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Rev.Adv.Mater.Sci. 24(2010) 10-25 G. Yan, L. Wang, and L. Zhang



Guangqing Yan, Li Wang, and Lei Zhang

State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang
University, Hangzhou 310027, DV a]Vt
dFVafS] Z
Received: December 10, 2009

Abstract. This review concentrates on the various chemical routes for synthesis of silver nanowires
by soft solution methods, and also the production of gold nanotubes and Pt nanotubes from
different templates. After a comprehensive comparison between the developed methods, it is
concluded that the soft solution method has obvious advantages and is the most promising
route for the mass production of silver nanowires. Herein its recent development is generalized
into two groups: surfactant-assisted soft chemistry method and soft template method of which
advantages and disadvantages will be discussed elaborately and separately. In addition, the
synthesis of Au and Pt nanotubes from resultant silver nanowires, although less researched
than other methods, is considered as the most convenient and facile route among the templated
methods. Due to their high thermal and electrical conductivities, these metal nanomaterials are
excellent candidates for the conductive filler in composite adhesive. Especially for one-dimen-
sional metal nanostructures, they show great promise in the improvement of current conductive

1. INTRODUCTION mass production of silver nanowires, gold and plati-

num nanotubes is necessary and of great signifi-
Nanomaterials have shown plenty of speciality and
superiority due to their small dimensions, and they
For the synthesis of silver nanowires, plenty of
have exhibited great applicable potential in the field
chemical routes have been developed during these
of high-performance catalyst [1-3], magnetics [4],
years. However, soft solution method has been
acoustics [5], optics [6] and electronics [7,8], at-
widely considered as the most feasible route to
tracting increasingly interests from the whole world.
large-scale production of silver nanowires. Xia et al.
Metal nanowires and nanotubes, as one-dimensional
first proposed a PVP (polyvinylpyrrolidone)-assisted
(1D) nanostructures, have been extensively studied
polyol process, which has become the most popu-
on their optical properties [9,10], and as well their
lar method nowadays [13]. Moreover, a variety of
potential use as conductive fillers to enhance the
other surfactants (capping agent) have been devel-
performance of the adhesives [11]. Due to the high
oped to guide the anisotropic growth of silver
electrical conductivity of bulk silver, gold and plati-
nanowires later during these years [14-16], and the
num, their nanowires and nanotubes are the most
diversity of surfactants provides many choices to
promising candidates to be used as conductive fill-
meet the various demands. Generally speaking, the
ers of high-performance adhesives [12]. Hence, the
Corresponding author: Li Wang, e-mail:

p) ( 5Ug
Vc7 %
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 11

mass production by soft solution process is the most and commonly are studied separately. For the sur-
hopeful and feasible for its convenience and high factant-assisted soft chemistry method, plenty of
efficiency compared with other methods. Besides, surfactants have been used to guide the one-dimen-
for the synthesis of gold and platinum nanotubes, sional (1D) growth of silver nanowires. The anisotro-
the guidance of templates is almost indispensable. pic growth of these silver nanowires is partially as-
However, among the numerous applied templates, cribed to the selective adsorption of these surfac-
silver nanowires are the most convenient and ex- tants onto the specific facet of the nanostructure
cellent ones because of the perfect crystallographic and leaving the bare facet still active for the further
match and no need for the additional procedures to deposition of silver atoms. Herein, we set the popu-
remove the templates after completing the reaction lar polyol method as the representative example to
[17,18]. elaborately illuminate the recent research progress
Totally this article mainly reviews the recent re- on the mechanism of the surfactant-assisted soft
search progress on synthesis of silver nanowires chemistry method.
by soft solution method and fabrication of gold and For the polyol synthesis of silver nanowires, Xia
platinum nanotubes from resultant silver nanowires. et al. [13] had contributed a lot to the basic research
Furthermore, it also pays much attention on the fea- and proposed many reasonable and important view-
sibility and significance of applying these points on the mechanism, which had been widely
nanomaterials to the improvement of conductive adopted and accepted by other peer-researchers
coatings. now. In most of the synthetic routes, AgNO3 was
usually adopted as the precursor and polyol always
2. PREPARATION OF SILVER acted as both solvent and reducing reagent, while
NANOWIRES BY SOFT SOLUTION the capping reagent varies in abundance of candi-
METHOD dates. After Xia et al. detected the presence of Gly-
colaldehyde (GA) in the polyol reactive system [20],
Nowadays, many non-chemical methods for fabri- the reaction formats were elucidated as follows:
cating nanowires have been developed out and some
of them may have obvious advantages over prepara- HOCH2 CH2 OH CH3 CHO H2 O, (1)
tion of peculiar morphological silver nanowires, but
they are usually complicated, highly energy-con- 2 Ag 2 CH3 CHO CH3 COOH3 2 Ag 2 H , (2)
suming and sophisticated. Therefore, the chemical
method has been the most promising way for the 2HOCH2 CH2 OH O 2 2HOCH2 CHO 2H2 O. (3)
large-scale fabrication of silver nanowires in future.
Among the various routes, the soft solution method They found that heating ethylene glycol (EG) in
is now the hottest point in the field of silver nanowires air resulted in its oxidative product (GA): a much
at present. Thousands of work has been devoted to stronger reductant than acetaldehyde. It was reported
the mechanical study, reactive condition explora- that, when temperature of the reactive system was
tion and application research during these years. above 150 o C, GA would become the predominant
Nowadays, some rapid progresses have already reductant in the presence of O2. So the reaction
been made on understanding the detailed mecha- format (3) should be added into this reactive sys-
nism and relatively fine control also has been taken tem. In addition, they also found the newly formed
on morphology, size and aspect ratio of the product silver nanoparticles could catalyze the oxidation of
[19]. Hopefully, large-scaled production of silver 9;e ;5 hYZ TYhRdUVW Z
_VURdq RfeTRe R] jeZ
nanowires through soft solution method can be re- WVTe r]ReVc % H d VVi eV_ee YZdeYV cjTR_Vi a]RZ_
alized in future. the influence of temperature and O2 on the final
morphology of product, and this information may
2.1. Preparation of silver nanowires also enhance the reproducibility and scalability of
by surfactant-assisted soft this polyol synthesis of silver nanowires [21].
As we all know, the fabrication of nanowires in
chemistry method
an isotropic solution would be quite easy and
2.1.1. Mechanism straightforward, when metal has an anisotropic crys-
talline lattice. But almost all the metals tend to crys-
Among various soft solution methods, they are usu-
tallize into highly symmetric face-centered cubic
ally divided into two groups: surfactant-assisted soft
lattices. Hence, we need the surfactant, namely the
chemistry method and soft template method, while
capping reagent, which not only protects nanowires
their mechanisms are quite different from each other
12 G. Yan, L. Wang, and L. Zhang

Fig. 2. Schematic model of the silver nanowires,

data from [26].

Fig. 1. Schematic illustration of the pentagonal

model of silver nanowire and MTP, see [13] for more
decrease and the crystal seeds would be gener-
ated more easily during the nucleation period. Once
the multiply-twinned particles formed, PVP would
from aggregating into bundles, but also promote the selectively adsorb onto the {100} facets by the co-
anisotropic growth of the silver nanowires. So far a ordination and induce the 1D growth. Furthermore
large number of capping agents have been used to the molar ratio between the repeating units of PVP
control the anisotropic growth of silver seeds to ob- molecules and the external silver atoms of nanowires
tain nanowires through soft solution reactions, such was calculated to be 1.5 through TGA and theoreti-
as PVP [13,22,23], CTAB [16], Sodium cal calculation.
Dodecylsulfonate (SDS) [14,19], Vitamin B2 [24] However, Zhang et al. [26] proposed another
and so on. mechanism later, in which they contributed the
To date, the most popular capping agent is PVP anisotropic growth to the effect of crystal strain rather
in the synthesis of silver nanowires and its detailed than the selective adsorption of surfactant. As de-
VT YR_Z d YRd _te jVe SVV_eY cfXY] jd e
fUZ VU fe % picted in Fig. 2, the penta-twinned crystal with 5-
It is believed that silver nanowires are derived from fold axis, which was shared by two {111} facets,
Multiply-Twinned Particles (MTPs), which are quite was formed by the stacking fault, because the theo-
different from the ordinary nanoparticles and only retical interfacial angle between two {111} facets on
can be generated under special situation [13]. As the top surface was just 360o /5 = 72o , while actu-
shown in Fig. 1, MTPs are covered by five {111} fac- ally it was usually 70.53ofor a perfect face-centered
ets at each end and the side surfaces of nanowires cubic (fcc) crystallite [27]. Thus, the angular mis-
are bounded by five {100} facets. The anisotropic match indicated that there must be lattice distor-
growth is realized by selectively covering the facets tion in the silver nanowires, and the atoms surround-
{100} with PVP as a result that {100} facets are ing the radial direction had to offset the mismatch
completely passivated, while {111} facets are largely by crystal strain and dislocation so as to form seam-
bare and still quite active. Hence the reduced silver less nanowires. It was obvious that crystal strain
atoms are preferentially deposited onto {111} fac- would augment with the diameter of nanowires in-
ets, leading to the anisotropic growth of silver creasing, and it would in return restrict the lateral
nanowires [25]. Gao et al. [23] further proved that growth of silver nanowires, and finally lead to the 1D
there was just a bed of Monolayer assembly ( PVP) growth.
on the surface of silver nanowires. In addition, they Recently, through designing a series of unique
further found that Ag+ would immediately coordinate experiments, Zhang et al. [28] proposed another
with the lone pair electrons of the oxygen atom on mechanism, in which the synergy between crystal
the carbonyl group of PVP, once PVP and silver strain and surface energy was considered to be re-
nitrate were simultaneously added into the reaction. sponsible for anisotropic growth of silver nanowires.
As a result, the chemical potential of Ag+ would It was reported that the crystal strain was not suffi-
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 13

Fig. 3. Mechanism of shape selective oxidative etching and crystal growth of Ag nanostructures
(modified), data from [31].

cient to provide enough restriction for 1D growth, In the first step, AgNO3 was reduced to form the
and the surface-capping agent was indispensable nucleus seeds at a quite low concentration. Then
for lowering surface energy difference between {100} the newly generated silver atom would selectively
and {111} facets to promote the growth of nanowires. deposit onto the seeds to induce the 1D growth at a
Following this mechanism, Ag wires with tunable relatively high concentration in the second step.
diameter and long length was obtained by control- Therefore, without adding additional control agents,
ling the lateral growth and the axial growth in two such synthesis of silver nanowires could not be
separate steps [28,29]. achieved in one step. To simplify the procedure and
improve the quality of the silver nanowires, plenty of
2.1.2. Synthesis of silver nanowires control agents had been developed out and different
with different control agents species would show quite different functions. Com-
monly these agents are divided into three groups:
Up to now, many research groups have been de- inorganic anions, metal cations and organic mol-
voted to exploring the synthetic conditions in the ecules. They either form the colloids with the silver
presence of PVP or other surfactants to promote ions to serve as the initial nucleus, or change the
the anisotropic growth of silver nanowires. Sun et rate of reduction and nucleation. Sometimes, these
al. [25] first proposed a polyol method to prepare control agents also can protect the penta-twinned
silver nanowires for mass production, and they in- crystal from being etching by the oxidant. Anyway
troduced PtCl2 to form the platinum nanoparticles all of these functions are favorable for the formation
serving as seeds for the heterogeneous nucleation. of the silver nanowires.
These platinum nanoparticles would grow into silver Due to the much stronger oxidation ability of
nanowires in the solution after reducing AgNO3 by H2PtCl6 than AgNO3, H2PtCl6 is the ideal precursor
ethylene glycol (EG). The product had uniform di- to provide the seed for the growth of silver nanowires.
ameters in the range of 30-40 nm and lengths up to Tsuji et al. [30] innovated to introduce the micro-
50 mm. wave to rapidly heat the reaction system in the pres-
As we all know, the polyol method traditionally ence of H2PtCl6 and a series of mixed one-dimen-
needed two steps to synthesize the silver nanowires: sional nanomaterials was achieved within a few min-
seeding process and nanowires-growing process. utes. Through repeating centrifugal separation, the
14 G. Yan, L. Wang, and L. Zhang

Fig. 5. Schematic illustration of PVP (polyvinylpyr-

rolidone) conformation on the surface of Ag
Fig. 4. Illustration of the role of Fe3+ and Fe2+ in the nanowires, data from [23].
polyol synthesis of silver nanowires, see also [35].

one-dimensional products were easily separated tion rate and it was known that the low reaction rate
from other three-dimensional particles and these was favorable for the formation of silver nanowires.
separated particles would further act as seeds to Despite of the Haloid anions, S2- ions were also
grow into longer and thicker 1-D products through added as the control agent: the precursor of cata-
repeating this reaction. However, recently a novel lytic seed. It was reported that Na2S could take a
viewpoint toward the roles of Pt seed and Chloride better control of the morphology of the product and
anions in this microwave-polyol method was pro- obtained more uniform silver nanowires by the polyol
posed. They did not think that the preformed AgCl method [32]. The authors also discovered that the
and Pt seeds were completely responsible for the lower concentration of Na2S caused the formation
nucleation and subsequent growth of the silver of nanocubes, while the high concentration yielded
nanowires, and they realized the free Cl- might also silver nanowires. Depressingly, until now, the de-
have a deep effect on the formation of the one-di- tailed mechanism was still not thoroughly disclosed
mensional nanostructure and other silver [34].
nanoparticles. To the best of our knowledge, differ- Inorganic anions, which are applied to control
ent morphological seeds would grow into different the morphology of the silver nanostructure, have very
nanostructures (as shown in Fig. 3). They found that obvious advantages for its convenience and relatively
the free Cl- would accelerate the re-dissolution of large-scaled fabrication. It really has great promis-
the formed nanoparticles and that was favorable for ing for the large-scaled fabrication of silver nanowires
the growth of silver nanowires and other one-dimen- through this method. However, there also exists
sional nanostructures [31]. some defects on the products, such as the intro-
It was reported that silver nanowires with adjust- duction of many impurities, relatively rough surface
able diameters could be synthesized by adding dif- and severe distortion of nanowires.
ferent control agents [32]. The additive Haloid an- Despite of the inorganic anions, the metal ions
ions not only just provided initial nucleus, but also were also used to induce the growth of silver
VU nanowires. It not only can provide the metal nucleus
mechanism had been elucidated by Chipara et al. seeds, but sometimes also can make good use of
[33] in their article. The reaction of Cl- with Ag+ could its oxidative capability, which can consume the newly
act as a buffer decreasing the concentration of free generated silver atoms to control the size of seed
Ag+ as a result that the potential of the Ag+/0 pair and decelerate the nucleation rate. Sun et al. [35]
would be reduced and the rate of formation of silver had succeeded in using Fe3+ and Fe2+ in the polyol
atom would also decrease. Besides, the presence method to synthesize nanowires (Fig. 4). They pro-
of Cl- would accelerate the oxidative dissolution of posed that Fe2+ could react with the absorbed
silver nanoparticles in the ambient atmosphere. atomic oxygen on the surface of silver
Therefore, these two factors both reduced the reac- nanostructures, preventing multiply-twinned particles
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 15

from being oxidatively etched. In addition, the newly Caswell et al. [37] had reported one seedless,
formed Fe3+ would, in return, be reduced into Fe2+ surfactantless, wet chemical synthesis of silver
by ethylene Glycol (EG) again. It was also reported nanowires in water. In this reactive system, the cit-
that, because of the oxidative etching by Fe3+ on rate not only strongly complexed the Ag+, but also
the surface of the seed, the small silver nuclei would performed as the reductant of silver ions and cap-
grow into nanowires with smaller diameter [32]. Simi- ping agent to silver nanomaterials. Moreover, hy-
larly, Skrabalak et al. developed a rapid synthesis droxide ions played very important roles in forma-
of silver nanowires through a CuCl- or CuCl2-medi- tion of silver nanowires, because it could complex
ated polyol process [36]. They made use of the re- with the silver ions as well. Nevertheless, due to no
ductive property of Cu+ to scavenge the absorbed surfactant existing in the system, the product tended
oxygen, which covered on the surface of the Ag seed to grow into bundles and sticked to each other.
preventing it from further Ag deposition. Moreover, Despite of the citrate, glucose, hypophosphite [26]
the introduction of chloride ions also reduced the and potassium tartaric [38] also can be used to
concentrations of initial free Ag+. Hence, both the synthesize the silver nanowires, but they only serve
cations and anions were added to enhance the ac- as capping agents without surfactants providing
cessibility to the silver nanowires. good dispersity. As a result, it was inevitable to clus-
Comparing with the inorganic control agents, the ter into bundles.
organic showed quite different and particular in the To obtain the product of good dispersity, some
polyol solution and some of them maybe acted as surfactants were added into the reaction, and they
the capping agent and surfactant for the anisotropic can serve as capping agent to guide the anisotropic
growth as well. These organic compounds usually Xche YRdhV] ]
% : cZ_d eR_T VDJDt d]_VaRZ cW e
tended to facilitate a much bigger radius of the prod- oxygen on the carbonyl group can strongly coordi-
uct, such as ascorbic acid, which could promote nate with silver atoms on the side surface while leav-
the fabrication of silver nanowires with a mean di- ing the end surface of nanowires uncovered for sil-
ameter of ~190 nm [32]. Since the organic control ver deposition [23,39]. PVP used as inducing agent
agents usually act as surfactants or reducing agents has been intensively studied during these years and
in the reactive system, we do not make a separate the correlative theories become more and more so-
discussion here, but will analyze it combining with phisticated. However, polyvinyl alcohol (PVA) and
capping agent later. polyethylene glycol with oxygen of lone pair tend to
coil into agglomerate, which is unfavorable for the
2.1.3. Synthesis of silver nanowires formation of one-dimensional structure.
with different capping agent Except for PVP, the Gemini surfactant was also
used to direct the growth of silver nanowires. Xu et
Sometimes silver nanowires can be fabricated in al. [40] had used the methenamine as the reducing
the absence of additional capping agents, because agent to synthesize the silver nanowires of high
some organic reactants can serve as both reducing aspect ratios with an average diameter of ~30 nm.
agents and capping agents. As a result, it seems In this reactive system, the Gemini provided Br- as
to be no capping agents. However, to obtain silver control agent and methenamine degraded to gener-
nanowires, the capping agents are almost indispens- ate HCHO and NH3. Then NH3 can complex with
able, because we usually need to fabricate the the Ag+ and HCHO would act as the reducing agent.
nanowires of a highly anisotropic crystalline lattice Finally, both the slow reaction rate and the Capping
in an isotropic solution and the silver nanowires can effect of Gemini surfactant contributed to the aniso-
not be fabricated just by the restriction of crystal tropic growth of sliver nanowires. This synthetic route
strain without selectively lowering the surface en- is quite advantageous, because it not only simpli-
ergy by capping agent. Most capping agents take fies the procedure, but also takes place in aqueous
advantage of the carbonyl group and amino group solution at a relatively low temperature.
to selectively adsorb onto the specific facets of the Cetyltrimethylammonium bromide (CTAB) is
silver nanowires inducing the 1D growth. The coor- another good choice for guiding the anisotropic
dination (N-Ag, O-Ag) would properly passivate the growth of silver nanowire and nanorod. Unlike PVP,
adsorbent facets {100}. However, different capping CTAB tends to selectively adsorb onto the side sur-
agents have different conformation and would pro- face of silver nanostructures through the coordina-
vide different steric repulsion. Therefore the silver tion between N on the amino group and silver atom.
nanowires with different morphology and different It was evidenced that CTAB formed the bilayer on
diameter would be obtainable. the metal surface to hinder the lateral growth of
16 G. Yan, L. Wang, and L. Zhang

nanowires or nanorods and its mechanism was the cially when the preparation is in a relatively high
dR VRdDJDt dO +(+)P % concentration. Recently, Zhang et al. [29] proposed
In the assistance of some special capping a route by adding stainless steel to restrain in situ
agents, silver nanowires of different morphology may nitric acidic etching. The stainless steel consumed
be synthesized for some special use, such as zig- HNO3 in advance, efficiently protecting the MTPS
zag morphology. He et al. [43] successfully fabri- from being dissolved. This mechanism may have
cated the silver nanowires of zigzag morphology great significance on the large-scale fabrication of
using N,N-dimethylformamide as the reducing agent silver nanowires, because the etching power of HNO3
in the presence of tetrabutyl titanate (TBT) and is quite strong even at a low concentration. Besides,
acetylacetone (AcAc). It was reported that TBT and the generated H2O and organic byproduct may also
AcAc could guide the silver nanoparticles selectively have significant effect on the morphology of the
aggregation along the preferred crystallographic axes nanomaterials. Unfortunately, there still needs much
to form short nanorods, while the zigzag morphol- work to do on this aspect. Moreover, the shielding
ogy should be contributed to the simultaneously gas not only greatly influences the reproducibility of
adsorbing one nanoparticle by two different nanorods. the experiment, but also has obvious effect on the
In another synthetic system, tetrabutylammonium morphology of the product [21]. It was said that the
bromide (TBAB) was used to guide the anisotropic inert gases were quite favorable for the repeatability
growth of silver nanowires through the reduction of of the experiment, while the existence of O2 would
the hydrazine in the presence of decanoic acid and promote the formation of silver nanowires. Hence,
dodecylamine. The role of TBAB is similar to PVP, the synthesis of the silver nanowires extremely
which can selectively cover the {110} and {100} needs us to take good control of all the factors, and
planes. The aspect ratio of the product can be con- consequently, we have to make a deeper insight
trolled ranging from 1-70 by varying the reaction time into this field.
and concentration [44]. Recently, a novel and inter-
esting mechanism was proposed for these situa- 2.2. Preparation of silver nanowires
tions [45], which was quite different from the previ- by soft template methods
ous one. They supposed that the formation of silver
nanowires based on the aggregation-based mecha- 2.2.1. Mechanism
nism It was reported that the silver aggregation of For 1D nanostructure, mesophases structures,
nanoparticles would form in the initial stage of the which are usually self-assembled from surfactants,
experiment, and it aggregated via the ion bonding provide a group of useful and soft templates for the
between the cysteine molecules on the surface of anisotropic growth of silver nanowires and nanorods
silver nanoparticles. So the pH value was quite cru- in relatively large quantities. It is well known that
cial for the formation of silver nanowire. However, in some surfactants tend to self-assemble into rod-
this system, the product tended to be needle-like, shaped micelles at its critical micellar concentra-
had low aspect ratio and extended along different tion (CMC). Therefore, the surfactants are commonly
directions. adopted to form the micelles and emulsion in the
Generally speaking, the capping agents are usu- soft template method, and then these mesophases
ally indispensable for the synthesis of uniform, regu- structures provide the micropores for the growth of
lar and mono-disperse silver nanowires. Their con- silver nanowires as shown in Fig. 6. Quite different
centration can make a good control over the mor- from the surfactant-assisted soft chemistry method,
phology, size and aspect ratio of silver nanowires in soft template method depends on the restriction of
the soft solution method. Furthermore different cap- the micelles and emulsion to guide the 1D growth
ping agents will induce the formation of different sil- of silver nanowires and nanorods but not the selec-
ver nanowires, which would meet the different de- tive adsorption of the surfactants to mediate the
mands. surface energy. It was reported that the surfactants
Except for the control agents and capping agents could initially induce the one-dimensional growth,
mentioned above, there are still many other influ- and the rod-like micelles would further promote the
encing factors which should be considered care- formation of silver nanowires [46,47]. Generally
fully. As we all know, the multiply-twinned particles speaking, the interface restriction from the surfac-
(MTPS) are responsible for the formation of silver tant molecules contributes to the growth of nanowire,
nanowires, while some byproducts may have pro- while the aspect ratios of silver nanowires are domi-
found effect on them. For example, the generated nantly decided by the morphology and sizes of the
HNO3 can consume the newly formed MTPS, espe- micelles and micro-emulsion. The concentration of
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 17

Fig. 6. Schematic illustration of typical soft template method for the synthesis of silver nanowires (modi-
fied), see [46] for more details.

precursors and surfactants also plays an important for the silver nanowires. Particularly experimental
role in these aspects of the products. results showed that the concentrations of the reac-
tant AgNO3 and tri-sodium citrate were interdepen-
2.2.2. Preparation of silver nanowires dent in the fabrication of the silver nanorods and
by different soft templates nanowires [15]. In addition, it was reported that sil-
ver nanorods and nanowires were obtained by a
Block copolymers formed by several immiscible seed-mediated growth approach in the rod-like mi-
segments can be exploited as the soft templates cellar media. The micellar media was formed in a
for the synthesis of silver nanowires. It was reported AgNO3/ascorbic acid/CTAB/NaOH solution. The
that some regular cylinders would formed in the pres- synthesized silver nanorods had 40nm long with
ence of block copolymer under appropriate condi- aspect ratio 2.5-15, and the silver nanowires even
tions, which are very similar to the micelles and had 1-4 m long with aspect ratio 50-350. The only
emulsion inducing the 1D growth [46,48]. difference between the preparations of silver
In the presence of AgNO3, Vitamin C and so- nanorods and silver nanowires was the relative con-
dium dodecyl sulfate (SDS), Liu et al. [14] had syn- centration of NaOH in the solution [47]. Recently, a
thesized the silver wires with high aspect ratio in novel soft template method of silver nanowires was
the ethanol solution. It was proposed that the mi- achieved in a reverse micellar solution, while it was
celles of SDS in the ethanol solution led to the ag- obviously distinct from the previous ones. Initially,
gregation of the silver clusters and the anisotropic silver nanotubes were formed through the self-as-
growth of the silver nanowires. It is well known that sembly of silver nanoparticles by the interaction of
the micelles in different surfactant concentration the coating surfactants ,and then as-synthesized
display different shapes, such as spherical, lay-like nanotubes were further sintered in air at 500 o C to
and rod-like. However, just the rod-like soft template obtain the silver nanowires. This method mainly took
would guide the anisotropic growth of the silver advantages of the self-assembly of octanoic acid
nanowires. Besides, the reducing rate of the pre- into nanotubes and depended on these tubular tem-
cursor is key to the formation of nanowires and the plates to fabricate the silver nanowires [49]. In addi-
detailed mechanism of this method still needs us tion, the mixture of polyethylene and ethylene gly-
to further study it. When the Vitamin C was replaced col was also reported to provide the micro-emul-
by a stronger reducing agent: tri-sodium citrate, the sion, which guided the one-dimensional growth of
reaction speed should be under better control. The silver nanowires [50].
concentration of tri-sodium citrate became more Until now, even if various surfactants have been
determinative and sensitive to the morphology and exploited as the soft templates to synthesize the
sizes of the product [19]. Besides, the anionic sur- silver nanowires, but their mechanism is still largely
factant dodecyl benzene sulfonic acid sodium (DBS) unclear. The soft template method is mainly depen-
was also reported to be used as the soft template dent on the micropores of the rod-like micelles and
18 G. Yan, L. Wang, and L. Zhang

micro-emulsion to restrict the lateral growth of sil- step, silver nanowires are oxidized to generate the
ver nanowires and nanorods. However, it is usually gold atoms, which are deposited epitaxially on the
very difficult to prepare the micellar phase and of surface of the templates, and the internal silver at-
low reproducibility, so still needs us to devote more oms also diffuse into the newly formed gold shell to
efforts to improve these methods. form the seamless surface of Au-Ag alloys. The
second step is dealloying process, in which the sil-
3. PREPARATION OF GOLD ver atoms are selectively removed from the uniform
NANOTUBES FROM RESULTANT alloyed wall and the concomitant morphological re-
SILVER NANOWIRES construction leads to the formation of pinholes in
the walls of the gold nanoshell [18,55,56]. The sil-
Traditionally gold nanotubes are prepared by depos- ver nanostructures are utilized to be templates of
iting the newly generated gold atoms onto the sur- the fabrication of gold nanotubes basically because
face of the templates, such as goethite rods [51], of the good matching between the crystalline struc-
silica wires [52] and polymer latexes [53], and then tures of gold and silver.
the template cores need to be selectively removed. When HAuCl4 solution is added into the reac-
However, using the silver nanowires as the templates tion system, some interior cavities are concomi-
may have some intrinsic advantages in fabrication tantly developed in each silver nanowire. With the
of gold nanotubes, because it need not selectively reaction continuing, consecutive hollow inside may
etch the cores after deposition and quite uniform form finally in the nanowires and the outside shell is
nanostructures will be obtained after the galvanic comprised by Ag-Au alloy. Meanwhile, some gen-
replacement reaction due to the perfect crystallo- erated openings on the surface of nanotubes are
graphic match between silver and gold. Furthermore, favorable for the diffusion of AuCl4-, Ag+, Cl- and Au.
the mechanism in this field has been studied and The various mass diffusion of gold and silver atoms
explored for a relatively long period. It is the most proceeds on the outer surface of template to result
popular method for fabricating gold nanotubes in the in the formation of smooth Ag-Au alloyed layer. Af-
laboratory now. ter that, if HAuCl4 continues to be added into the
system, the silver atoms in the alloy layer would
3.1. Mechanism start to be consumed. According to the stoichio-
metric relationship in the reaction formation, the
Xia et al. [54] first proposed the galvanic replace-
expense of three silver atoms only generates one
ment method for the synthesis of gold nanoshell.
gold atom, which forms numerous lattice vacancies.
The gold shell was normally obtained by adding
To release these lattice vacancies, the nanowires
HAuCl4 to the dispersion of silver nanostructures at
will reconstruct its morphology via Ostwald ripen-
a quite mild temperature. Then silver nanostructures
ing. Finally, the nanostructures tend to coalesce
would be oxidized by HAuCl4 according to the fol-
and collapse into small fragments of pure gold
lowing reaction equation.
[18,54,55]. The typical morphological evolution with-
3 Ag(s)
AuCl4 (aq) Au(s) out the inducing agents is just as Fig. 7 shows.
(4) It was reported that the template-engaged re-
+ -
3 Ag (aq) 4 Cl (aq). placement reaction in the presence of CTAB or PVP
was quite different from the previous one on the mor-
The gold atoms generated in this system were
phological evolution. After HAuCl4 was added into
confined to the vicinity of the template surface and
the reactive system containing CTAB or PVP, some
then adsorbed onto it. After their nucleation and
small holes would immediately form on the side
growth into nanoparticles, they would form a thin
surfaces of silver nanowires. As the reaction pro-
shell around the templates. Meanwhile the tem-
ceeded, the small holes would transform into one
plates: silver nanostructures were oxidized into Ag+
uniform and regular channel along the axis in each
and then diffused into the bulk solution. Moreover
facet. Meanwhile, the gold deposition started to
the gold nanoshell would retain the morphological
cover the nanowires from the edges to the midsec-
feature of the silver templates. In other words, silver
tion [57]. CTAB not only served as a stable agent,
nanospheres templated the growth of spheric gold
but also acted as the inducing agent for the aniso-
nanoshell; silver nanowires induced the fabrication
tropic growth of gold nanotubes. These gold
of gold nanotubes and so on.
nanotubes protected by CTAB possessed perfect
Generally, the template-engaged replacement
structures, smooth surfaces, highly crystalline walls,
reaction includes two distinctive steps. In the first
and similar cross-sections to that of the silver tem-
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 19

plate Unfortunately, until now, some detailed mecha-

nism is still under investigation.
It was said that temperature played a quite im-
portant role in this system, because the diffusion
rates of silver and gold atoms had high impact on
the morphology of final product. For example, at
room temperature, the precipitate of AgCl would
hinder epitaxial deposition of the newly formed gold
atoms and the slow diffusion of Ag and gold would
also induce the product with rough surfaces [18].
Hence the replacement reaction was commonly
manipulated at 100 o C.
The templated-engaged replacement reaction
was not only suitable for the aqueous system, but
also fit for the organic medium. Xia et al. [56] had
studied the replacement reaction between silver
particles and HAuCl4 in chloroform. They found the
details of reaction were quite different from previous
study and the addition of oleylamine was quite criti-
cal for the formation of uniform nanoshell free of AgCl
contamination due to the complex between AgCl
and Oleyamine. Fig. 7. TEM images taken from silver nanowires (A)
before and (B-F) after they had reacted with differ-
3.2. Advantages and disadvantages of ent volumes of 1 mM HAuCl4 solution [18].
silver-nanowires template on
synthesis of gold nanotubes
It is obvious that synthesis of gold nanotubes from
the silver-nanowires template is of prominent and
attractive advantages. The tubular structure can be tion, this method only can proceed at a quite low
achieved directly and there is no need for the addi- concentration if we want to avoid the contamination
tional operations to remove the template cores. The from the precipitate, because AgCl has an extremely
as-synthesized gold nanotubes have a relatively high low solubility even at 100 !.
purity and almost no impurity is introduced into the Except for the silver nanowires, there are plenty
nanotubes from the templates. The produced of other nanostructures applied as the templates
nanotubes can completely retain the morphological for the synthesis of gold nanotubes. Spuch-Calvar
feature from the silver-nanowires templates and keep et al. [51] utilized the Goethite rods as the sacrifi-
a quite uniform structure. The galvanic replacement cial templates to obtain submicrometer gold
reaction is performed at a mild temperature and in nanotubes using the formaldehyde as reducing
the aqueous solution. Therefore fabrication of gold agent. The product had a length of a few hundreds
nanotubes from silver-nanowires templates is low nanometers, while only had an aspect ratio between
energy-consuming and environmentally friendly to 3 and 4. The thickness and surface roughness can
some extent. However, the morphology of the as- be adjusted by varying the concentration ratio be-
synthesized nanotubes is quite sensitive to the tween modified goethite rods and HAuCl4. Besides,
amount of added HAuCl4. Different molar ratio of the the SiOx and silica nanowires was also reported to
precursor to silver-nanowires template will result in be applied to fabricate the gold nanotubes [52,58],
completely different gold nanotubes. Hence this however their fabrications by these kinds of tem-
method is of relatively low reproducibility, but the plates are quite complicated because it needs to
introduction of some surfactants will improve this remove template cores after galvanic replacement
situation and fabricate the product with higher qual- reaction.
ity. For instance, in the presence of CTAB, the syn- Despite the nanowires, sometimes
thetic gold nanotubes would become quite uniform, nanoparticles would also be utilized as the sacrifi-
smooth and well-dispersive, while they tend to bundle cial templates. Schwartzberg et al. [59] had reported
together if replacing the CTAB by PVP [57]. In addi- that gold nanotubes were synthesized via magnetic
20 G. Yan, L. Wang, and L. Zhang

Fig. 8. Schematic illustration of the experimental procedure that generates Pt nanotube from silver
nanowires(modified), see [54] for more detail.

alignment of Cobalt Nanoparticles. When the exter- attracting more and more attentions from all over
nal magnetic field was strong enough, the cobalt the world. Except for gold, the silver-engaged tem-
nanoparticles would align into chains along the plate replacement reaction, in principle, is applicable
magnetic field vector. As long as appropriate quan- to many other metals, if only their standard reduc-
tity of sodium citrate was added into the precursor, tion potentials are higher than that of Ag+/Ag. There-
the consecutive gold nanotubes would be generated. fore the fabrication of Pt nanotubes from silver-
Due to the existence of Cobalt, the alignment of nanowires templates is feasible and of great signifi-
gold nanotubes can be easily controlled by mag- cance.
netic field. But the product was not so uniform and Generally speaking, the mechanism of this pro-
their surface was uneven. Besides the cobalt cess synthesizing Pt nanotubes from silver
nanoparticles was also difficult to be removed with- nanowires is largely similar with that of gold
out destruction to the nanotubes. nanotubes. Xia et al. [54] first mentioned this tem-
The templated-engaged method seems to be the plate method for Pt nanotubes and they proposed
only way for the fabrication of gold nanotubes. Com- that Pt(CH3COO)2 was reacted with silver template
pared with the other used templates, silver nanowires to induce the selective deposition of Pt atoms, and
are considered as the most promising templates the as-synthesized Pt nanotubes exhibited the simi-
for the mass product of uniform gold nanotubes due lar morphology with the gold nanotubes. However,
to avoidance of template-removal process and fac- after further study, they found that the surface of Pt
ile reaction operation. However, it still needs us to nanotubes appeared rougher and was commonly of
devote more time and energy to exploring and dis- discrete nanoparticles. Finally, this phenomenon
covering the underlying mechanism and optimizing was attributed to relatively higher melting point of
reaction conditions to perfect this synthesis route. Pt and the wall of Pt nanotubes could not be effec-
tively reconstructed through the Ostwald ripening
4. PREPARATION OF PLATINUM process at 100 o C in aqueous solution. Conse-
NANOTUBES FROM RESULTANT quently, to solve this problem, another suitable sol-
SILVER NANOWIRES vent with a higher boiling point should be selected
[17]. In addition, H2PtCl6 was also used as the pre-
4.1. Mechanism cursor of metallic Pt in this galvanic replacement
Comparing with gold nanotubes, the articles on Pt reaction [2] (Fig. 8). However, the wall of the tubes
nanotubes are relatively less reported. However, as was polycrystalline and the surface was quite rough
one kind of excellent metallic catalyst for many or- as well, but it inherited the morphological charac-
ganic reactions, the fabrication of Pt nanotubes is ters of the silver-nanowires template as well.
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 21

4.2. Advantages and disadvantages of crystallinity and uniform structure. The high purity
silver-nanowires template on of the product allows it wide-range application with
synthesis of platinum nanotubes less limitation. However, fabricating Pt nanotubes
by the silver-nanowires method still encounters
Except for silver nanowires, there were a variety of some problems, such as rough and porous surface,
other templates, which could be used to synthe- low-efficiency. There is still a lot of work needs to
size Pt nanotubes. Shaislamov et al. [60] utilized be done before the mass production is feasible and
porous alumina templates wetted into the precur- economical.
sor solutions containing polymeric source and ob-
tained Pt nanotubes. However, the synthetic proce-
dure was largely trivialized by the removal of alu-
mina template. Some tubular polymer was also re- Nanocomposite has been a hot field for a long time
ported to be applicable for the fabrication of Pt and its application in the coatings would bring dra-
nanotubes. Yu et al. [61] attempted using sequenced matic change in the performances, such as physi-
peptide-functionalized nanotubes as templates and cal and mechanical properties, anti-corrosion per-
controlled the morphology of Pt coating by adjust- formance and so on. Most researches in this field
ing the pH to switch Pt nucleation sites among the mainly focus on using inorganic nanomaterial for
amino acids. In addition, Kumara et al. also illus- the betterment of ordinary coatings. Some of them
trated the possibility that used flagella nanotubes have been already commercialized, such as SiO2,
as templates [62]. However all of these templates ZnO, and TiO2.
were quite difficult to be separated from the Pt In the past, silver nanomaterials were added into
nanotubes and most of the nanotubes were as- the adhesive just for the antibacterial property. How-
sembled by the small Pt nanocrystal. Therefore ever, recently silver was introduced into adhesive
these Pt nanotubes were synthesized without for the enhancement of its conductivity. As a kind of
smooth and consecutive surface and commonly noble metal, the amount of bulk silver added into
concomitant with the organic impurities. Recently, the adhesive was expected to be reduced so as to
the dual templates were utilized to fabricate the cut costs and improve adhesive strength.
mesoporous Pt nanotubes [63]. A reduced pressure In most researches, it commonly exploited resin
procedure was contained in this system with the as the polymer matrix, such as epoxy resin [64,65],
combination of hard templates and soft templates. acrylic resin [66], and so on. The silver conductive
The nanotubes were proved to be the assembly of filler might have different size, morphology and con-
Pt nanoparticles with a size ca.3 nm. Actually this tent as a result that the ECA correspondingly
method was quite low-efficiency and the operation showed different characteristics and properties [67].
were usually performed trivially. Recently another Traditional silver ECA usually was filled with micro-
novel and attractive method had been reported to sized particles and expected to be applied for the
fabricate silver nanotubes and the synthesis of the microelectrical packaging. Comparing with Sn/Pb
final nanowires was achieved through sintering the solder, traditional ECA indeed had some prominent
prefabricated silver nanotubes. Unlike the previous advantages. It can improve linear distinguishing ability
methods, these silver nanotubes were fabricated and lower processing temperature, while it also had
without additional templates, while they were ob- some limitations and deficiencies, such as poor joint
tained through the self-assembly of nanoparticles performance, unstable contact resistance and lower
in a reverse micellar solution. Although, this method conductivity. To perfect its performance, Ye et al.
was reported for the fabrication of silver nanotubes, [68] firstly introduced silver nanoparticles into the
but the possibility of applying it to the fabrication of filler and studied the conductivity change of the coat-
Pt nanotubes was stated by the author as well [49]. ings. They suggested that the resistance between
So far, silver nanowires have been the most ideal two particles was composed of constriction resis-
and prominent candidate to template the growth of tance (from direct contact) and the tunnelling resis-
Pt nanotubes among the above mentioned tem- tance (from nanogap), while the nanoparticle-con-
plates. It was proved that the nanotubes would in- taining adhesives were controlled by tunnelling ef-
herit the morphological characters of the silver- fect. Furthermore, Lee et al. [69] found that the ad-
nanowires template faithfully as a result that the dition of doped silver particles (doping the
morphology of the product was in a good control. nanoparticles into the microparticles) could effec-
Due to the good crystallographic match between tively reduce the resistivity of ECA, when the total
Ag and Pt, Pt nanotubes are usually of the good content of silver in the ECA was near a percolation
22 G. Yan, L. Wang, and L. Zhang

Fig. 9. Conductive scheme of ECA filled with Ag micro-particles, nanowires or nanoparticles (modified)
[according to Refs. 12 and 71].

threshold. They proposed a reasonable mechanism probability of contact and contact area much more
to illuminate this phenomenon. Near the percola- than the undoped cases [70]. Wu et al had proved
tion threshold, the silver microparticles still could that ECA filled with silver nanowires (mass fraction
not completely contact with each other and the ad- 56%) had intrinsical resistivity 6 times lower than
dition of silver nanoparticles could help to form the that filled with silver particles (mass fraction 75%).
continuous conductive network so as to lower the Moreover, it also showed higher shear strength (17.6
resistivity of ECA. Due to the small dimension, for a MPa on Al substrate) due to the reduced amount of
fixed amount of silver, the nano-sized silver contained the conductive filler [71]. They explained these phe-
more particles than the micro-sized did. The larger nomena just as shown in Fig. 9. Firstly the fibroid
number of particles would be beneficial for the inter- shape of nanowires made them have larger contact
connection between micro-sized ones. Certainly it area and fewer contact points compared with Ag
would increase the contact resistance, but the tun- particles or dendritic, when they were filled into the
nelling effect between the nanogap would reduce polymer matrix. Secondly, the contact points were
the bulk resistance of conductive adhesives. more stable and the conductive network was more
In most occasions, high conductance and good easily formed. Thirdly, due to the existence of silver
bonding strength of such ECA seem to always con- nanoparticles in the nanowires system, the tunnel-
flict with each other. Because conductance is con- ling effect of these particles would lead to the for-
tributed by silver filler and the bonding strength is mation of a more stable conductive network. As
mainly derived from resin matrix. So if we want to shown in Fig. 9, the total resistance of ECA filled
obtain ECA of both high conductance and good bond- with silver nanowires was Rc+Rb+Rt (Rc was con-
Z_Xde c
d tact resistance, Rb was intrinsic resistance and Rc
c aY ]XjR_UT_e RTeWc eZacg V975t dT_ was tunnelling resistance), and the total resistance
ductance rather than increase silver quantity. It was of ECA filled with silver particles was Rc+Rb. For
reported that the doped nanowires were favorable silver, its intrinsic resistance Rb was quite negli-
for perfecting linkage among particles and made the gible and through theoretical calculation, Rt was also
Recent research progress on preparation of silver nanowires by soft solution method, preparation... 23

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