Nanoscale

View Article Online

PAPER
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.

View Journal | View Issue

One-pot stirring-free synthesis of silver nanowires

Cite this: Nanoscale, 2016, 8, 18121
with tunable lengths and diameters via a Fe3+ & Cl−
co-mediated polyol method and their application
as transparent conductive films†
Kan Zhan, Rui Su, Sihang Bai, Zhenhua Yu, Nian Cheng, Changlei Wang, Sheng Xu,
Wei Liu,* Shishang Guo* and Xing-Zhong Zhao*

Received 21st June 2016,
Accepted 27th September 2016
DOI: 10.1039/c6nr04972a
www.rsc.org/nanoscale
The properties of nanomaterials are highly dependent on their size, shape and composition. Compared
with zero-dimensional nanoparticles, the increased dimension of a one-dimensional silver nanowire
(AgNW/Ag NW) leads to extra challenges on synthesizing it with controllable sizes. Here, a convenient
way for the synthesis of AgNWs with tunable sizes has been developed simply by adjusting the amount of
salt additives, i.e., ferric chloride (FeCl3), or Fe(NO3)3 & KCl. The average diameter and length of nanowires
are readily tailored within 45–220 nm and 10–230 μm, respectively. The distinctive roles of Fe3+ and Cl−
played during the growth stages of Ag NWs were revealed by comparative experiments and a hetero-
geneous nucleation model with the assistance of oxidative etching was proposed to elucidate the growth
mechanism. Afterwards, transformations in XRD patterns from nanometer-size effects and quantitative
relation for size-dependent peak wavelength of surface plasmon resonances (SPRs) in UV-vis spec-
troscopy of these nanowires were studied. In addition, as transparent conductive materials (TCMs), these
metal nanowires were utilized to fabricate transparent conductive films (TCFs), and the effects of their
diameters and lengths were elucidated. Very/ultra-long nanowires with a high aspect ratio up to 1600
achieved impressive properties of R = 12.4 ohm sq−1 at T% = 90.1% without any post treatment. This facile
method for the size-tunable growth of uniform AgNWs with high yield is attractive and ready to be
home-made, which is believed to promote research in their potential applications, especially in opto-
electronic devices and flexible electronics.

1. Introduction bility, and have comparatively high chemical stability due to

The past few decades have witnessed a drastic increase in
research activities of nanomaterial-related science and techno-
logy. Compared with their bulk counterpart, nanomaterials
always have distinctive properties which are strongly correlated
with their size, shape, composition, etc. Among them, one-
dimensional (1D) nanomaterials received particular attention
due to their unique properties and applications.1 As an essen-
tial family member of 1D nanomaterials, silver nanowires
(AgNWs) have drawn intensive attention these years. The pro-
perties which make them intriguing are mainly based on their
excellent optical2,3 and electrical properties.4–6 Besides,
AgNWs do also bear a high mechanical robustness, good flexi-
School of Physics and Technology, Key Laboratory of Artificial Micro/Nano Structures
of Ministry of Education, Wuhan University, Wuhan 430072, China.
E-mail: xzzhao@whu.edu.cn, wliu@whu.edu.cn, gssyhx@whu.edu.cn
† Electronic supplementary information (ESI) available: More details of the
Experimental section, some tables and figures. See DOI: 10.1039/c6nr04972a
their weak reactivity (more stable than copper nanowires7). All
of the above-mentioned properties make them an outstanding
material for transparent conductive films (TCFs), especially for
the fabrication of flexible transparent conductive electrodes
(TCEs), which are essential components in various opto-
electronic devices.8–11 Besides, their 1D nanostructure is a
good template for the synthesis of some other composite
nanostructures with special functions.12
In the past few decades, accompanying the research needs,
a series of strategies have been exploited successively to fabri-
cate AgNWs.13–17 The most widely studied and most powerful
approach for their synthesis is undoubtedly the polyol method
among various approaches. Adopted firstly by Fievet et al.18 for
the synthesis of metal nanoparticles (NPs), and later broad-
ened by Xia and coworkers19 to synthesize 1D silver nano-
structures, the polyol method typically employs polyol as the
solvent and a weak reductant for Ag+, with a polymer such as
PVP acting as an efficient capping agent essential for aniso-
tropic growth, and the reactions are typically conducted at

This journal is © The Royal Society of Chemistry 2016 Nanoscale, 2016, 8, 18121–18133 | 18121

Paper
high temperatures (150–180 °C) with the assistance of stirring.
Afterwards, the polyol method has undergone widespread
investigations by numerous research groups.20–24 Various
factors influencing the ultimate products have been studied,
including the reaction temperature, the concentration of ingre-
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
dients, the ratio between different chemicals (especially
AgNO3 : PVP), stirring and injection speed, etc.21,25–29
So far, although numerous polyol reaction processes have
been designed, there are many existing challenges in the syn-
thesis of AgNWs, which can generally be classified into two
aspects: (I) high yield, uniformity and aspect ratios; and (II) a
wide range of adjustable sizes. Most previous studies remain
at achieving the first goal, scarcely any step into the second.
The first challenge has been largely overcome now,
especially by introducing additives to the polyol synthesis. It
has been reported that addition of chlorides such as NaCl or
KCl can greatly promote the formation of multiply twinned
particles (MTPs), hence help gain a high-yield synthesis of
AgNWs.21a,24,26,30 Besides, other anions (like S2− and
Br−)15c,20b,31 and cations (like Cu+ and Fe2+)22,24 have also been
shown to produce a strong influence on the growth of AgNWs.
Yet, the roles of various additives during the growth of AgNWs
remain obscure, and there is a large potential that the syn-
thesis of AgNWs can be greatly promoted via further optimiz-
ation of additives.
The second challenge, on the basis of resolving the first
one, is more difficult to be conquered. Meanwhile, the pre-
ferred sizes of AgNWs for different application areas can vary
much. The sizes of AgNWs, typically the length, diameter and
aspect ratio (i.e., AR = L/D), are the main parameters for the
estimation of property characteristics and their application as
a plain material. For instance, thinner and longer nanowires,
so as to gain higher ARs, are superior for applications in TCFs.
AgNWs with smaller diameters have a weaker light scattering
effect and a lower haze index, especially advantageous for
display applications. However, too thin a width is less robust,
making metal nanowires prone to easy breakage as a result of
repeated bending, heating, or even the intrinsic residual
force.1 In contrast, thick nanowires with mechanical robust-
ness have stronger self-restoration ability to bear deformation,
which accounts for tolerance to higher annealing temperature
and more bending times.32 At the same time, AgNWs with
larger diameters tend to scatter more light, beneficial for
capture of light in solar cell devices.
Since NWs with different sizes have individual strengths
and weaknesses, it is urgent that an efficient protocol for the
synthesis of AgNWs with tunable sizes should be exploited to
meet different requirements or preferences among wide-
spreading application fields. To gain AgNWs with adjustable
sizes, the available strategies, in principle,33 can be divided
into two types: (i) control the growth time or the amount of
consumed Ag+ for a specific number of seeds; and (ii) change
the number of seeds for AgNWs under a specific amount of
Ag+ source. In practice, the former is harder to control since
special care needs to be taken to monitor the growth process
and/or avoid the formation of exotic seeds.25,34 In contrast, it
18122 | Nanoscale, 2016, 8, 18121–18133
View Article Online
Nanoscale
will be fairly convenient if the formed seeds in a certain
volume of solution could be varied according to need, where
fewer seeds lead to NWs with larger sizes and vice versa.
However, due to the great challenge in controlling the nuclea-
tion stage, past studies25,26,35 have only affected the generated
number of seeds by indirect ways, such as the concentration of
PVP, AgNO3, or reaction temperature, etc., which is inefficient
to gain wide size control.
In particular, oxidative etching is a powerful method to
gain better control over the concentration of metal atoms by
reactive dissolution. It has been recognized as a facile way to
reach better control of metal nanoparticles.36,37 However, it is
widely considered that oxidative etching is adverse for the
formation of seeds with twinned structures, which are
more inclined to be etched away and reorganize to be
single-crystal.
Here, based on our experimental results, however, we
manage to demonstrate that oxidative etching could serve as a
highly effective route to promote the manipulation on concen-
tration of MTPs, so as to gain AgNWs with tunable sizes. This
is achieved by employing Fe3+ & Cl− as dual control agents,
where Fe3+ is a strong etchant. To ascertain the delicate and
distinctive roles Fe3+ and Cl− take on respectively during the
growth process of AgNWs, we designed a series of comparative
experiments to show the growth rules, taking advantage of an
one-pot stirring-free route for the facile synthesis of AgNWs,
which is superior as a simple reaction procedure, thus highly
repeatable. Moreover, making use of different sizes of nano-
wires attained during this study, nanometer-size effects on
XRD patterns and diameter-dependent surface plasmon reso-
nance (SPR) effects are presented. Finally, the synthesized
AgNWs with several typical sizes are employed to fabricate
TCFs. The effects of NW diameter and length on the properties
of TCFs are discussed and the potential of AgNWs gained in
this study as excellent TCMs is demonstrated.
2. Experimental section
2.1 Synthesis of silver nanowires
In a typical synthesis procedure, 0.485 g PVP was firstly added
to 40 mL EG in a conical flask. The mixture was vigorously
stirred at room temperature to complete dissolution of PVP in
EG. Then different amounts of KCl and/or Fe(NO3)3, or a
single FeCl3 solution, were injected into the as-prepared trans-
parent and uniform solution, followed by addition of 0.725 g
AgNO3 powder, after which the flask was immediately wrapped
with an aluminum foil to avoid light exposure. Afterwards, the
flask was transferred to an oven preheated to 140 °C to start
the reaction. The synthesis process was maintained for
4.5 hours to ensure sufficient conversion of the AgNO3 source
to Ag nanostructures. To be more specific, here, the addition
amounts of inorganic salt solution in EG are very important.
For convenience of comparison, the concentration of three salt
solutions was prudently chosen. The concentrations of FeCl3
and Fe(NO3)3 were both 11.2 mM, while the concentration of
This journal is © The Royal Society of Chemistry 2016

Nanoscale
KCl was 33.6 mM. Hence, the concentrations of Fe3+ in the
standard Fe(NO3)3 solution and Cl− in the standard KCl solu-
tion were both equal to that of the standard FeCl3 solution,
respectively. In the standard reaction (labeled FeCl3-STD),
0.4 mL FeCl3 solution was injected to the mixed solution.
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
More details about materials, the fabrication of AgNW films
and characterization are provided in the ESI.†
3. Results and discussion
3.1 Controllable synthesis of AgNWs
3.1.1 Effectivity of FeCl3 additive
Product of the standard reaction. The effects of promotion
induced by salt additives, especially chlorides, have been widely
recognized and trialled by various research groups.16,20,26,30
However, different salt species can lead to distinct products of
silver nanostructures. Here ferric chloride (FeCl3) was
employed at first to efficiently synthesize AgNWs. Fig. 1a and b
show the SEM images of AgNWs synthesized under the stan-
dard reaction, with the addition of 0.4 mL FeCl3 solution.
Their sizes are slender and uniform. Their lengths are clearly
presented by optical microscopy (OM) image in Fig. 1c. The
diameter and length distribution of the AgNWs are summar-
ized by counting over 150 wires, and their distribution images
are shown in the inset of Fig. 1b and d, respectively. The
average diameter is 94.5 nm, and the length is 38.0 μm, which
will be larger if the weight factor of mass is included. Overall,
the synthesized AgNWs from FeCl3-STD are fairly uniform,
with a high aspect ratio. In the meantime, the nanowire yield
of the standard reaction was checked by calculating the weight
Fig. 1 The length and diameter distributions of Ag NWs from the stan-
dard reaction. (a), (b) SEM images of FeCl3-STD product with low and
high magnification, respectively. (c) An optical image to observe the
length of nanowires. (d) Statistical distribution of length from optical
image. Inset in (b) shows the statistical distribution of diameter. Inset in
(c) is a digital image presenting the visual colors of solution after
reaction.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Paper
ratio between the final weight of the AgNW product and the
source content of silver. The weight of the precipitate after
cleaning and drying was 0.448 g, corresponding to a yield of
97.3%, verifying the high-yield nature of the reaction.
The reasons why the standard reaction can yield high-
quality AgNWs are ascribed to three aspects. The primary
factor is the combined promotion effects from Fe3+ and Cl−.
With only Fe3+, Cl− or neither of them, the gained products
cannot attain AgNWs with such a high yield and/or high AR,
as will be demonstrated later. Secondly, temperature has been
prudently selected to ensure a nice reaction. The reduction
ability of polyol is determined by the temperature,25,38 thus the
reaction speed. A fast reaction at high temperature is favorable
for the formation of thermodynamically more stable structures
(e.g., Ag NPs),24,39 but not AgNWs. AgNWs are more prone to
be generated at a low reduction rate of Ag+ based on kinetic
promotion.24,26 Meanwhile, too low a temperature will lead to
a longer reaction time, if not degraded products. As a conse-
quence, we chose a moderate reaction temperature of 140 °C
throughout this study, which could release a suitable
reduction ability of ethylene glycol. Thirdly, the mixed reactant
solution was placed in an oven without stirring. The reaction
in the liquid without agitation could inhibit the possible
adhesion and erosion of silver nanowires by oxygen atoms,22
enabling sufficient growth with less disturbances, while
excluding the necessity of a shielding gas (N2 or Ar).20a
Moreover, despite the absence of stirring, the uniformity of the
reaction process was ensured by the inner flow circulation of
the reaction solution, which was produced by the heat
migration and air motion in the convection oven. A visual illus-
tration of the oven heating is provided in section 3.2 to help
comprehension. Additionally, the dark conditions in the oven
avoid possible negative effects induced by light exposure.40
Comparison of NONE, only Fe3+, only Cl− and Fe3+ & Cl−. In
order to verify the combined advantage of Fe3+ & Cl−, we con-
ducted comparative experiments to check the individual effect
of Fe3+ and Cl−. At first, the reaction without any additives
(denoted as NONE) was carried out. Fig. 2a shows that all the
products were quasi-spherical Ag NPs, without the presence of
Ag rods or wires, in accordance with previous studies.26,41 The
possible reason is the omission of the self-seeding process
incorporated in Xia’s protocol.19 When only Cl− was applied
(labeled 0.4 mL KCl by adding 0.4 mL standard KCl solution),
similar to previous studies,26,29 a high yield of AgNWs could
also be achieved, as shown in Fig. 2c, confirming the necessity
of Cl− in AgNW generation. We presume Cl− has the ability to
introduce seeds for 1D Ag, and the detailed interpretation will
be given in section 3.1.2. Despite the fact that AgNWs pro-
duced from 0.4 mL KCl were pure and uniform, their length
was much shorter than NWs from FeCl3-STD, mostly within
10–20 μm. If Cl− was absent, with Fe3+ added merely, the
product mainly consisted of Ag particles and sparse Ag wires
or rods (Fig. 2b). It seems a little unexpected that without the
addition of Cl−, thus missing the introduction of exterior
seeds, could also produce 1D Ag structures. Considering
there is a small portion of MTPs formed naturally during the
Nanoscale, 2016, 8, 18121–18133 | 18123

Paper
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
Fig. 2 Product comparison of four different recipes, including reaction
(a) without any additive, (b) with only Fe(NO3)3, (c1, c2) with only KCl,
and (d1, d2) with the combined addition of Fe(NO3)3 and KCl. The results
verify that combined addition of Fe(NO3)3 and KCl is equal to single
addition of FeCl3 with the same amount of Fe3+ and Cl−.
nucleation stage,42 the Fe3+ possibly facilitated the generation
of MTPs by reducing the supersaturation degree, and pro-
moted their growth to develop a 1D appearance rather than be
etched or blocked by oxygen. Finally, Fe3+ and Cl− were
together added to the mixed solution by sequential injection
of Fe(NO3)3 and KCl solution. This time, identical to the
product gained from FeCl3-STD, a high yield of AgNWs with
high AR was achieved (Fig. 2d). This trial verifies the equi-
valent functions between a combined addition of Fe(NO3)3 &
KCl and a single addition of FeCl3 solution during the AgNW
growth. A summary of the reaction conditions and size data is
provided in Table S1.† With the above narration, a preliminary
understanding of different roles played by Fe3+ and Cl− indivi-
dually has been erected.
3.1.2 KCl control. The efficiency of KCl salt in promoting
AgNW formation has already been demonstrated in section
3.1.1. Although the synthesized AgNWs have shorter lengths
compared with the FeCl3-added reaction, it’s quite possible for
single Cl− ions as an effective control agent to adjust the ulti-
mate size of AgNWs. A series of KCl addition amounts were
carried out. The size data and SEM images of derived AgNWs
are shown in Fig. 3 and S1,† respectively. From the data in
Fig. 3, it is clear that both the length and diameter of
NWs decreased fast at first (0.1–0.7 mL) and then gradually
slowed down (0.7–3 mL) and remained steady at a small size
(D ∼ 45 nm, L ∼ 10 μm) finally. In addition, it should be noted
18124 | Nanoscale, 2016, 8, 18121–18133
View Article Online
Nanoscale
Fig. 3 Size distributions of AgNWs gained from reactions with different
addition amounts of KCl. The trialled amounts are 0.1 mL, 0.4 mL,
0.7 mL, 1.5 mL, 3 mL and 10 mL. The red line and black line are a visual
aid to see the respective variation tendency of diameter and length. The
error bars are one standard deviation in each size distribution.
that the yields of AgNWs among these trials were all fairly
high, not less than 90%.
To have a good understanding of the effect of Cl− ions, poss-
ible reasons are searched for. It is speculated that dual effects
induced by Cl− account for its high efficacy. On one hand, Cl−
ions can reduce the supersaturation degree of the Ag0 in the
solution and slow down the Ag nucleation event, beneficial for
the formation of MTPs.31 On the other hand, as the solubility
of AgCl is very low with a Ksp = 1.8 × 10−10 (RT in water), it is
reasonable that AgCl colloids will form, probably acting as
heterogeneous seeds in favor of the formation of MTPs in the
same time.20,43 This is supported by the consistency of the ten-
dency observed in Fig. 3 with the general rule, which suggests
an increased number of seeds (from an increased amount of
Cl−) leads to a decreased size of nanocrystals under conditions
of a constant source amount.25,43 Definitely, AgCl nanoparticles
serving as a platform for AgNWs to grow on has been con-
firmed in section 3.2. Although the exact origin of the boost
from Cl− ions in promoting the formation of the 1D Ag struc-
ture is not completely disclosed, here we propose that the
addition of Cl− ions is equal to the addition of seeds for
AgNWs to grow out, and the number of seeds introduced by
them will monotonically increase with increasing addition
amount within a certain concentration range.
In addition, from the above-mentioned results, it’s clear
that single addition of Cl− is not sufficient to control the size
of AgNWs efficiently. By changing the addition amount of KCl,
the tunable range of length and diameter is 10–18 μm and
45–80 nm, respectively, only within a narrow range.
3.1.3 FeCl3 control. Since the single addition of Cl− has
already presented the ability to tune the size of NWs to a large
degree, we then pay more attention to the variation tendency
of different addition amounts from the combined addition of
Fe3+ & Cl−. In pursuit of disclosing the distinctive roles of Fe3+
and Cl− played during the AgNW growth process, we mounted
an extensive parameter study, based on our reaction protocol
This journal is © The Royal Society of Chemistry 2016
 View Article Online

Nanoscale Paper

with simple procedures and a relatively slow reaction speed.
Here, for convenience, simple addition of different amounts of
FeCl3 solution, instead of double addition of Fe(NO3)3 and KCl
solutions, were performed first to provide Fe3+ and Cl− ions as
effective control agents.
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
the decreased yield and purity of AgNWs derived from the reac-
tion with too high a concentration of FeCl3 additive, which was
adverse for the production of high-quality AgNWs.
In general, the variation tendency for increasing amounts
of FeCl3 additive is distinct from that of KCl, where the size of

When the addition amount of FeCl3 was gradually
increased from 0.05 mL to 3 mL, the size of attained nanowires
increased at first and then gradually decreased, as clearly
shown in Fig. 4(i). The AgNWs with the largest average dia-
meter of 221.2 nm was gained in the 0.7 mL FeCl3 reaction,
and their length was 150.2 μm, with an aspect ratio as high as
679 (Fig. 4e). The cross section of a thick nanowire is pre-
sented in the inset of Fig. 4(e2), maintaining a good penta-
gonal shape. Afterwards, a further increment of FeCl3 amount
led to AgNWs with a decreased diameter, as well as a lower
yield of AgNWs. An addition amount up to 3.0 mL would gene-
rate more irregular particles in the final products (Fig. 4g and
h). In addition, there was a thick layer of precipitate existing
on the bottom of the flask with dark gray red color, which was
ascertained to be a mixture of irregular Ag NPs and AgCl NPs
by EDS analysis (Fig. S2†). This result helps us to understand
NWs shows a decreasing trend. The differences should be
mainly attributed to the effect of Fe3+ ions. Since the Fe3+ is a
kind of strong oxidant, it can react with newly-reduced Ag0
atoms in the solution via oxidative etching, exerting tremen-
dous influence on the formation of Ag nuclei by reducing the
supersaturation level of Ag0 at the nucleation stage. The size of
AgNWs produced from FeCl3 reactions increases rapidly with
increasing amount of FeCl3 (0.05–0.7 mL) at first, probably
originating from the restriction of Fe3+ over the nuclei number
of MTPs, since fewer seeds will lead to a more sufficient
growth and enlarged sizes of the final products. However, a
further increase of FeCl3 amount (1.0 mL–3.0 mL) results in a
decreased diameter of AgNWs, possibly resulting from the
negative corrosion effect of excess Fe3+ and the dominating
role of Cl− concentration against Fe3+ in controlling the nuclei
number of AgNWs. The rising concentration of Cl− will lead to

Fig. 4 Product comparison of reactions with different addition amounts of FeCl3. The amount of injected FeCl3 solution is (a1, a2) 0.05 mL, (b1, b2)
0.1 mL, (c1, c2) 0.3 mL, (d1, d2) 0.5 mL, (e1, e2) 0.7 mL, (f1, f2) 1.0 mL, (g1, g2) 1.5 mL, and (h1, h2) 3.0 mL, respectively. The statistical results of size
characteristics are summarized in (i), where the red line and black line are visual aids to see the respective variation tendency of diameter and length.
The error bars are one standard deviation in each size distribution. The scale bars are all 1 μm in SEM images. The inset in (e2) shows a cross section
image of thick NWs with a diameter of 230 nm, where the scale bar is also 1 μm.

This journal is © The Royal Society of Chemistry 2016 Nanoscale, 2016, 8, 18121–18133 | 18125
 View Article Online

Paper Nanoscale

higher seed concentration for AgNW formation, as well as a

stronger inhibition of lateral growth of NWs since more free
Cl− ions interact more frequently with Ag atoms on (100)
facets, in a way similar to Br− ions.38
Overall, the addition of FeCl3 in an appropriate amount is
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.

efficient to synthesize AgNWs with high ARs. Compared with

KCl-mediated reactions, the adjustment ability of FeCl3 is
much more powerful, and the size of AgNWs can be controlled
within a broad range (D = 80–220 nm, L = 13–230 μm).

3.2 Growth mechanism of Ag NWs

3.2.1 Tracking the reaction process by SEM and UV-vis. To
confirm the significant role of Cl− as a seed producer, samples
taken from the primary reaction stage (ca. t = 1 hour) of the
standard reaction were checked. After centrifugation, the pre-
cipitates were collected and observed under SEM, as shown in
Fig. 5a and b. In these two pictures, a lot of quasi-spherical
particles with a typical size around 500 nm are presented. The
main composition was ascertained to be silver chloride by
EDS. It’s quite interesting that a lot of tiny AgNPs and short
rods grow out from the surface of AgCl particles. Some silver
nanorods protruding out are particularly impressive as shown
at the positions where arrows point to in Fig. 5b. If we scruti-
nize short rods, an even more fancy view exists of some rods
inserting into the body of AgCl particles, marked by oval lines
in the figure. The insertion of these rods probably resulted
from the preformed nanorods at the surface of AgCl colloids
which were wrapped by subsequent deposition of AgCl as the
growth of AgCl NPs proceeded for a long time (≥1 hour).
Therefore, the role of AgCl colloids as an AgNW nuclei provi-
der is validated based on the SEM observations.
As a facile tool to monitor the growth evolution of silver
Fig. 5 (a) and (b) Products from primary stage of standard reaction
nanostructures, the UV-vis spectrum was employed to investi- (ca. 1 h) were observed by SEM with (a) low and (b) high magnifications.
gate samples taken from different reaction stages, especially Arrows in (b) identify silver nanorods that protrude from the surfaces of
those after the Ag nanorods had formed. In practice, aliquots AgCl nanoparticles, while oval marks highlight that some parts of pro-
of FeCl3-STD solution were taken from the reacting solution truding silver nanorods are wrapped by AgCl bodies. (c) UV-vis spectra
demonstrating the time evolution process of the standard reaction. Two
via a glass pipette at different times, and the recorded spectra
black arrows were added in the graph to highlight the progress of red
are shown in Fig. 5c. At the primary reaction stage, the main shifts in SPR peaks from Ag NPs and 1D Ag nanostructures. Samples
products were AgNPs deduced from a single narrow peak.19 were gained by taking aliquots at different times shown in the picture.
The size of AgNPs gradually grew from t = 30 min to t = 1 h
15 min, as their peak red-shifted from 410 nm to 435 nm.
Then a mixed peak was present at t = 1 h 25 min, suggesting moments. For instance, in the standard reaction of FeCl3, the
the coexistence of AgNPs and 1D Ag nanostructures, with the solution immediately turned slightly white after heating for
sign peaks of 1D silver located at λ = 350 nm and 375 nm, orig- 5 minutes, indicating the formation of AgCl colloids. Then,
inating from their transverse surface plasmon resonance (SPR) similar to reactions conducted at higher temperatures,16,19 a
modes.3a Finally, an extinction spectrum with two predomi- yellow solution emerged (ca. 15 min) as a result of the for-
nant peaks around 350 nm and 390 nm was left, indicating mation of tiny AgNPs. Afterwards, the mixed solution under-
the products comprise almost pure AgNWs. It’s worth noting went a series of color variation from orange red (ca. t = 30 min)
that the characteristic peaks of AgNWs also went through a red to pink (ca. 45 min), gray accompanied by slight green (ca. 1 h
shift as a result of increased diameter, and the detailed 15 min), and eventually turned opaque gray white (ca. 2 h)
relationship between the wire diameter and the SPR peak wave- with evident silver strips, an essential sign for successful syn-
length will be discussed later (section 3.3). thesis of AgNWs, which was maintained to the end, as shown
The direct observation of visual color changes of the reac- in the inset of Fig. 1c. A collection of digital images recording
tion solution is another simple and convenient method to the color change process is shown in Fig. S3† for clarity. In
obtain a general grasp of reaction stages. During the reaction contrast, the end color of 0.4 mL KCl appeared earlier than
process, a series of color changes occurred at different FeCl3-STD, while the earliest is the NONE reaction.

18126 | Nanoscale, 2016, 8, 18121–18133 This journal is © The Royal Society of Chemistry 2016

Nanoscale
Based on the detailed results shown above, an effective
model is proposed, as illustrated in Fig. 6, to help understand
the essence of our experimental results. In our reaction protocol,
Cl− ions serve as the primary “director” of Ag nuclei, which
will not only confine the aggregation of free Ag+ in reaction
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
solution, but also promote preferred nucleation of Ag nuclei
on the surface of AgCl NPs (i.e., promoting heterogeneous
nucleation43). The reduced concentration of free Ag+ in solu-
tion leads to a lower supersaturation degree of Ag0 at the
primary growth stage, therefore facilitates the formation of
MTPs and helps maintain the high yield of AgNWs in final Ag
products (Path I). However, NWs gained by single addition of
Cl− are quite thin and short. In the meantime, if Fe3+ ions join
the reaction in the solution (Path II), the control over the for-
mation of Ag nuclei can be greatly enhanced based on the
etching effect of Fe3+. It is proposed that extra addition of Fe3+
can further lower the supersaturation degree compared with
mere addition of Cl− by oxidative etching. As a result, the ten-
dency of AgCl colloids to form Ag nuclei is weakened, which
leads to the reduced number of Ag nuclei, as well as the size
enlargement of the final AgNW products.
To demonstrate the growth process more clearly, an
enlarged reaction profile is depicted at the bottom of the
scheme. During the reaction, one AgCl nanoparticle could
produce several silver nanorods with different sizes at first.
Without the corrosion from Fe3+ ions, these nanorods will all
transform into nanowires finally after sufficient growth. When
Fe3+ ions are incorporated, they will dissolve Ag0 atoms on the
surface of silver nuclei gradually, and the preformed nanorods
Fig. 6 Schematic illustration of the growth mechanism inside an oven.
The growth pathway of AgNWs is subjected to a heterogeneous nuclea-
tion way, where AgCl nanoparticles could grow out nuclei for growth of
AgNWs. This process is shown in Path I, where single addition of Cl− is
enough to produce AgNWs with high-yield, although quite short and
thin. In the meantime, when Fe3+ ions are added apart from Cl−, the
number of produced nuclei during the nucleation phase is reduced to
some degree. Consequently, the derived nanowires in Path II are thick
and long. A more clear illustration showing the function of Fe3+ is pre-
sented at the bottom.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Paper
with smaller sizes are more easily etched away. Hence, the
remaining number of AgNW nuclei will be reduced to some
degree, depending on the relative concentration of Fe3+, and
will generate nanowires with larger sizes finally. Although in
both pathways, the sizes of nuclei formed at the primary stage
are polydisperse, they will grow into NWs with close sizes as a
result of the focusing effect,44 thus uniform products can be
gained ultimately. In addition, AgCl NPs will gradually dissolve
(small ones) or grow up and sediment (larger ones) by Ostwald
ripening. A sample taken from the bottom of the flask after
the reaction completed is shown in Fig. S4.†
3.2.2 Further verification of distinctive roles played by Fe3+
& Cl−. In order to further reveal the growth rule of AgNWs, as
well as a verification of the growth model demonstrated in
Fig. 6, the concentrations of Fe3+ and Cl− are varied indepen-
dently to demonstrate their distinctive effects. For conven-
ience, the amount of Fe3+ and Cl− added into the mixed solu-
tion will be written in short as Fe(m)Cl(n), where (m) represents
the portions of Fe3+, and (n) is the portions of Cl−. Typically,
Fe1Cl1 means the reaction with the combined addition of one
portion (i.e., 0.1 mL) of standard Fe(NO3)3 solution and one
portion (0.1 mL) of standard KCl solution. Accordingly, the
FeCl3-STD reaction can be denoted as Fe4Cl4.
Fe4Cln reactions. When the amount of Fe3+ is fixed at an
amount as much as that of Fe3+ added in the FeCl3-STD (i.e.,
0.4 mL Fe(NO3)3), different amounts of Cl− were injected to
inspect its individual change effects. The trials of varied
amounts of Cl− were selected as 1, 7 and 10 portions, and the
results are shown in Fig. 7(A) and S5.† In the Fe4Cl1 reaction,
compared with FeCl3-STD, the amount of Cl− is reduced,
which leads to a decreased number of seeds. Consequently,
each nucleus of Ag NW could receive more Ag0 to grow, produ-
cing a thicker width at the primary growth stage, while the
average length is shorter due to the limited amount of the
silver precursor to maintain growth extending to a larger
length. If the heterogeneous seeds for AgNWs to grow out are
increased, as in the case of Fe4Cl7 and Fe4Cl10, the ultimate
products of AgNWs will have smaller sizes, since the amount
of silver source for each seed falls.
FenCl4 reactions. Similarly, the individual effects of Fe3+ were
specially studied by comparison of reactions with the same
amount of Cl− (0.4 mL KCl) and varied amounts of Fe(NO3)3.
The results are presented in Fig. 7(B) and S6.† As the number
of AgCl NPs were all the same in these trials due to the fixed
amount of Cl−, their tendency to produce silver seeds was
directly dependent on the concentration of Fe3+. The size of
AgNWs in the Fe1Cl4 reaction diminished compared with the
FeCl3-STD reaction, suggesting the developed Ag nuclei would
be more abundant with a small amount of Fe3+. In contrast,
the Fe7Cl4 reaction produced AgNWs with a larger size. This is
attributed to stronger oxidative etching from more abundant
Fe3+ ions, which will produce stronger restriction on Ag nuclei
formation from the surface of AgCl NPs and decrease the
number of seeds. However, further increasing the amount of
Fe3+ could not produce AgNWs with larger diameters, although
the length could be broadened, as shown in Fe10Cl4. The
Nanoscale, 2016, 8, 18121–18133 | 18127
 View Article Online

Paper Nanoscale
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.

Fig. 7 Size distributions of AgNWs gained from (A) Fe4Cln-reactions with the same concentration of Fe3+ but varied Cl− and (B) FenCl4-reactions
with the same concentration of Cl− but varied Fe3+. Data of Fe4Cl4 are from FeCl3-STD. The red line and black line are a visual aid to see the
respective variation tendency of diameter and length. The error bars are one standard deviation in each size distribution.

activities of Fe3+ in the Fe10Cl4 reaction are complex. The pre- 3 mL KCl, FeCl3-STD, and 0.7 mL FeCl3, and their samples
formed seeds were limited due to limited Cl− ions, thus they composed of thick and uniform films were prepared via
were likely to be removed by Fe3+ easily. However, the excessive vacuum filtration of cleaned AgNWs ink solutions. The
dissolution of Ag nuclei also consumed the Fe3+ ions, while detected peak distributions of AgNWs with different diameters
abundant AgCl nanoparticles remained active in the solution, are presented in Fig. 8.
continuously developing new seeds for AgNWs. Afterwards, the At first glance, the overall peak distributions of all three
Ag NW seeds produced in the second stage could grow samples are highly consistent with the PDF card of bulk silver
sufficiently, without the disturbance of Fe3+ but rather assisted (JCPDS 04-0783), confirming the high purity of silver products.
by the protection of Fe2+.27 Furthermore, careful examinations reveal that some differ-
Overall, in this section, the individual effects of Cl− and ences do exist between the patterns of AgNWs and that of bulk
3+
Fe are further clarified by comparative trials. Despite the fact Ag, which are relevant to the nanometer-size effect. Overall,
that the results seem quite similar to previous sections (3.1.2 there are three major differences. Firstly, the peak intensity
and 3.1.3), the results here do further demonstrate the ratio between (111) and (200) peaks increases due to the
different roles performed by Cl− and Fe3+ and have additional enrichment of (111) planes in AgNWs.19 The respective peak
implications. By changing the molar ratio between Fe3+ and intensity ratios of NW samples from 0.4 mL FeCl3 and 0.7 mL
Cl−, i.e., employing non-stoichiometric addition of Fe3+ and FeCl3 are 6.93 and 5.06, much larger than bulk Ag (2.5 from
Cl− compared with direct addition of FeCl3, we are able to PDF card). However, it should be pointed out that this ratio
further extend the ability of our protocol to synthesize AgNWs index is highly changeable for the same sample with different
with varied sizes. This strategy can not only broaden the range
of length and diameter of AgNWs, but also introduce a judi-
cious way to tackle the problem of slight but non-ignorable
pollutants contained in the solvent (EG), especially the varied
content of Fe3+.22,45 It has been reported that variation of
those trace amount of ion species will lead to erratic products
under the same reaction conditions. In particular, it’s quite
upsetting that a set of parameters appropriate to produce
excellent Ag NW products using a previous batch of solvent
generate degraded products in the next batch. Therefore, it
remains to be resolved how a reaction system can minimize
the effects of the solvent if it has to meet the demand of mass
production. We believe the protocol introduced here has pro-
vided a convenient way to cope with that uncertainty.

3.3 Characterization of size-dependent structural and optical

properties of AgNWs
3.3.1 XRD study of nanometer-size effects. X-ray diffraction
(XRD) measurement is an essential tool to certify the general
structural characteristics of materials. To ascertain the crystal
Fig. 8 XRD patterns of silver nanowires with three different sizes. The
structure of AgNWs synthesized above, especially spectral diameters in samples I, II, III are about 45 nm, 95 nm, and 220 nm,
characteristics from nanometer-size effects, AgNWs with three respectively. At the bottom, (IV) the XRD pattern of bulk silver from PDF
representative sizes were selected, including samples from card is presented for comparison.

18128 | Nanoscale, 2016, 8, 18121–18133 This journal is © The Royal Society of Chemistry 2016
 View Article Online

Nanoscale Paper

thicknesses. To support this, films with thinner thickness and

some powder samples were prepared and tested by XRD (detail
is shown in Fig. S7†). In addition, the ratio index of 3 mL KCl
is much smaller (2.07), probably originates from the co-exist-
ence of Ag cubes and bipyramids, which are common products
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.

when high concentration of chloride is used in the reaction.30

Therefore, the peak ratio between (111) and (200) is only a
slight indicator of AgNW products but should not be
exaggerated.
Secondly, there is a line-broadening effect46 shown in the
patterns of NWs, and is most evident in the pattern of the
sample from 3 mL KCl, which has the thinnest NWs. The
indexes of full width at half-maximum (FWHM) of (111) peaks
from samples I, II and III are 0.366, 0.156 and 0.103, respec-
tively, presenting a sequential decrease when the NW diameter
increases. Thirdly, there are some obvious deviations of XRD
patterns from AgNWs compared with the bulk one, high-
lighted in the picture by vertical lines. These deviations
include peak shifting and peak asymmetry (e.g., (220) peak),
which mainly result from residual stress.47 The overall right
shifting of the peaks indicates those AgNW films were in com-
pression. The forces that led to the compression were likely to
be produced by the upper and lower pressure difference
during vacuum filtration, as well as the surface tension or
capillary force arising during the evaporation of the solvent.
3.3.2 UV-vis study of size-dependent SPR effects. The UV-
vis extinction spectrum is an efficient tool in detecting the
shape and size of noble metal nanostructures, as a result of
their strong coherent interaction with electromagnetic waves,
especially in the region of visible light.2a To search how UV-vis
spectra can function as a reflection of different silver nano-
structures, especially their variation tendency for AgNWs with
different diameters, several products among the above-men-
tioned reactions were selected as representatives. The derived
spectra are organized in Fig. 9(A). In this figure, each spectrum
of nanowires presents a characteristic double peak distri-
bution, differing from the quasi-spherical nanoparticles (e.g.,
product of NONE reaction), which only possesses one evident
peak. The origin of the left peak located at ca. 350 nm is attrib-
uted to quadruple resonance,48,49 while the right peak orig-
inates from the dipole resonance, which has a sensitive vari-
ation law with dimensions of silver nanostructures.50 Both
peaks originate from the transverse plasmon resonance modes
of nanowires, which are associated with the pentagonal cross
section shape of AgNWs,3a while the longitudinal plasmon res-
onance is absent as the aspect ratios of all tested AgNWs are
far above 5.19,48
To proceed with further consideration, we carried out a
quantitative study on the position dependence of the SPR peak
from dipole resonance on the diameter of AgNWs. It will be
rather convenient to determine the average diameters of
AgNWs if there is a quantitative correlation between the SPR
peak wavelength (λm) and diameters. On the basis of numer-
ous trials and abundant samples gained during the rules
seeking phase, we are able to show the quantitative relation-
ship between the SPRs peak wavelength and AgNWs diameter,
Fig. 9 (A) UV-vis spectra of AgNWs with different sizes, including a
series of reaction products from KCl reactions, as well as FeCl3 reactions
(arranged in the embedded graph). The Ag NP sample with an average
diameter of 207 nm from NONE reaction is also incorporated in the
inset. (B) A quantitative statistics of relationship between SPRs peak
wavelength (λm) and NWs diameter. The experimental data can be well
fit by an exponential equation, as shown in the text.
as shown in Fig. 9(B). The data in the picture are well fitted by
an exponential equation below (R2 = 0.987, see the dashed line
in Fig. 9B).
λm ¼ λ0 þ a expðb  DÞ ðλ0 ¼ 360; a ¼ 8:33; b ¼ 0:0138Þ
All data in the graph were gained by counting at least 50
strips of nanowires in the selected samples, all with fairly
uniform dimensions. This exponential relationship is quite
similar to that of gold NPs.51 Besides, it’s worthwhile to note
that the data of very thick NWs (e.g., 0.7 mL FeCl3) are not
included. For AgNWs from 0.7 mL FeCl3, there is no obvious
peak point as the broadened peaks become quite flat. The
extinction intensity maximum of 0.7 mL FeCl3 located at the
wavelength of 410 nm, a number smaller than the peak wave-
length of AgNWs with smaller diameters (D = 150 nm, λm =
430 nm), indicates the breakup of monotonously increasing
tendency of SPR peak wavelength with larger diameters. Thus,
the derived equation is only applicable for NWs with a dia-
meter within 150 nm. In addition, it should be noted that our
data were gained by dispersing AgNWs in ethanol. Deviations
may arise when different solvents are used.
3.4 The preliminary application of AgNWs by fabricating
pristine AgNW TCFs
One of the major applications of AgNWs is to fabricate high-
performance transparent conductive films (TCFs) as an excel-
lent substitute for ITO.52–54 Perceiving that great potential, pre-
viously, many researchers have employed AgNWs to conduct

This journal is © The Royal Society of Chemistry 2016 Nanoscale, 2016, 8, 18121–18133 | 18129

Paper
comparative studies with the ITO counterpart in various
devices, paving the way to develop excellent transparent con-
ductive electrodes (TCEs) made of AgNWs.9–11,55 However,
most previous research studies are quite preliminary, paying
little attention to the size effect of AgNWs on various issues.
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
Although there are a great many techniques to enhance the
properties of Ag NW-based TCFs, the intrinsic properties of
the AgNWs themselves certainly matter much. In order to gain
a good understanding of NWs’ size effects in TCF applications,
as well as the potential of AgNWs synthesized in our scenario
as transparent conductive materials (TCMs), several products
were selected to prepare pristine AgNW films, and the data of
their electrical and optical properties are depicted in Fig. 10.
The films were all prepared by spin-coating, due to its relative
simple operation with good uniformity and high repeatability
compared with some other film preparation methods.56
For silver nanowires from FeCl3-STD, the derived TCFs
demonstrate excellent properties. At a high transmittance (T%)
of 94.4%, the sheet resistance (Rs) was as low as 52.4 ohm sq−1,
easily stepping across the “doorsill” of R ≤ 100 ohm sq−1
when T% = 90%, which is the minimum standard for indus-
trial production of TCFs.57 The T% was maintained at a high
level of 86.5% when Rs was reduced to 10 ohm sq−1. For com-
parison, nanowires of 0.4 mL KCl were selected, which have a
low AR and is a good representative of products in many
studies employing the single Cl−-promoted reaction.10a,58 The
TCFs were tested, presenting a much inferior Rs and T%
(labeled R & T hereafter) performance. When the Rs was ca. 15
ohm sq−1, films produced from 0.4 mL KCl had a T% of 80%,
which was 8% lower than that of FeCl3-STD (ca. 88%), and the
gap would be larger if diffusive T% rather than specular was
Fig. 10 Comparative study of R & T properties of pristine transparent
conductive films composed of AgNWs with different sizes. Data of T%
are specular transmission of films at 550 nm. The selected samples are
NWs from 0.4 mL KCl, 10.0 mL KCl, FeCl3-STD, 0.7 mL FeCl3 and
Fe10Cl4. The sizes are ca. 60 nm–15 μm, 45 nm–11 μm, 95 nm–38 μm,
220 nm–150 μm, 140 nm–226 μm, respectively. The R & T properties of
0.4 mL KCl is the inferior, while 10 mL KCl and FeCl3-STD are close and
good, 0.7 mL FeCl3 and Fe10Cl4 being close and superior. The shadow
area represents TCFs with ultrahigh quality.
18130 | Nanoscale, 2016, 8, 18121–18133
View Article Online
Nanoscale
chosen.58 The degraded performance of nanowires from
0.4 mL KCl mainly results from their shorter length and lower
AR, which will result in worse wire connectivity and more den-
sified junction points. These differences highlight the advan-
tages of selecting NWs with high ARs for TCF fabrication, in
accordance with theoretical prediction.59 Besides, the larger
line resistance (resistance across a certain length) of NWs
from 0.4 mL KCl also make a contribution due to a smaller
diameter.25,60
As the length of nanowires was further improved, the
quality of films could be expected to be upgraded. In the series
of FeCl3 reactions with different addition amounts, AgNWs of
0.7 mL FeCl3 with high AR and the largest diameter has a
better performance than the FeCl3-STD product. The achieved
T% was as high as 88% when Rs was reduced to 10 ohm sq−1.
Accordingly, the films prepared by AgNWs from the Fe10Cl4
reaction, which have the largest length and the highest aspect
ratio up to 1600, gained a property of Rs = 12.4 ohm sq−1 at T%
= 90.1%, exhibiting the best R & T performance when T% >
90%. As far as we can see, this property is one of the best
among pristine AgNW films.9,21b,25,28,55b However, it is only
slightly better than the products from the 0.7 mL FeCl3 recipe,
which seems to be a little unexpected considering the apparent
superiority in length and AR of NWs (almost twice the index of
that from 0.7 mL FeCl3). To analyze the reason, except higher
line resistance induced by the thinner diameter, this probably
originates from the fact that longer wires are more inclined to
twist and intertwist (or have entanglement effect61). The
former will result in a lengthened pathway compared with
straight wires, while the latter will cause plentiful agglomera-
tion of particles in the films (Fig. S8†). Consequently, as the
wire density of the Fe10Cl4 film increased later, the uniformity
deteriorated and T% lagged behind the position of 0.7 mL
FeCl3 under the same Rs. These results suggest that NWs with
higher AR always means higher R & T performance,55b,59 but
too high an aspect ratio could generate extra problems and
probably is not the most practical one for TCFs application.
In the meantime, smaller diameter will also produce posi-
tive influences despite higher line resistance when reduced to
a very low level (within ca. 50 nm). As seen in Fig. 10, the nano-
wire films from 10 mL KCl have good performance very close
to FeCl3-STD samples, much better than NWs of 0.4 mL KCl
with a similar AR. It should be noted that the length of NWs
from 10 mL KCl is only one fourth of that from FeCl3-STD,
while the diameter is about half of the latter one. These results
seem quite astonishing when analyzed in terms of conductivity
and geometric optics.60 The major reason then could only be
attributed to the diameter-dependent extinction efficiency of
nanowires.25 This is exactly reasonable as the haze index
under the same area coverage fraction (a direct reflection of
extinction efficiency) demonstrates a near exponential incre-
ment with increasing NW diameters within the diameter range
of 1–100 nm.62 Therefore, the extinction efficiency of NWs
from 10 mL KCl is only half (or less) of that from FeCl3-STD. In
other words, four strips of these thin nanowires have an extinc-
tion intensity equal to one strip of a thick nanowire, provided
This journal is © The Royal Society of Chemistry 2016

Nanoscale
their lengths are all the same. As a result, under the same T%,
the nanowire density of Ag NW films from 10 mL KCl is about
16 times (4 × 4) the density of that from FeCl3-STD, and the
increased wire density will generate more conduction pathways
and reduce parallel resistances, efficient to compensate for the
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
weakness of conductivity in a single nanowire. A visual com-
parison of AgNW TCFs from different sizes with a T% all
around 90% is shown in Fig. S9† to help compare their wire
densities.
Based on the above comparison, we conclude that the effect
of diameter is stronger than the effect of length. Under the
same T%, TCFs composed of thin NWs will have larger wire
density. Despite inferiority in conductivity, a diameter small
enough can produce great advantage for low extinction
efficiency, promising to achieve high-quality TCFs with low
haze. In contrast, thick NWs lose competitiveness in optical
aspects. However, our experiments demonstrate that NWs with
large diameters can also achieve high performance compar-
able to or even better than NWs with a small diameter and
high AR,63 which result from the superiority in conductivity, as
well as the length, since thick wires are more prone to gain
longer length. Moreover, NWs with a medium diameter (e.g.,
60–80 nm) seem to be inferior due to the combined mediocrity
in R & T performance. Hence, the R & T property has a
V-shaped dependence on the diameter.25,64
4. Conclusions
In summary, we have introduced a one-pot stirring-free
manner to efficiently synthesize AgNWs by the polyol method
incorporating additives of inorganic salts, which is superior
for its high yield, high uniformity, and high repeatability, as
well as scalable and cost-effective, which is the basic advan-
tages of polyol synthesis. After carrying out a series of com-
parative trials, the individual functions of ion species (i.e., Fe3+
& Cl−) in these salts were clarified. We found that the major
role of Cl− was to slow down the reduction speed of Ag+, and
to produce AgCl NPs which could serve as heterogeneous
nuclei for subsequent growth of AgNWs, ensuring high yield.
In the meantime, Fe3+ ions, as a strong etchant, could effec-
tively reduce the supersaturation degree via oxidative etching,
so as to restrict the formation of AgNW nuclei. By adjusting
the amount of dual control agents, i.e., Cl− & Fe3+, where the
amount of Cl− set the basic seed concentration, while Fe3+
further tailored the number of active seeds by etching away
some of them, we managed to tune the size of AgNWs in a
broad range (D = 45–220 nm, L = 10–230 μm), much wider
than the single addition of Cl− (D = 45–80 nm, L = 10–18 μm).
This improvement was well explained by direct control of seed
concentration developed at the initial phase.
Taking advantage of various sizes of AgNWs synthesized
above, we were able to study well the size-related variation ten-
dency lying in common characterization methods. The XRD
patterns demonstrated diameter-dependent nanometer-size
effects, which would lead to a larger FWHM index and peak
This journal is © The Royal Society of Chemistry 2016
View Article Online
Paper
transformations compared with bulk Ag. UV-vis spectra
revealed that there was an exponential relationship between
SPRs’ peak wavelength and diameters for NWs in the range of
45–150 nm.
When several products of AgNWs were selected as represen-
tatives, the effects of sizes on the properties of pristine Ag NW
TCFs were studied. Based on contrastive analysis, we found
that the diameter of NWs had more pronounced influences,
than length, on the combined properties of Rs and T%, pre-
senting a V-shaped dependence. NWs with a small or large dia-
meter are both inclined to achieve high performance, while a
medium diameter leads to a mediocre quality. If the R & T pro-
perties of pristine AgNW TCFs are expected to be further
improved, it’s vital that their diameter needs to be restricted to
a width below 50 nm, which is possible to be achieved by a
high pressure reaction or transverse growth inhibition by
Br−.63,65 At the same time, their average length should be pro-
longed to approach an aspect ratio of 500 or higher.
In brief, we have developed a protocol that provides a con-
venient strategy to reach the synthesis of AgNWs with tunable
sizes, and this strategy is believed to be applicable for the syn-
thesis of some other nanomaterials. Besides, it has been
shown that AgNWs are very promising TCMs with excellent R &
T properties. We anticipate that our results will promote the
research interest and studies of AgNWs for potential appli-
cations, especially as an excellent material for TCEs.
Acknowledgements
This work is financially supported by the National Basic
Research Program of China (2011CB933300), the National
Natural Science Foundation of China (Grants 51132001,
61474084, 51272184, 81572860 and 81272443), the National
Science Fund for Talent Training in Basic Science (no.
J1210061) and the Fundamental Research Funds for the
Central Universities (Grant 2014202020202). The authors
acknowledge the support from the teachers in the Center of
Nanosci. & Nanotech. Research and the Center for Electron
Microscopy in Wuhan University. K. Zhan conceived the main
experiments and wrote the paper. R. Su assisted in experiment
design and materials synthesis. Z. Yu and N. Cheng helped in
data analysis. X. Zhao helped revising the manuscript. All
authors gave beneficial comments on the manuscript. The
authors also thank Dr Bo Cai and Dr Kiran Kumar
Kondamareddy for helpful discussions during the preparation
of the manuscript. Kan Zhan thanks Dr Haoning Wang for
some experimental help.
Notes and references
1 Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin,
F. Kim and H. Yan, Adv. Mater., 2003, 34, 353–389.
2 (a) S. Link and M. A. EI-Sayed, Annu. Rev. Phys. Chem.,
2003, 54, 331–366; (b) Y. Fang, Z. Li, Y. Huang, S. Zhang,
Nanoscale, 2016, 8, 18121–18133 | 18131

Paper
P. Nordlander, N. J. Halas and H. Xu, Nano Lett., 2010, 10,
1950–1954.
3 (a) J. P. Kottmann, O. J. F. Martin, D. R. Smith and
S. Schultz, Phys. Rev. B: Condens. Matter, 2001, 64, 235402;
(b) A. Tao, F. Kim, C. Hess, J. Goldberger, R. He, Y. Sun,
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
Y. Xia and P. D. Yang, Nano Lett., 2003, 3, 1229–1233.
4 Y. H. Wang, N. N. Xiong, Z. L. Li, H. Xie, J. Z. Liu, J. Dong
and J. Z. Li, J. Mater. Sci.: Mater. Electron., 2015, 26, 7927–
7935.
5 (a) D. S. Hecht, L. Hu and I. Glen, Adv. Mater., 2011, 23,
1482–1513.
6 (a) K. G. Nair, D. Jayaseelan and P. Biji, RSC Adv., 2015, 5,
76092–76100; (b) S. Yao and Y. Zhu, Nanoscale, 2014, 6,
2345–2352.
7 (a) A. R. Rathmell, S. M. Bergin, Y. L. Hua, Z. Y. Li and
B. J. Wiley, Adv. Mater., 2010, 22, 3558–3563;
(b) I. E. Stewart, A. R. Rathmell, L. Yan, S. Ye, P. F. Flowers,
W. You and B. J. Wiley, Nanoscale, 2014, 6, 5980–5988.
8 J. Lee, P. Lee, H. Lee, D. Lee, S. S. Lee and S. H. Ko,
Nanoscale, 2012, 4, 6408–6414.
9 Z. Yu, Q. Zhang, L. Li, Q. Chen, X. Niu, J. Liu and Q. Pei,
Adv. Mater., 2011, 23, 664–668.
10 (a) J. Y. Lee, S. T. Connor, Y. Cui and P. Peumans, Nano
Lett., 2008, 8, 689–692; (b) L. Dong-Seok, E. Angharad,
F. Mark, N. Jenny, D. D. C. Bradley and J. C. de Mello, Adv.
Mater., 2011, 23, 4371–4375.
11 G. Fei, A. Hamed, H. Yi, P. Thomas, H. Mengyao, B. Carina,
L. Stefan, S. Erdmann, F. Karen and C. J. Brabec,
Nanoscale, 2015, 7, 1642–1649.
12 (a) Y. Sun, J. Phys. Chem. C, 2010, 114, 2127–2133;
(b) Y. Yin, Y. Lu, Y. Sun and Y. Xia, Nano Lett., 2002, 2, 427–
430.
13 (a) J. Choi, G. Sauer, K. Nielsch, R. B. Wehrspohn and
U. Gösele, Chem. Mater., 2003, 15, 776–779; (b) V. M. Cepak
and C. R. Martin, J. Phys. Chem. B, 1998, 102, 9985–9990;
(c) N. R. Jana, L. Gearheart and C. J. Murphy, Chem.
Commun., 2001, 617–618.
14 (a) J. Q. Hu, Q. Chen, Z. X. Xie, G. B. Han, R. H. Wang,
B. Ren, Y. Zhang, Z. L. Yang and Z. Q. Tian, Adv. Funct.
Mater., 2004, 14, 183–189; (b) K. K. Caswell, C. M. Bender
and C. J. Murphy, Nano Lett., 2003, 3, 667–669.
15 (a) Z. Wang, J. Liu, X. Chen, J. Wan and Y. Qian, Chem. –
Eur. J., 2004, 11, 160–163; (b) X. Sun and Y. Li, Adv. Mater.,
2005, 17, 2626–2630; (c) X. Jian, J. Hu, C. Peng, H. Liu and
H. Ying, J. Colloid Interface Sci., 2006, 298, 689–693;
(d) E.-J. Lee, Y.-H. Kim, D. K. Hwang, W. K. Choi and
J.-Y. Kim, RSC Adv., 2016, 6, 11702–11710.
16 L. Gou, M. Chipara and J. M. Zaleski, Chem. Mater., 2007,
19, 569–576.
17 M. Tsuji, K. Matsumoto, N. Miyamae, T. Tsuji and
X. Zhang, Cryst. Growth Des., 2006, 7, 311–320.
18 F. Fievet, J. Lagier and M. Figlarz, MRS Bull., 1989, 14,
29–34.
19 (a) Y. Sun, B. Gates, B. Mayers and Y. Xia, Nano Lett., 2002,
2, 165–168; (b) Y. Sun, Y. Yin, B. T. Mayers, T. Herricks and
Y. Xia, Chem. Mater., 2002, 14, 4736–4745.
18132 | Nanoscale, 2016, 8, 18121–18133
View Article Online
Nanoscale
20 (a) C. Chen, L. Wang, G. Jiang, J. Zhou, X. Chen, H. Yu and
Q. Yang, Nanotechnology, 2006, 17, 3933–3938; (b) C. Chen,
L. Wang, H. Yu, J. Wang, J. Zhou, Q. Tan and L. Deng,
Nanotechnology, 2007, 18, 4473–4476.
21 (a) J. Jiu, K. Murai, D. Kim, K. Kim and K. Suganuma,
Mater. Chem. Phys., 2009, 114, 333–338; (b) J. Jiu, T. Araki,
J. Wang, M. Nogi, T. Sugahara, S. Nagao, H. Koga,
K. Suganuma, E. Nakazawa, M. Hara, H. Uchida and
K. Shinozaki, J. Mater. Chem. A, 2014, 2, 6326–6330.
22 B. Wiley, Y. Sun and Y. Xia, Langmuir, 2005, 21, 8077–
8080.
23 B. Li, S. Ye, I. E. Stewart, S. Alvarez and B. J. Wiley, Nano
Lett., 2015, 15, 6722–6726.
24 K. E. Korte, S. E. Skrabalak and Y. Xia, J. Mater. Chem.,
2008, 18, 437–441.
25 S. M. Bergin, Y. H. Chen, A. R. Rathmell, P. Charbonneau,
Z. Y. Li and B. J. Wiley, Nanoscale, 2012, 4, 1996.
26 S. Coskun, B. Aksoy and H. E. Unalan, Cryst. Growth Des.,
2011, 11, 4963–4969.
27 J. Ma and M. Zhan, RSC Adv., 2014, 4, 21060.
28 J. Han, S. Yuan, L. Liu, X. Qiu, H. Gong, X. Yang, C. Li,
Y. Hao and B. Cao, J. Mater. Chem. A, 2015, 3, 5375–
5384.
29 Y. H. Chang, Y. C. Lu and K. S. Chou, Chem. Lett., 2011, 40,
1352–1353.
30 W. C. Zhang, X. L. Wu, H. T. Chen, Y. J. Gao, J. Zhu,
G. S. Huang and P. K. Chu, Acta Mater., 2008, 56, 2508–
2513.
31 D. Chen, X. Qiao, X. Qiu, J. Chen and R. Jiang,
Nanotechnology, 2010, 21, 025607.
32 (a) H. Lu, D. Zhang, J. Cheng, J. Liu, J. Mao and
W. C. H. Choy, Adv. Funct. Mater., 2015, 25, 4211–4218;
(b) M. Lagrange, D. Langley, G. Giusti, C. Jiménez,
Y. Bréchet and D. Bellet, Nanoscale, 2015, 7, 17410–
17423.
33 (a) V. K. LaMer and R. H. Dinegar, J. Am. Chem. Soc., 1950,
72, 4847–4854; (b) F. Wang, V. N. Richards, S. P. Shields
and W. E. Buhro, Chem. Mater., 2014, 26, 5–21.
34 Y. Yin and A. P. Alivisatos, Nature, 2005, 437, 664–670.
35 W. Zhang, P. Chen, Q. Gao, Y. Zhang and Y. Tang, Chem.
Mater., 2008, 20, 1699–1704.
36 (a) Y. Zheng, J. Zeng, A. Ruditskiy, M. Liu and Y. Xia, Chem.
Mater., 2014, 26, 22–33; (b) R. Long, S. Zhou, B. J. Wiley
and Y. Xiong, Chem. Soc. Rev., 2014, 43, 6288–6310.
37 Q. Zhang, W. Li, C. Moran, J. Zeng, J. Chen, L.-P. Wen and
Y. Xia, J. Am. Chem. Soc., 2010, 132, 11372–11378.
38 B. Wiley, Y. Sun and Y. Xia, Acc. Chem. Res., 2007, 40, 1067–
1076.
39 (a) Y. Xia, Y. Xiong, B. Lim and S. E. Skrabalak, Angew.
Chem., Int. Ed., 2008, 48, 60–103; (b) Y. Wang, J. He, C. Liu,
W. H. Chong and H. Chen, Angew. Chem., Int. Ed., 2015, 54,
2022–2051.
40 Z. Yang, H. Qian, H. Chen and J. N. Anker, J. Colloid
Interface Sci., 2010, 352, 285–291.
41 D. Chen, X. Qiao, X. Qiu, J. Chen and R. Jiang, J. Mater.
Sci.: Mater. Electron., 2011, 22, 6–13.
This journal is © The Royal Society of Chemistry 2016

Nanoscale
42 P.-Y. Silvert, R. Herrera-Urbina and K. Tekaia-Elhsissen,
J. Mater. Chem., 1997, 7, 293–299.
43 (a) W. M. Schuette and W. E. Buhro, ACS Nano, 2013, 7,
3844–3853; (b) H. Yu, P. C. Gibbons, K. F. Kelton and
W. E. Buhro, J. Am. Chem. Soc., 2001, 123, 9198–9199;
Published on 27 September 2016. Downloaded by CHONNAM NATIONAL UNIVERSITY on 3/23/2023 6:48:19 AM.
(c) H. Yu and W. E. Buhro, Adv. Mater., 2003, 15, 416–419.
44 X. G. Peng, J. Wickham and A. P. Alivisatos, J. Am. Chem.
Soc., 1998, 120, 5343–5344.
45 B. J. Wiley, T. Herricks, Y. Sun and Y. Xia, Nano Lett., 2004,
4, 1733–1739.
46 X. Chen and S. S. Mao, Chem. Rev., 2007, 107, 2891–2959.
47 M. S. Haque, H. A. Naseem, A. P. Malshe and W. D. Brown,
Chem. Vap. Deposition, 1997, 3, 129–135.
48 R. L. Zong, Z. Ji, L. Qi, D. Bo, L. Bo, F. Ming, X. W. Qi,
L. T. Li and S. Buddhudu, J. Phys. Chem. B, 2004, 108,
16713–16716.
49 K. L. Kelly, E. Coronado, L. L. Zhao and G. C. Schatz,
J. Phys. Chem. B, 2003, 34, 668–677.
50 P. K. Jain, K. S. Lee, I. H. El-Sayed and M. A. El-Sayed,
J. Phys. Chem. B, 2006, 110, 7238–7248.
51 H. Wolfgang, N. T. K. Thanh, A. Jenny and D. G. Fernig,
Anal. Chem., 2007, 79, 4215–4221.
52 K. Akshay and Z. Chongwu, ACS Nano, 2010, 4, 11–14.
53 S. De and J. N. Coleman, MRS Bull., 2011, 36, 774–781.
54 S. Ye, A. R. Rathmell, Z. Chen, I. E. Stewart and B. J. Wiley,
Adv. Mater., 2014, 26, 6670–6687.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Paper
55 (a) T. Tokuno, M. Nogi, M. Karakawa, J. Jiu, T. T. Nge,
Y. Aso and K. Suganuma, Nano Res., 2011, 4, 1215–1222;
(b) H. L. Jin, P. Lee, D. Lee, S. S. Lee and S. H. Ko, Cryst.
Growth Des., 2012, 12, 5598–5605.
56 M. Batmunkh, M. J. Biggs and J. G. Shapter, Small, 2015,
11, 2963–2989.
57 S. Vittorio, C. Richard, P. E. Lyons, R. David and
J. N. Coleman, Small, 2011, 7, 41–48.
58 L. Hu, H. S. Kim, J. Y. Lee, P. Peumans and Y. Cui, ACS
Nano, 2010, 4, 2955–2963.
59 R. M. Mutiso, M. C. Sherrott, A. R. Rathmell, B. J. Wiley
and K. I. Winey, ACS Nano, 2013, 7, 7654–7663.
60 P. C. Hsu, S. Wang, H. Wu, V. K. Narasimhan, D. Kong,
L. H. Ryoung and Y. Cui, Nat. Commun., 2013, 4, 2522.
61 S. Kang, T. Kim, S. Cho, Y. Lee, A. Choe, B. Walker, S.-J. Ko,
J. Y. Kim and H. Ko, Nano Lett., 2015, 15, 7933–7942.
62 G. Khanarian, J. Joo, X. Q. Liu, P. Eastman, D. Werner,
K. O’Connell and P. Trefonas, J. Appl. Phys., 2013, 114, 024302.
63 E. J. Lee, M. H. Chang, Y. S. Kim and J. Y. Kim, APL Mater.,
2013, 1, 042118.
64 S. Sorel, P. E. Lyons, S. De, J. C. Dickerson and
J. N. Coleman, Nanotechnology, 2012, 23, 185201–185209.
65 (a) K. Zhang, Y. Du and S. Chen, Org. Electron., 2015, 26,
380–385; (b) R. R. da Silva, M. Yang, S.-I. Choi, M. Chi,
M. Luo, C. Zhang, Z.-Y. Li, P. H. C. Camargo, S. J. L. Ribeiro
and Y. Xia, ACS Nano, 2016, 10, 7892–7900.
Nanoscale, 2016, 8, 18121–18133 | 18133