. As shown in Fig. 3, the structures in the obtained

AgNW networked films could be categorized into five groups: random network (black line),

aggregated (green line), partially aggregated (blue line), branched (purple line), and web-like

(red dashed line).

9
 First, a random network structure (black line) was obtained when the EG concentration was

0 vol.% or the EG contact angle was lower than 60°. Under these conditions, the dewetting

velocity of the liquid thin film was too low owing to the low surface tension of IPA (when EG

= 0 vol.%) and the low contact angle with the substrate. Therefore, the dewetting holes hardly

propagated and the AgNWs settled on the substrate without being dragged by the dewetting

flux as the liquid film dried, resulting in a random AgNW network structure.

As the contact angle increased to 65°–75° (blue line), the dewetting of the liquid film began

to slightly influence the formation of the AgNW networked film. In these films, partial

aggregation occurred because the increase in dewetting velocity caused by increasing the

contact angle resulted in some rearrangement of the AgNWs by the dewetting flux before

sedimentation. However, numerous AgNWs were still randomly scattered on the substrate

because the dewetting velocity of the liquid thin film was not high enough to eliminate AgNW

sedimentation.

When the EG contact angle was further increased to 70°–90°, AgNW networked films with

dewetting-driven self-assembled structures were observed, but the obtained structures were

also affected by the EG concentration. Under these conditions, the dewetting velocity was high

enough to drag the AgNWs before sedimentation, resulting in clear dewetting-driven patterns

including web-like, branched, and dot structures. Interestingly, in this contact angle range, the

radius of the open space became significantly larger by increasing the EG concentration from

0.25 to 10 vol.%. When the EG concentration was 0.25 or 0.5 vol.% (red dashed line), AgNW

networked films with web-like structures were obtained, resulting from the arrangement of the

AgNWs along the dewetting flux of the EG-rich liquid thin film. However, the web-like AgNW

films obtained at an EG concentration of 0.5 vol.% had a significantly lower pattern density

than those obtained at an EG concentration of 0.25 vol.%. In other words, the radius of the

10
open space in the web-like AgNW films increased at higher EG concentrations. As the EG

concentration increased, the thickness of the EG-rich liquid film also increased, resulting in an

increased energy barrier for the formation of dewetting holes (Eq. 4). Thus, a dewetting hole

can propagate further without encountering another dewetting hole. In addition, as shown by

Eq. 5, a higher dewetting velocity can be achieved at higher EG concentrations because IPA

has a contact angle of ~0° while EG has a contact angle of 70°–90°. Therefore, at higher EG

concentrations, fewer dewetting holes are generated during the dewetting of the liquid film,

and the generated dewetting holes can be propagated further and faster, resulting in a larger

domain size for the AgNW patterns. Even larger domain sizes were observed at higher EG

concentrations of 1–3 vol.% (purple line). In this region, the number of dewetting holes was

further decreased but the propagation speed was much higher, resulting in dewetting hole

growth. Therefore, the radius of the open space became much larger and percolation was lost

in the AgNW networked films. When the EG concentration was further increased to 10 vol.%

(green line), dot patterns were observed. The EG-rich liquid thin film became quite thick and

few dewetting holes were generated, resulting in the shrinkage of the liquid thin film at a high

dewetting velocity, which produced a dot pattern of AgNWs.

The AgNW networked film structure could also be controlled by adjusting the coating

parameters such as the deposition velocity and injected solution volume, which determined the

initial thickness of the liquid thin film. Based on the Landau–Levich–Derjaguin (LLD) model,

the thickness (ℎ) of a liquid thin film formed by MDD can be estimated using Eq. 6 [4,44-46].

ℎ = 1.34 ( )𝑟
𝜇𝑉
𝜎
3
(6)

where 𝜇 is the viscosity of the liquid, 𝑉 is the deposition velocity, 𝜎 is the surface tension,

and 𝑟 is the radius of the meniscus. Therefore, the thickness of the liquid thin film can be

11
adjusted by varying the deposition velocity as well as the injected solution volume between the

coating plate and the substrate, which determines 𝑟. Under fixed conditions where a web-like

AgNW networked film was produced (EG concentration of 0.5 vol.% and EG contact angle of

85°–90°), the effects of the deposition velocity and injected solution volume on the structure

were investigated. First, the deposition velocity was varied from 1 to 4 cm s-1 (Fig. 4). As shown

by the optical images in Fig. 4a, in the AgNW networked films, web structures with larger

domain sizes were obtained as the deposition velocity increased. For example, upon increasing

the deposition velocity from 1 to 4 cm s-2, the average width of the AgNW bundles increased

from 0.48 to 1.94 μm and the radius of the open space increased from 15.9 to 50.9 μm (Fig.

4b). This increase in the domain size at higher deposition velocities resulted from the decreased

probability of dewetting hole formation in thicker liquid films. As indicated by Eq. 4, the free

energy barrier for dewetting hole formation is increased by increasing the thickness of the

liquid thin film. Therefore, dewetting holes can propagate further, resulting in web-like

structures with larger domain sizes. The sheet resistance and transmittance of the obtained

AgNW films were also measured (Fig. 4c). As the deposition velocity increased, the sheet

resistance of the web-like AgNW film decreased from 58.9 to 25.8 Ω sq-1 and the transmittance

decreased from 95.7% to 91.4%. These changes were ascribed to the higher AgNW content in

the thicker initial liquid film at higher deposition velocities.

The effects of the solution volume on the structure of the web-like AgNW films were also

investigated (Fig. 5). As the solution volume was increased from 10 to 40 μL, the average width

of the AgNW bundles increased from 0.53 to 1.88 μm and the corresponding radius of the open

space increased from 13.9 to 45.2 μm (Fig. 5a and 5b). Similar to the effects of the deposition

velocity on the morphology of the AgNW networked films, the liquid thin film became thicker

as the injected solution volume increased, because the radius of the meniscus increased. Thus,

owing to the higher energy barrier for the formation of dewetting holes in thicker liquid thin

12
films, fewer dewetting holes were generated; nevertheless, they were propagated further at

larger injected solution volumes, resulting in web-like AgNW films with larger domain sizes.

The effects of the solution volume on the sheet resistance and transmittance were also evaluated

(Fig. 5c). Both, the sheet resistance and the transmittance, of the web-like AgNW films

increased at larger solution volumes because the content of AgNWs in the solution increased.

The performance of the web-like AgNW networked films was further analyzed using the

percolation theory. The sheet resistance (Rs) of a one-dimensional nanomaterial can be

estimated using the statistical percolation theory followed by [47,48]

𝑅𝑠 ∝ (𝑋 ― 𝑋𝑐) ―𝛼 (7)

where X is the surface density of a one-dimensional nanomaterial, 𝑋𝑐 is the percolation

threshold, and α is the percolation exponent, which is correlated to the dimensionality of the

percolated film. The surface concentration of the AgNWs was estimated by calculating the

mass of AgNWs in the liquid thin films formed by MDD using the LLD model. The

dependence of the sheet resistance on the surface concentration is shown in Fig. 6a for films

with random networks and web-like structures, where the solid lines correspond to the fit of

the data to Eq. 7. The percolation exponent (𝛼) was calculated to be 1.30 for the web-like

structures and 1.53 for the random networks. Both percolation exponents were similar to that

of the theoretical two-dimension model (α = 1.33). Interestingly, the percolation threshold (𝑋𝑐)

of 0.26 μg cm-2 obtained for the AgNW web-like structure was significantly lower than that

obtained for the random network structure (2.53 µg cm-2). That is, the AgNWs in the web-like

structures are more effectively connected to each other than those in randomly networked films,

effectively creating conductive pathways. The change in the transmittance with respect to the

sheet resistance (Fig. 6b) also corresponded well to the result expected based on the percolation

theory. The sheet resistance of the randomly networked AgNW film significantly increased

13
when the transmittance was close to 95%, indicating a loss of percolation with few effective

connections formed between AgNWs, thereby decreasing the conductivity of the AgNW

networked film. In contrast, the transmittance of the web-like AgNW networked film reached

up to 97%, indicating that more effective connections were formed between AgNWs in the

web-like structure than in the randomly networked AgNW film.

To evaluate the feasibility of the AgNW networked films as transparent electrodes, the

figure of merit (FoM) was calculated from the ratio between the electrical conductivity (σDC)

and the optical conductivity (σOP), as follows [29,49]:

σDC 188.5
FoM = σOP = 1 (8)
𝑅𝑠( 𝑇
― 1)

where 𝑅𝑠 is the sheet resistance and T is the transmittance. The FoM values calculated for the

randomly networked AgNW films and web-like AgNW networked films are shown in Fig. 6c.

Notably, for the web-like AgNW networked films, a maximum FoM of 290 was achieved at a

transmittance of 96%, whereas for the randomly networked AgNW films, the FoM rapidly

decreased at transmittances higher than 90%. Considering the industrial requirement of a FoM

of 220 (T > 90%) for transparent electrodes [50], the excellent combination of transmittance

and sheet resistance achieved by the web-like AgNW network electrodes is promising for the

development of next-generation transparent electrodes. The performance of the web-like

AgNW electrodes was also compared to those of recently reported AgNW-based transparent

electrodes (Fig. 6d) [17,25,29,37,38,41]. Although the performance of AgNW networked films

is highly dependent on the properties of the AgNWs themselves, a wide transmittance range

was achieved with competitive electrical conductivity. Besides the enhancement of the

optoelectronic properties of transparent conductors with the web-like AgNW network, large

scale coating of the AgNW thin films is also important for their practical applications. As

shown in Fig. S2, we demonstrated the fabrication of a uniform and large area (7.5×7.5 cm2)

14
web-like AgNW thin film. The size of web-like AgNW networked films produced by the MDD

technique can be easily scaled by simply using wider deposition plates.

4. Conclusions

In this study, we demonstrated the scalable one-step fabrication of dewetting-driven self-

assembled web-like AgNW networked films using an MDD process. Dewetting of the liquid

thin film containing AgNWs was finely controlled by optimizing the surface energy of the

substrate and the composition of the AgNW dispersion with EG, which affected the formation

of dewetting holes. Based on this strategy, a strong dewetting flux was developed by the

propagation of dewetting holes, resulting in the arrangement of the AgNWs along the dewetting

pattern to produce AgNW networked films with web-like structures. The obtained web-like

AgNW networked films exhibited a significantly lower percolation threshold (0.26 μg cm-2)

than randomly networked AgNW films (2.53 μg cm-2). Effective percolation in the web-like

AgNW films enabled an excellent combination of transmittance and sheet resistance (32.8 Ω

sq-1 at T = 96%, FoM = 290). Thus, we expect this work to offer important insights into the

fabrication of highly transparent AgNW-based electrodes as next-generation TCEs to replace

ITO.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests.

Acknowledgements

15
This work was supported by a National Research Foundation of Korea (NRF) grant funded by

the Korean government (MSIT) (grant number 2019R1A2C1006413 and

2019R1C1C1007560).

Appendix A. Supplementary Data

Supplementary data to this article can be found online at https://doi.org/xxxx

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Fig. 1. Schematic illustration of the fabrication process for web-like AgNW networked films.

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Fig. 2. (a)–(f) Sequential optical images of the AgNWs in a liquid thin film after MDD. FE-
SEM images of (g) a bundle and (h) a junction in a web-like AgNW networked film. The
AgNW networked film was prepared on a glass slide with an EG contact angle of 85°–90°
using 20 μL of the AgNW dispersion with 0.25 vol.% EG by MDD (DN = 3, deposition speed:
2 cm s-1).

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Fig. 3. Optical images of AgNW networked films with various CAEG or CAW values and EG
concentrations. The AgNW networked films were prepared by MDD using 20 μL of the AgNW
dispersion (DN = 3, deposition speed: 2 cm s-1).

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Fig. 4. (a) Optical images of web-like AgNW electrodes produced at varying deposition speeds
from 1 to 4 cm s-1 (DN = 3) using 20 μL of the AgNW dispersion with 0.25 vol.% EG. (b)
Width of the AgNW bundle and radius of the open space with respect to the deposition velocity.
(c) Sheet resistance and optical transmittance at 550 nm with respect to the deposition velocity.

25
Fig. 5. (a) Optical images of web-like AgNW electrodes produced by varying the solution
volume from 10 to 40 μL (DN = 3, deposition speed: 2 cm s-1) using a AgNW dispersion with
0.25 vol.% EG. The scale bars correspond to 100 μm. (b) Width of the AgNW bundle and
radius of the open space with respect to the solution volume. (c) Sheet resistance and optical
transmittance at 550 nm with respect to the solution volume.

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Fig. 6. Characterization of web-like AgNW electrodes. (a) Sheet resistances of web-like
AgNW networked films and randomly networked AgNW films with respect to the surface
concentration of AgNWs. (b) Sheet resistance and (c) FoM of AgNW networked films with
respect to the transmittance. (d) Performance comparison with recently reported AgNW-based
electrodes.

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