Vous êtes sur la page 1sur 16

Routes to self-assembly of nanorods

Karthik Ramasamya) and Arunava Guptab)


Center for Materials for Information Technology and Department of Chemistry, University of Alabama,
Tuscaloosa, Alabama 35487

(Received 29 November 2012; accepted 24 January 2013)

Self-assembled nanostructures often exhibit unique properties that are distinct from those of bulk
materials. During the past decade, significant progress has been made in the assembly of nanorods and
understanding some of the self-directing assembly mechanisms, particularly related to gold nanorods.
Nonetheless, methods that can be scaled up to large areas for device-scale applications are yet to be
established. This review describes various routes that are being actively pursued to achieve assembly
of nanorods. Self-assembly methods that utilize external forces such as electric field or gravitational
forces are reviewed. Additionally, self-assembly schemes using chemical and biomolecule linkers are
presented. Other important routes, such as template assisted assembly, Langmuir-Blodgett, and
nanorod assembly methods carried out in solution phase are also discussed. The latter includes
recently reported approaches to produce superstructured particles through self-assembly. Solvent
evaporation and drying can also strongly contribute to the assembly of nanostructures. The final
section presents self-assembly routes that primarily exploit the drying kinetics of solvents.

I. INTRODUCTION assembled gold nanorods. It should be noted that controlled


One-dimensional (1D) nanostructures such as wires, assembly of 1D nanostructures is distinct from their 0D
rods and tubes often exhibit enhancement in electrical counterpart as shape anisotropy can result in multiple
and thermal transport properties as compared with zero- orientation configurations. Large area assembly of nano-
dimensional (0D) nanostructures.1,2 The 1D structures are rods requires appropriate control of the interparticle inter-
also promising for fabrication of electronic, optoelectronic actions that can be influenced by the solution chemistry or
and electrochemical devices. Carbon nanotubes are one of applied external field. A better understanding of nanorod
the well-studied 1D nanostructures exhibiting unique self-assembly mechanism has enabled the development of
mechanical and electrical properties.3,4 The usefulness of strategies that can transform individual nanorods into well-
inorganic 1D nanostructures for applications in solar cells, defined two-dimensional (2D) or three-dimensional (3D)
light emitting diodes and transistors has been investigated structures. Over the past decade, a number of assembly
for more than a decade.5–7 Unusual electronic properties in methods have been developed, e.g., with application of an
1D nanostructure arise primarily from spatial confinement applied electric field, drying kinetics, dipole-dipole in-
of electrons, phonons and electric field near the surface. A teraction, nanorod surface chemistry, hydrogen bonding,
variety of methods have been developed for the shape- and using selective binding ligands, etc. Recently, the self-
size-controlled synthesis of 1D nanostructures of various assembly and properties of various anisotropic nanostruc-
materials, including templated growth,8,9 vapor-liquid-solid tures have been reviewed.17–20 The primary objective of this
growth,10–12 solvothermal route,13,14 and hot-injection review is to provide the readers a concise illustrative report
synthesis.15,16 on various nanorod self-assembly methods that have thus far
For harnessing the unique properties of 1D nanostructure been successfully demonstrated.
for practical applications, they need to be assembled over
large areas. Assembled nanorods often provide enhanced II. DIFFERENT SELF-ASSEMBLY ROUTES
properties as compared with those that are randomly
oriented. For example, assembled semiconductor nanorods A. Electric field-assisted assembly
offer directed electron and hole transport leading to more Assembly of 1D inorganic material utilizing external
efficient charge separation. Likewise, orientation-dependent forces has been demonstrated in recent years. 1D wurtzite
surface plasmon resonance is observed in unidirectional structures such as cadmium selenide (CdSe), cadmium
sulfide (CdS) and zinc oxide (ZnO) generally possess
a permanent dipole moment along their axes. The
Address all correspondence to these authors.
a)
e-mail: kramasamy@mint.ua.edu permanent dipole moment of wurtzite CdSe nanorods
b)
e-mail: agupta@mint.ua.edu has been determined from transient electric birefringence
DOI: 10.1557/jmr.2013.26 measurements, and it has been postulated that dipole

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 Ó Materials Research Society 2013 1761
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

moment originates from noncentrosymmetric crystallo- Saeedi et al.24 reported the assembly of nanorods on
graphic lattice.21 The dipole moment of the material can be a prefabricated template. E-beam lithography was used to
manipulated for the assembly of 1D nanostructures into pattern a spin-coated poly(methyl methacrylate) (PMMA)
2D or 3D superstructures with application of an external resist. Deep reactive ion etching (DRIE) process was carried
electric field. Materials with low polarizability can also be out after depositing the metal films (Cr/Au). Y- or U-shaped
induced to assemble using an electric field when the receptors were fabricated to trap the nanorods. For assembly
energy input exceeds the random thermal energy (kT). of nanorods, the template was placed inside a centrifuge tube
Ryan et al.22 reported placing CdS nanorods of dimension and a specific volume of the nanorod solution dropped inside
30 nm (l) and 5 nm (d) suspended in toluene solution the centrifuge tube. The tube was then centrifuged at
between parallel electrodes, with the solution then allowed different speeds. The centrifugal force pushed the nanorods
to dry under an applied DC electric field of 1 V/µm. and trapped them inside the receptor sites on the template.
Packing of nanorods into a 2D structure on a substrate was Nearly 92% of receptor sites were occupied with nanorods,
achieved during the evaporation process. The induced out of which 38% were filled with single nanorods and
dipole moment of CdS nanorods, estimated to be ;220 D, remaining contained more than one nanorod. This assembly
was effectively utilized to vertically orient the nanorods method is advantageous as it is not being limited to the
along the applied electric field. Subsequent drying of the nature of the material. Mirkin’s group reported the assembly
solvent brought the nanorods in close proximity to form of multiple component rod-like building blocks consisting
a 2D array. Figures 1(a) and 1(b) show schematic represen- of gold nanorods and polymer.25–27 They used templates for
tations of the experimental set up used for the electric field- the synthesis of nanorods, which also played a significant
assisted assembly process. 2D assembled domains obtained role in the assembly process. Spheres, tubular and hemi-
with this process consisted of ;4  103 nanorods. With sphere-shaped mesoscopic superstructures were obtained by
higher concentration of nanorods, a 3D assembly hexagonal assembly. Gold nanorods were prepared by electrodeposit-
AB stacking was observed. A similar electric field-assisted ing gold into anodized alumina template and then pyrrole
assembly process was carried out on CdSe nanorods, in was polymerized electrochemically. Nanorods were released
which poly(methyl methacrylate) (PMMA) polymer was from the template after etching with sodium hydroxide
used to freeze the nanorod assembly for preventing the (NaOH). Self-organization of nanorods-polymer composite
destabilization of nanorods assembly when the electric field into various mesoscopic architecture including bundles,
is turned off.23 In a typical experiment, a droplet of tubes and sheets consisting of hundreds of thousands of
chloroform solution of CdSe nanorods with PMMA was rods was demonstrated. Figures 2(a)–2(d) show schematic
placed on a silicon oxide-coated silicon wafer. The droplet representations of nanorods assembly into superstructure.
was allowed to evaporate with an applied electric field of 107 The shape and size of the final architecture could be
V/m. The CdSe nanorods used for this assembly experiment controlled by adjusting the gold to polymer ratio. The
had a higher dipole moment value of ;1450 D. authors proposed that interaction between polymer ends of
the composite bring the nanorods closer to form secondary
B. Templated assembly superstructures.
Templated assembly is another approach by which
nanorods are assembled at predetermined locations to form C. Gravity driven assembly
secondary superstructures. Depending on the nature of the Spontaneous assembly of anisotropic nanostructure to
template, nanorod concentration and aspect ratio, different form columnar array with the aid of the gravitational
superstructures of assembled nanorods can be obtained. force has been reported. Smith et al.28 reported an

FIG. 1. Schematic of electrode assembly for nanorod alignment. (a) 3D drawing. Each electrode measures 35  15  5 mm and is separated at
a distance of 1.2 mm. The electrode assembly in a horizontal orientation is placed in a glass vial with 1 mL of toluene to create a saturated atmosphere.
(b) 2D close up of trapped meniscus. The substrate (carbon-coated electron microscopy grid or silicon nitride membrane window) is placed between
the electrodes, and 50 µL of nanorod toluene solution is deposited forming a meniscus between the upper and lower electrode. Reprinted with
permission from Ryan et al.,22 copyright 2006 American Chemical Society.

1762 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

FIG. 2. Superstructure shape control. (a) SEM image of the pores of a bare AAO membrane used as a template for nanorod generation. (b) The AAO
template is patterned with photoresist (darker elevated pattern). The areas covered by photoresist are not exposed to the plating/polymerization
solution and rods are electrochemically deposited exclusively in the uncovered areas (rods are the light areas at the bottom of the template). (c) After
the template is removed the rods assemble into a superstructure (in this case a hemisphere) whose shape is determined by the photoresist pattern in
conjunction with the template. The insets show typical two-part AuPpy rods, which comprise the curved superstructures. (d) A scheme showing each
step of the assembly process. Scale bars in panels a, b, and c are 2, 300, and 100 lm, respectively. Inset scale bars are 1 lm. Reprinted with permission
from Ciszek et al.,27 copyright 2010 American Chemical Society.

interesting finding that controlled sedimentation of nano- bromide (CTAB) binds to gold nanorods on their long side
tubes with large density differences at the ends of nano- rendering them positively charged and carboxylate ends of
tubes result in vertical assembly. For demonstration, adipic acid are negatively charged. Interaction between
partially gold-filled silica nanotubes were prepared by these two opposite charged molecules is triggered at high
electrodepositing 2 lm of Au and Ag into alumina pH leading to side-by-side assembly of the nanorods. For
membranes, followed by coating of 30-nm silica, and confirming the assembly mechanism, the process was
finally completed with selective etching of Ag. The carried out using other carboxylic acids. Assembly using
partially filled nanotubes were dispersed in water and hexanoic acid (same carbon chain length as adipic acid) and
a 100-lL aliquot was placed in a 0.64 cm2 glass coverslip dodecanedioic acid (twice the chain length of adipic acid)
to sediment on the surface. In this process, the nanotubes gave only isolated and disordered aggregates. Nonassembly
initially sedimented parallel to substrate surface, and in the case of hexanoic acid can be explained as it is
subsequently with high particle surface coverage, verti- a monocarboxylic acid and does not have the ability to
cally standing nanotubes were observed as dots in optical bridge the nanorods. In the case of dodecanedioic acid, it
microscope images. The authors established that density was suggested that the acid binds to the nanorods surface in
difference between ends of nanotube was crucial to obtain- a looped conformation, which makes it chemically equiv-
ing vertically standing arrays, otherwise only a smectic alent to hexanoic acid. The preferential attachment of
assembly was achieved. The maximum number of vertically CTAB molecule to the surface of gold nanorods plays
standing tubes (nearly 90%) was obtained after 12.5 min of a major role in the side-by-side assembly. Selective coating
sedimentation. The vertically standing nanotube sedimenta- of nanorods surface with photochemically active molecules
tion percentage differed depending primarily on the con- can also be utilized for the organization of nanorods, as
centration of nanotubes dispersion. demonstrated for gold nanorods.30 The side faces of the
gold nanorods with face-centered cubic structure are
terminated with (110) planes, whereas the tips display
D. Surfactant and chemically assisted assembly either the (111) or (100) planes. Exploiting the preferen-
The use of surfactants that bind to specific surfaces of tially binding of CTAB on the (110) planes of Au, Fava
the nanorods is an effective approach for self-assembly. et al.30 coated gold nanorods with CTAB on the side faces
For example, assembly of gold nanorods into 2D structures and poly(N-isopropylacrylamide) (PNIPAm) on the tips.
by manipulating the pH, which effects the electrostatic The nanorods were then photoilluminated at the longitudi-
interaction between the cationic surfactant bilayer around nal plasmon band wave length. The nonradiative energy
the nanorods and the negatively charged self-assembled released from light absorption was sufficient to heat the
monolayers, has been demonstrated using different di- PNIPAm polymer molecules above the lower critical
carboxylic acid molecules.29 Cetyl trimethyl ammonium solution temperature (LCST). This induced transformation

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1763
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

of the polymer from the coil to globular form, thereby superstructures as DMSA, but the extent of order was
triggering end-to-end nanorod assembly. The proposed not as good.
binding mechanism was confirmed by the red shift in the The end-to-end assembly of gold nanorods was further
longitudinal absorption band. The hydrogen bonding ability demonstrated using sodium citrate, which selectively
of carboxylic acid groups can also be utilized for the end-to- binds to the tips of nanorods. In this study, nanorods
end assembly of gold nanorods.31 This mechanism was with two different aspect ratios (3 and 16) were used for
proposed in the assembly process using mercaptocarboxylic assembly.35 Four different possible mechanisms were
acid- and CTAB-protected gold nanorods.32 As described proposed for the observed assembly of gold nanorods,
earlier, CTAB preferentially binds to the side faces of the including electric charge neutralization of CTAB coated
gold nanorods, making the tips available for the thiol group gold nanorods, interdigitation of carboxylic groups of
of mercaptocarboxylic acids to bind. Hydrogen bonding CTAB caused by low coverage of the molecules on the
between the unbound carboxylic acid groups enables the nanorod surface, electrostatic interaction between cationic
nanorods to assemble in an end-to-end fashion, which was CTAB head group and citrate anions, and intermolecular
confirmed in transmission electron microscope (TEM) hydrogen bonding of citrate carboxylate groups. The
images as isolated linear arrays of gold nanorods. The authors conceptualized that the end-to-end assembly in
hydrogen bond-assisted assembly was extended using the case of gold nanorods with aspect ratio of 3 occurred
4-mercaptophenol, cysteine and glutathione molecules through electric charge neutralization, and in nanorods with
and the role of H-bonding in the end-to-end assembly was aspect ratio of 16 through interdigitation of carboxylic
evidenced by measuring the extinction spectra at different groups of CTAB. The selective functionalization of gold
pH. The use of chemicals that induce assembly of nanorods nanorods using a coordination complex-containing ligand
by selectively binding to specific faces on the surface was bearing a thiol group can also induce end-to-end assembly.
explored in yet another study of gold nanorods. A series This was demonstrated recently using iron(II) coordinated
of dithiol molecules were used for linking of the nano- with a thiol containing ligand 49-(4-mercaptophenyl)-
rods, including 1,3-propanedithiol, 1,5-pentanedithiol, 2,29:69,299-terpyridine (tpySH).36 Zhao et al.37 reported an
1, 6-hexanedithiol, 1,8-octanedithiol and 1,9-nonanadithiol.33 interesting approach to assemble Au-tipped CdSe hetero-
For the assembly process, gold nanorods of 2.9 aspect ratio structure nanorods in which hydrogen bonding between
were suspended in a mixture of water and acetonitrile and carboxylic acid groups of 11-mercaptoundecanoic acid
microliter quantity of dithiols were added to the mixture. (MUA) attached to the gold tips was utilized to stabilize
The dithiol molecule-induced nanorod assembly was mon- the self-assembled structure. In the Au-CdSe heterostruc-
itored by absorption spectroscopy, which showed a decrease ture nanorods, the CdSe surface was covered with octade-
in the intensity of the longitudinal surface plasmon band at cylphosphinic acid (ODPA) and hexylphosphonic acid
700 nm and the formation of interplasmon coupling band in (HPA) and the Au tips were capped with didodecyldime-
the near infrared region. thylammonium bromide (DDAB) and dodecylamine
The addition of dimercaptosuccinic acid (DMSA) to (DDA). To achieve side-by-side assembly utilizing the
CTAB-coated gold nanorods solution was reported to anisotropic attraction force between the nanorods and
induce assembly of the nanorods to form 1D, 2D, and 3D solvents, ligands on the Au surface were exchanged with
superstructures.34 The concentration of DMSA played 11-mercaptoundecanoic acid (MUA) by adding a solution
a major role in the formation of the superstructures. At of MUA in dimethylformamide to the toluene solution of
the lowest concentration (0.5 mM) of DMSA, nanorods nanorods. The authors reported that the nanorods self-
were assembled side-by-side to form a tape-like 1D assembled for minimizing interaction between the nonpolar
structure. With increasing the DMSA concentration to ligands and the polar solvent. SEM and dark-field TEM
0.8 mM, a perpendicular sheet-like structure was obtained, images of the Au-CdSe nanorod assembly are shown in
and increasing the concentration even further resulted in Figs. 3(a)–3(d). In a subsequent publication, the authors
the formation of 2D sheets and 3D superstructure of parallel reported the assembly of single tip Au-CdSe nanorods using
sheets. The mechanism for the formation DMSA-assisted the same method.38 A schematic representation of the
superstructure was proposed as charge neutralization. When assembly process is given in Fig. 3(e). Another novel
DMSA was added to the CTAB bilayer-coated gold nano- method for assembly of binary nanostructures has recently
rod solution, the negatively charge carboxylate ions neu- been reported.39 The assembly was carried out by adding
tralize the CTAB bilayer by formation of a CTA1-DMSA toluene solution of triphenylphosphine (TPP) to a mixture
complex, thereby bringing the nanorods together to form of gold nanoparticles and CdSe/CdS nanorods. TEM
a superstructure. Intermolecular disulfide bond forma- images of the sample showed eight to ten close-packed
tion in DMSA helps to further stabilize the superstruc- nanoparticles aligned linearly between two nanorods, with
ture assembly. The involvement of disulfide bond in a distinct spacing of 2.0 nm between the nanoparticles and
the formation of nanorods assembly was tested using 1.9 nm between the nanoparticles and nanorods. It is
mercaptosuccinic acid, which yielded similar ordered believed that the presence of triphenylphosphine additive

1764 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

ferred onto a solid substrate. This method has been utilized


for the 2D monolayer assembly of nanorods.42 Addition-
ally, pressure-induced liquid crystalline phase transition
(isotropic-nematic-smectic) can be achieved. To demon-
strate these methods, BaCrO4 nanorods were prepared
by reacting barium bis(2-ethylhexyl) sulfosuccinate
[Ba(AOT)2] reverse micelle with Na2CrO4 containing
NaAOT. The nanorods suspension was spread drop wise
on the water surface of a Langmuir-Blodgett trough and
consequently the surface was compressed to increase the
surface pressure. When the surface pressure was raised up
to ;30 mN/m, nematic arrangement of nanorods was
observed which then transformed to smectic arrangement
at ;35 mN/m surface pressure. The liquid crystalline 1D
smectic phase was further transformed to 3D nematic on
increasing the surface pressure to ;38 mN/m.

F. Solution phase assembly of nanorods


A simple solution phase nanorod assembly method
utilizing the depleted attraction force was demonstrated
recently.43 Depletion force can be defined as an attractive
FIG. 3. (a) Dark-field TEM image of Au-tipped CdSe NRs in toluene, force between large spheres results from competition
taken 1 h after NR preparation. (b) Dark field TEM image (top view) of between large solute and small solvent particle entro-
the close-packed NR array, inset shows the magnified image and the pies.44 This type of attractive interaction force is compa-
scale bar represents 50 nm (c, d) Side view SEM images of the NR rable to other attractive forces, such as van der Waals and
arrays. TEM and SEM images in (b–d) were taken 1 day after the
addition of dimethylformamide solution of MUA. Reprinted with
hydrogen bonding.45 The depleted attraction force be-
permission from Zhao et al.,37 copyright 2009 American Chemical tween nanorods is sufficient to induce the oriented binding
Society. (e) Solution-based self-assembly of single-tip Au-CdSe NRs. of nanorods to form well-defined assembly. Assembly of
Reprinted with permission from Zhao et al.,38 copyright 2011 John trioctylphosphine oxide (TOPO) coated CdSe/CdS nano-
Wiley & Sons. rods was induced by addition of oleic acid (OA) and poly
(ethyleneglycol) methacrylate (PEG-MA) additives.43 As-
is crucial for the formation of binary assembly, which binds sembled nanorods were precipitated from the nanorod
to the both the gold nanoparticles and CdSe/CdS nanorods. dispersion after injecting additives (OA and PEG-MA)
Micrometer-range self-bundled arrays of CdS nanorods above the threshold concentration. Nanorod assembly was
were prepared by a solution-based method, in which observed as isolated 2D sheets in the size range of
trioctylphosphine (TOP) and tetradecylphosphonic acids 50–200 nm in cryo-TEM images. By adjusting the
(TDPA) were used as cosurfactants.40 The intermolecular concentration of rods and additives, interaction time and
force among the hydrocarbon chains of surfactant molecules stirring conditions, the lateral size of 2D sheets could be
was suggested as a reason for the assembly of nanorods, increased to 1–2 lm. It has been noted that surfactants that
sufficient to overcome the interfacial force between the are commonly used for the synthesis of nanocrystals, such
adsorbed head groups of surfactant and the surface of the as oleylamine, hexadecylamine, oleic, and stearic acids,
nanorods. p-p stacking interaction between cyclic hydro- can induce self-assembly in nanorods dispersion through
carbon surfactants of gold nanorods can also assemble them depleted attraction force.43 We recently demonstrated
in a well-organized side-by-side manner.41 To achieve such a simple solution-based approach for the vertical assembly
an assembly, perylene thiol (PDI-SH) monolayer protected of nanorods utilizing the dipole-dipole interaction between
gold nanorods were synthesized by mixing CTAB coated the nanorods and the solvent.46 To demonstrate the
gold nanorods with perylene thiol. assembly, wurtzite phase Cu2CdxZn1-xSnS4 nanorods
were synthesized by reacting a mixture of thiol molecules
E. Nanorod assembly by Langmuir-Blodgett with metal salts of copper, zinc/cadmium and tin at 150–
method 155 °C, followed by nucleation and growth at a higher
Langmuir-Blodgett (LB) method is perhaps the most temperature. The synthesis process yielded wurtzite phase
promising scheme for the preparation of monolayer thick nanorods with uniform shape and size. For the vertical
and highly ordered thin films. In the LB method, a molec- assembly, the samples were first dispersed in hexane by
ular layer film spread at the water/air interface is trans- sonication and ethanol was then added to the dispersion.

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1765
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

Assembly of the nanorods was accomplished by con- dipole-dipole interactions dominate, which cause the nano-
trolled centrifugation and air-drying. The assembly of the rods to assemble into a 3D structure. The dipole-dipole
nanorods was observed in domains with maximum size of interaction energy provided by the polar solvent is sufficient
around 600–700 nm. High-resolution field emission scan- to overcome the Brownian motion and the thermal energy
ning electron microscope (HR-FESEM) images of nanorod barrier. The advantage of this assembly process is that it
assembly in Fig. 4 indicate vertical assembly of nanorods. does not require an external electric field, functionalization
TEM images in inset to Figs. 4(a) and 4(b) clearly show of nanorods, or a substrate template. Moreover, the process
smectic phase ordering of nanorods with uniform distances is simple, reproducible and scalable to large quantities of the
and well-defined lattice fringes. The self-assembly process sample, and the assembly can be carried out on any
can be explained based on dipole-dipole interaction of the substrate. However, the size and shape uniformity of the
nanorods and solvents. The absence of a center of symmetry nanorods is vital for this assembly process.
in a hexagonal unit cell creates partial charge polarization in
the nanorods, which induces a permanent dipole moment G. Nanorods to superparticles through
along the c-axis. Indeed, we observed that nanorods in self-assembly
nonpolar solvents, such as hexane or toluene, are randomly Superparticles are well-defined nano/mesostructures
oriented as the dipole-dipole interactions and Columbic that form through ordered arrangement of the primary
repulsions are in competition with each other. When a polar nanocrystals.47 The superparticles exhibit collective prop-
solvent is introduced into the randomly oriented nanorods, erties of the building blocks due to coupling effect. Due to
their potential as a new class of building blocks for
nanofabrication, a considerable amount of work has been
focused on the synthesis of superparticles using various
methods. The synthesis of superparticles using various
nanocrystals have recently been reviewed in detail, in-
cluding theoretical considerations for the nucleation and
growth of superstructures.48 Superstructure formation using
colloidal nanorods was initially reported by Zhuang et al.49
In this work, CdSe/CdS nanorods in chloroform was mixed
with an aqueous solution of dodecyl trimethylammonium
bromide and the chloroform was removed by bubbling
argon. The resultant mixture was injected into a vessel
containing ethylene glycol to which dithiol (Tween-20-SH)
was added. The mixture was heated to 80 °C and maintained
at that temperature for 1 h. The isolated superparticles were
disk-shaped with ;56 nm height. The authors postulated
that the formation of superparticles resulted from combined
interparticle interaction between the CdSe/CdS nanorods
and repulsive solvophobic interaction between the super-
particles and ethylene glycol. Recently, the same group
reported a detailed investigation of the growth of super-
structures from the nanorods along with small angle x-ray
scattering studies.50 They observed double-domed cylindri-
cal structures when the number (N) of constituent nanorods
was less than ;80,000, and irregular multidomain or
double-domed cylinders when N was more than this
number. Figure 5 shows the synthesis scheme of super-
particles and TEM images of the double-domed cylinder and
irregular-multidomain particles. Further, when CdSe/CdS
nanorods were incubated with octylamine for 6 days, single-
domain elongated needle-like superparticles were obtained
instead of cylindrical superstructures.

FIG. 4. (a and b) Top view SEM images of vertical nanorod assembly H. Nanorods assembly using biomolecules
by solution method. Side and top view TEM images of nanorods
assembly [inset to (a and b)]. Reprinted with permission from The use of biomolecules to influence nanorod assem-
Ramasamy et al.,46 copyright 2012 Royal Society of Chemistry. bly is being actively explored to produce well-organized

1766 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

FIG. 5. (a) Scheme for the synthesis of superparticles from CdSe-CdS nanorods: (i) nanorod-micelle formation, (ii) superparticle formation.
Numbered images: (1) Proposed model for a CdSe-CdS nanorod functionalized with ODPA and octylamine; (2) proposed model for a nanorod micelle
prepared using DTAB; (3) proposed model for a double-domed cylinder; (4) proposed model for an irregular-multidomain particle. (b–p) TEM images
of superparticles made from nanorods of l 5 28.0 6 1.5 nm and d 5 6.7 6 0.3 nm. Reprinted with permission from Wang et al.,50 copyright 2012
American Association for the Advancement of Science.

assemblies of nanomaterials. Following the ability of allowed to hybridize by mixing, and a three strand system
gold nanospheres to self-assemble on immobilizing oligo- where two short noncomplementary thiolated oligonucleo-
nucleotides and hybridization to form duplexes, the pro- tides were immobilized on the nanoparticles and treated
cess has been extended to gold nanorods to investigate the with a nonthiolated third strand, which was complementary
assemblage of anisotropic nanomaterials.51 For this work, to both the immobilized strands. TEM images from both the
gold nanorods were prepared by converting gold anodic two and three strand hybridized systems showed bundles
material into nanoparticles in a coelectrolytic surfactant of nanorods aligned in parallel stacks. The 3D nanorod
system. The nanoparticles were subject to treatment with bundles were observed to have alternate and superimposed
two oligonucleotide systems—a two strand complementary stacking, contrary to the nonduplexed suspensions that
system each consisting of thiolated oligonucleotides immo- formed completely random aggregates. A 6-nm interparti-
bilized on to nanoparticle suspensions individually and then cle distance was observed for the assembled nanorods,

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1767
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

which is higher than the surfactant bilayer (;3 nm) and is UV-Vis spectroscopy and TEM. UV-Vis spectra showed
also comparable to the 24-base pair helix containing propyl bands at 520 and 720 nm corresponding to transverse
spacers (6.5–9 nm). The UV-Vis spectra of the three- plasmon resonance and longitudinal plasmon absorption
stranded system displayed characteristic peaks at 520 nm bands, respectively. The nanorods were 60 nm in length and
(transverse plasmon band) with red shift, 850 nm (longitu- 20 nm in diameter with CTAB bilayer preferentially bound
dinal band) with a blue shift and at 260 nm (nucleotides). to the (100) ends, making the (111) ends available for
The two strand system showed a similar spectrum with the disulfide groups of TA to bind. Highly selective molecular
peak intensity decreasing on hybridization but with no recognition of immune receptor-ligand system (interaction
observed wave length shift. Melting analysis of the two between antimouse IgG and mouse IgG) facilitated the end-
systems confirmed that the three-strand system had to-end assembly between the nanorods resulting in a chain-
hybridized irreversibly whereas the two-strand system like formation with distance between individual rods of
was duplexed reversibly. This variation was probably 10–15 nm arising from the steric effect of immunoglobulin.
due to various sizes of nucleotides in comparison to the However, on increasing the concentration to 10 lM of
surfactant bilayers. mouse IgG, nonspecific binding was observed and was
The high binding affinity of biotin and streptavidin has overcome to obtain the linear assembly by adding the
been widely exploited to achieve nanorod assembly.52 mouse IgG five times in equal quantities with 3-h intervals
Gold nanorods were synthesized by seed-mediated growth for incubation. Figures 6(a)–6(d) shows the TEM images of
in water and surfactant. High-resolution crystallography the linked nanorods.
studies revealed pentahedral twin nanorods with the (111) Oligonucleotide hybridization was also performed on
and (100) faces pointed toward the ends and the length of nanorods obtained with seed-mediated growth.56 After
the rods, respectively, which was suggested as a conse- treatment with surfactant CTAB, mercaptoalkyloligonu-
quence of the size of the surfactant head group. The cleotide in PBS buffer was added to the nanorods and
nanorods were bound to biotin disulfide (EZ-biotin-HPDP) allowed to react for 40 h at 25 °C. Target oligonucleotides
molecules. This was achieved by treating a mixed solution were added to the mercaptoalkyl probe-modified nanorods
of the nanorods with biotin disulfide, then stirring, sonicat- and incubated for 48 h at room temperature. TEM analysis
ing and allowing it to set overnight. Centrifugation was showed unexpectedly high proportion of end-to-end
carried out to remove excess unbound biotin disulfide and linked nanorods separated by 10- to 15-nm spacings,
nanoparticles other than the rods. The sample was added to which matched the target oligonucleotide size. The end-
streptavidin in saturating quantities and then added to the to-end linking of the nanorods was due to the preferential
biotin disulfide-coated nanorods and mixed followed by binding of the SH group to the (111) ends of the nanorods,
centrifugation to separate the linked and unlinked nanorods. whereas a natural preference of the nanorod assembly is
The resulting TEM analysis revealed end-to-end linked side-to-side. Even a mixture of nanosphere and nanorod
gold nanorods with interparticle spacings of 4–5 nm, which showed linear assembly on addition of the target oligonu-
correspond to the size of streptavidin molecules and the cleotide. UV-Vis spectroscopy exhibited a red shift in the
orientation angles match with the four biotin-binding sites absorption bands at 530 and 680 nm on addition of the target
of the protein. The reason for the observed amount of end- as a consequence of the rod-rod and rod-sphere assemblies,
to-end linked product was suggested to be due to either the which further hybridized to yield larger assemblies. The half
inability of biotin to replace the surfactant bilayer attached width of the absorbance bands was found to increase with
on the length of the rods and consequently binding to the increasing incubation time; also the varying size of the rod-
(111) face preferentially, or because of the steric hindrance rod and rod-sphere assemblies led to different spectral
posed on the streptavidin molecule causing it to bind only at maxima and hence broader bands. The nanoparticle sol-
the ends.53 utions exhibited different colors–nanospheres presented a
In another study, gold nanorods grown by seed medi- pink solution, nanorods a jade green solution and rod-sphere
ation were treated with surfactant (CTAB) and thioctic mixture exhibited a deep red solution. On addition of the
acid (TA) and allowed to react at room temperature for 4 h various components, different colors were obtained depend-
and then centrifuged to remove excess CTAB and TA.54 ing on target concentrations and the system was capable of
The carboxyl groups on TA bound to the gold nanorods detecting up to 1 pM of nucleotide.
were activated by adding sulfo-N-hydroxysuccinamide and Salant et al. treated semiconductor nanorods with Au
1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide in phos- to grow nanorods with gold tips on either ends, referred
phate buffer for 30 min. Antimouse IgG was added to the to as nanorod dumbells (NDBs) owing to their unique
bifunctional linker-modified gold nanorods for 30 min and shape.57 The self-assembly of these NDBs was attempted
centrifuged to remove the supernatant containing unbound with avidin-biotin-specific interaction. The NDBs were
antimouse IgG. The derivatized gold nanorods were then treated with EZ-link biotin HPDP and mixed overnight.
incubated with mouse IgG for 3 h. The self-assembled Addition of biotin in two different molar ratios (1:1 and
nanorods obtained after incubation were analyzed using 1:2) yielded type 1 and type 2 NDBs, respectively.

1768 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

FIG. 6. TEM images of (a) di-, (b) tri-, and (c) tetra-gold nanorods assembly. The antimouse IgG provides an anchoring site at the end surface of
nanorod and interacts with mouse IgG for assembly. (d) Gold nanorods were assembled into successive chains via stepwise increasing the
concentration of mouse IgG. Reprinted with permission from Chang et al.,54 copyright 2005 Royal Society of Chemistry. (e) Illustration of surface
modification of Au NR with DPPTE and 1D and 2D self-assembled configurations of the NR complex on a solid surface. Reprinted with permission
from Nakashima et al.,58 copyright 2008 American Chemical Society. TEM images (taken prior to separation) of (f) dimers of NDBs in different
conjugation angles, (g) trimers, and (h) flowers (50 nm scale bars). Reprinted with permission from Salant et al.,57 copyright 2006 American Chemical
Society.

On addition of avidin to type 1 NDBs in a 1:2 ratio dimers, revealed 20% trimers before avidin addition and 35% after
head to tail binding through the Au tips were obtained. addition. After separation, the top fraction was found to
However, this was not observed in unconjugated NDBs, have 20% trimers and the bottom fraction contained 30%
nonbiotinylated NDBs with avidin and CdSe rods without trimers. This experiment elucidates the broad distribution
gold tips. Trimers were formed on changing the concen- range in combined conjugates and the limitation of avidin-
tration ratio to 1:2 excess avidin. The avidin-terminated biotin to control NDB chain lengths. In addition to dimers,
type 1 NDBs were mixed with type 2 NDBs in a ratio flower-like assembly of NDBs were observed and suggested
2:1, which resulted in dimers trimers and individual to be formed due to several reasons, including tetramer-
NDBs. The results confirm assembly due to selective binding sites in avidin, consequence of more than one biotin-
conjugation. The differences in the methods of self- disulfide molecule binding to the NDB Au tips and small
assembly were elucidated by separating the dimer and diameter of the gold tips and rods. Although present, these
trimer conjugates in solution. The dimer experiment structures were relatively less in quantity as compared with
revealed a significant population of monomers and NDBs the dimers indicating that their formation was not favorable
assembled in head-to-tail manner from nonselective bind- in the presence of dimers. The formation of dimers, trimers
ing before separation. Addition of avidin resulted in an and flowerlike structures is shown in Figs. 6(f)–6(h).
increase in dimer-conjugated NDBs. After separation, the In another attempt toward biomolecule-driven self-
upper fraction was high in monomer content and the lower assembly of nanorods, gold nanorods prepared by seed-
fraction contained 55% dimers. The trimer experiment mediated growth and treated with CTAB were exposed to

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1769
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

polystyrene sulfonate (PSS) solution and centrifuged to linking of the gold nanorods. The interfacial forces on
remove the excess PSS and redispersed in phosphate evaporation result in the side-to-side ordering due to
buffer saline.55 The modified gold nanorods were then translational entropy, and spin coating was reasoned
mixed with goat anti-h-IgG solution. After removing the to reduce the collective density of the nanorods giving
excess unbound antibodies, bovine albumin serum was rise to the 1D configuration. SEM images of the 2D self-
added to the nanoparticles to block the unbound sites and assembly showed that the assembly was dependent on the
then mixed with the h-IgG. The UV-Vis spectra showed hydrophilic or hydrophobic nature of the silicon substrate
that the gold nanorods produced a peak at 711 nm, and on with a uniform interparticle distance of 5.0 nm. Recently,
addition of PSS there was a red shift to 722 nm due to a simple approach for end-to-end assembly of gold nano-
change in the dielectric function. On addition of the goat rods was reported based on the ability of thiamine-rich
anti-h-IgG, further red shift of the longitudinal band to DNA to specifically and strongly bind to mercury ions
737 nm was observed owing to the high refractive index of (Hg21) leading to the configuration T-Hg21-T.59 The
the protein in comparison to PSS. The transverse band of longitudinal band of the absorption spectrum at 748 nm
the spectra did not show any wave length shift indicating was shifted 759 nm on the addition of Hg21 ion, indicating
that the longitudinal band responded more to target bio- the formation of T-Hg21-T complex. The addition of
molecule binding. After addition of h-IgG, the peak Cu21, Ni21, Zn21, and Cd21 ions did not affect the
intensity of the longitudinal band reduced considerably longitudinal band position, confirming the specific bind-
and red-shifted to 765 nm. This was attributed to the side- ing of Hg21 ions with the thiamine base pairs. SEM
to-side assembly driven by antibody-antigen binding. The images also clearly indicated end-to-end linking of the
result also explained the influence of GNR aggregation nanorods in the presence of mercury ions, which was not
and refractive index variation on the position, intensity and evident in the DNA-functionalized gold nanorods.
shape of the LSPR band. The protein detection limit in this Reversible end-to-end gold nanorod assembly was also
method was 60 ng m/L. achieved using disulfide polypeptide biomolecules.60
As yet another approach to nanorod assembly, gold Gold nanorods prepared by solution-based approaches
nanorods were arranged by incorporating surface an- were treated with poly vinyl pyrrolidone (PVP) for 24 h
chored lipids.58 The nanorods were prepared by chemical with gentle vortex mixing and were then centrifuged to
reduction of HAuCl4 followed by photoirradiation. remove excess unbound molecules. Disulfide-modified
1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) c-benzyl-L-glutamate was converted to disulfide-modified
was dispersed in water with sonication and added to the poly(L-glutamic acid) (SSPLGA) by debenzylation. The
gold nanorods and the products were centrifuged to remove PVP-modified gold nanorods were diluted in ethanol and
excess CTAB and DPPTE. A chloroform solution of DPPTE placed in a scintillation vial and under vortex mixing
was then added to the nanorod solution and stirred vigorously added with the SSPLGA and allowed to react undisturbed
for 1 h. The color of the nanorods was transferred to the for 24 h for the self-assembly to occur. Irreversible
organic phase from the formation of nanorod-DTTPE com- linking was achieved by adding 1,6-hexanedithiol to
plex, which was extracted and redispersed in chloroform. the PVP-stabilized nanorods in ethanol. UV-spectra of
1D assembly of the nanorod-DTTPE complex was carried the PVP-modified nanorods did not show any wave
out by spin coating on to a silicon substrate and drying. 2D length shift of the longitudinal bands. However, the gold
assembly was achieved by placing the nanorod-DTTPE nanorods treated with SSPLGA and 1,6-hexanedithiol
complex on to a silicon substrate and evaporating the solvent showed similar wave length shifts due to aggregation of
followed by simultaneous addition of chloroform to the nanorods in the end-to-end fashion in both cases. The
sample and annealing at 60 °C, and repeating the drying difference between the two methods was attributed to the
process three times. Schematic representations of the 1D tendency of the SSPLGA to undergo conformational
and 2D assembly are shown in Fig. 6(e). The initial zeta changes with pH variation. At high pH, the polypeptide
potential value of the nanorod-lipid complex in water was was deprotonated and hence was in a random coil
measured to be 24.0 mV and it decreased with addition of form, while at low pH it formed a helical structure
DPPTE, suggesting effective replacement of CTAB by possessing dipole-dipole and hydrophobic interactions
DTTPE. The UV spectra indicated longitudinal and trans- and hence reversible self-assembly was facilitated. Very
verse bands at 702 and 521 nm of which the former recently, high aspect ratio gold nanorods were prepared
underwent a red shift to 726 nm as a result of nanorod by seed-mediated growth and used to achieve end-to-end
aggregate formation induced by intermolecular interac- assembly by two methods—surfactant control and
tions of the lipids attached to the surface. Increase in the oligopeptide support.61 The study demonstrated that
DPPTE concentration led to a blue shift in the longitudinal cysteine-terminated oligopeptides of different lengths
band indicating increased side-to-side interaction of the and additional functional groups allowed to react with
nanorod complex or due to lipid bilayer formation. SEM surfactant-modified gold nanorods enable the establish-
images of the ID self-assembly confirmed side-to-side ment of linear end-to-end assembly.

1770 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

I. Nanorods assembly by solvent evaporation


Solvent evaporation and drying can also strongly
contribute to the assembly of nanoparticles. Nikoobakht
et al.62 prepared gold nanorods by electrochemical method
and treated them with cationic surfactant hexadecyltrime-
thylammonium bromide (HTAB) and CTAB as cosurfac-
tant and subjected to electrolysis. After extensive dilation
and centrifugation, the samples were free from unbound
surfactants and diluted with NaCl in a 1:1 ratio and
deposited on TEM grids using two methods. In the first
method, the nanorod solution was placed on the grid and
allowed to dry (1 h), and in the second method the TEM
grid was immersed halfway in the nanorod solution and
then allowed to dry. The latter method of deposition was
favorable in terms of self-assembly and reproducibility.
TEM images showed that a 0.001 M concentration
solution produced the most ordered structures. Various FIG. 7. Images of liquid crystalline phase in concentrated solution of
regions could be differentiated, such as monolayers with CdSe nanocrystals under a polarizing optical microscope. Isotropic
random orientations, 2D long nanorod chains, and assem- phase appears dark in these images. All the bright areas in the image
blies with varying thicknesses. The orientations of the correspond to the liquid crystalline phase, with dark lines corresponding
to disclinations or the area where the orientation of the nanorods are
nanorod assemblies were shown to be along the (100) and parallel to either of the polarizers. (a) Droplets of liquid crystalline phase
(110) planes. The self-assembly could be attributed to mixed with isotropic phase. (b) Interface between a big liquid crystalline
lateral immersion or capillary forces which in turn are droplet (right) and isotropic phase (left). (c and d) Disclinations of
related to the interparticle distance, particle radius, surface strength of 1/2 (c) and 1 (d), respectively. The arrows point to the
tension and meniscus deformation of the particles. The disclinations. Reprinted with permission from Li et al.,63 copyright 2002
American Chemical Society.
study clarified the factors that influence the assembly
process, such as the rate of water evaporation, the ionic
strength, the surfactant concentration, and the particle size nanorods to deposit as the solvent evaporated.64 TEM
and shape distributions. images showed structures with complete orientation along
In another study, CdSe nanorods were prepared by with some random multidomain structures, with the CdSe
pyrolysis of organometallic precursors of Cd and Se in nanorods connected in a head-to-tail manner as linear
hot surfactant mixture.63 Varying surfactant concentration arrays. Additionally, they contained vortex structures,
led to nanorods with aspect ratios ranging from 1–15, with which were proposed to arise from nematic phases, and
widths of 3–7 nm and lengths of 3–70 nm. The CdSe also monolayer structures with periodicity in both directions
nanorods were modified with amphiphilic molecules with originating from the smectic-A phase. The ability to control
the polar group bound to the nanocrystal surface and the liquid crystalline phase of the nanorods enabled control
protrusion of the alkyl chain, which enhanced the solubil- over their orientation. In another experiment, ZnS nanorod
ity in organic solvents. The liquid crystalline phases were solution was dispersed in a 1:1 mixture of toluene and
analyzed using birefringence studies. At low nanorod ethanol and deposited on a carbon-coated copper grid for
concentrations, complete extinction was observed and the solvent evaporation. HRTEM analysis showed 1D arrange-
isotropic solution revealed no pattern. As the concentration ment of the ZnS nanorods.65 The solvent evaporation pro-
increased, birefringent red droplets were observed due to cess reduced the free volume between the rods and causes
the band gap of CdSe nanocrystals and the intensity of the them to align side-by-side. The alignment was favored by
transmitted light indicated orientation of the nanorods. capillary forces and van der Waals attraction. Three factors
Analysis of the liquid crystalline and isotropic phases, and primarily affected the aggregation–concentration of nano-
studying droplets of various sizes, showed how the anisot- rods, nature of capping molecules and evaporation rate of the
ropy and other optical properties of the liquid crystalline solvent. The 1D assembly was converted into a 2D array by
phase of CdSe make them attractive for electrooptical dewetting in toluene-ethanol mixture.
devices. The liquid crystalline phases of CdSe studied with Talapin et al.66 reported preparing CdSe and CdS
optical microscopy are illustrated in Fig. 7. nanorods with narrow size distribution and aspect ratio
In another study, CdSe nanorod assembly was obtained by use of n-octylphosphonic acid. Copper grids pretreated
by slow solvent evaporation method wherein a mica with carbon were placed inside vials with the colloidal
sheet coated with carbon thin film was immersed vertically solution. Solvent evaporation was carried out under
into CdSe nanorod solution in cyclohexane, allowing the ambient and reduced pressure conditions. Addition of

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1771
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

hexadecylamine resulted in an increased quantity of the and suspended in chloroform, and allowed to dry at room
nanorods aligned perpendicular to the TEM grid. The temperature.70 SEM images at low nanorod concentrations
CdSe nanorods were observed to be assembled as tracks indicated spontaneous formation of perpendicular nanorod
and superstructures with smectic-A ordering. Orientation assembly in a superlattice packing with hexagonal geom-
of the CdSe nanorods for favorable antiparallel pairing of etry. The vertical orientation of the nanorods was lost and
the dipole moments of individual rods was suggested. parallel aggregation in side-by-side arrangement on the
High-resolution SEM analysis showed CdSe nanorods substrate was observed with decreasing concentration. At
assembled as flat sheets with evidence of internal packing high concentrations, parallel stripes were observed in SEM
inside the sheets. The self-assembled rods also showed images with the distance between the stripes ranging
specific birefringence, wherein spherical assemblies with between 100–200 lm. Pietrobon et al.71 demonstrated
maltese crosses were observed confirming the high order self-assembly of silver nanorods, synthesized from thermal
of nanorod assembly. Ghezelbash et al.67 prepared CdSe regrowth of decaheadral silver nanoparticles with citrate
nanorods by high temperature “multiple injection” reducing agent, into 3D arrays in smectic phases. This self-
arrested precipitation in the presence of tetradecylphos- assembly has been observed by the notable optical proper-
phonic acid and trioctylphosphine and its oxide. When the ties with sharp variable plasmon resonances.
nanorods were subjected to drop casting from anhydrous Self-assembly of CdSe nanorods into laterally oriented
chloroform with comparatively low surface coverage, arrays has also been reported.72 Various concentrations of
network of “stripes” were observed with parallel align- CdSe nanorods in toluene were deposited onto SiO2 sub-
ment to the lattice direction. Increase in the concentration strates and left for solvent evaporation at ambient temper-
of nanorod solution led to changes in the orientation and ature. Pinning and depinning were observed with the
alignment, similar to a smectic phase. The ability of the retraction of contact line as solvent evaporation occurred.
nanorods at high concentrations to form phase boundary After complete solvent evaporation, fringes consisting of
regions of high and low nanocrysal concentration leading dense nanorods were observed from SEM analysis. Ribbon-
to phase separation during drying was a factor affecting like assembly with side-by-side arrangement was seen.
the observed assembly pattern, along with dipole-dipole Using a higher concentration of nanorods (1 lM) for
interactions and van der Waals forces. In another exper- deposition yielded self-assembly with very high order.
iment, CdS nanorods synthesized by pyrolysis route and Nanorods aligned in smectic structures with the long axis
redispersed in toluene were trapped between a block of parallel to circular fringes were displayed in high magnifi-
highly ordered pyrolytic graphite and gold-coated silicon cation images along with parallel stripes on the fringes of
wafer, protected from contamination and allowed to dry varying density.
for several hours.68 SEM analysis showed perpendicular Semiconductor nanorods have also been directed to
orientation of nanorods as monolayers that were essentially assemble as 1D and 2D supercrystals by modifying the
defect-free. However, cracks from supercrystal formation surface charge. Singh et al.73 prepared CdSe nanorods
during toluene evaporation were observed at the outer edge capped with phosphonate/TOPO to produce hexagonal
of the crystal that showed vertical nanorod alignment. This perpendicular 2D array assemblies with 7  10 7 mol/L
correlated with the tendency of anisotropic assemblies in concentration. Elongation of the nanorods was observed
the absence of electric field to show parallel to perpendic- with increasing pyridine concentration, and when com-
ular orientation from the edges to the center, and hence the pletely exchanged by pyridine resulted in ring formation
mechanism of assembly was driven by supercrystal growth. as observed through SEM analysis. This was attributed to
Wang et al.69 synthesized WO3 nanorods by a hydro- pinning resulting from the receding solvent causing de-
thermal process and dispersed them in deionized water. position of material. The occurrence of discrete 1D and 2D
The suspension was placed on conductive ITO-coated array assemblies based on single surfactant or two surfac-
glass and allowed to dry at room temperature for 48 h. tant systems due to exchange between the pyridine and
TEM images showed uniform transparent nanorods of phosphonate/TOPO. The reduction in center-to-center
;100 nm diameter and 2 µm length. HRTEM images of distance in 1D arrays as compared with 2D arrays was
single nanorod showed clear lattice fringes confirming suggested to be a consequence of reduction in the ligand
their crystalline nature. High magnification FESEM spacing between the rods due to replacement of phospho-
images also showed compact assembly with a high degree nate/TOPO with shorter length pyridine.
of orientation. The aggregation-deposition mechanism Yi et al.74 reported preparing Cu1.94S-ZnS nanorod
observed for the WO3 nanorods assembly at room tem- heterostructures by multistep injection of Zn(acac)2-
perature is governed by the capillary forces and van der dodecanethiol into a hot solution of Cu(acac)2-dodecanethiol,
Waals attraction along with large surface tension of water. generating Cu1.94S nanoparticles. The morphology of the
In a related experiment, n-octadecyltrimethoxysilane pat- final Cu1.94S-ZnS was tuned by changing molar ratios
terned self-assembled monolayers on silicon substrates of Zn(acac)2:Cu(acac)2 and injection times of Zn(acac)2-
were immersed in hydrophobic gold nanorods, synthesized dodecanethiol and reaction times. Zipper-like self-assembled

1772 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

structures were obtained by dripping tiny drops of the nanorods between nanowires at various concentrations
nanorods in toluene on to a carbon-coated copper grid and showcasing the ability of nanowires treated with OA to
allowing the solvent to evaporate. TEM images showed direct assembly of nanorods in arrays and tune their optical
zipper-like Cu1.94S-ZnS nanorods self-assembled to form response by altering the distance between nanoparticles.
arrays, attributed to electric dipole-dipole interactions. Symmetric circular and semicircular superlattice assembly
Binary self-assembly of gold nanorods was achieved of multilayer of vertical gold nanorods has also been
by gold nanowire-driven oriented assembly.75 The Au reported.76 Gold nanorods prepared by seed-mediated
nanorods were transferred to organic phase by treating method and treated with CTAB were modified to hy-
with cationic surfactant and DTT and dissolved in THF droxyl-terminated hexa(ethylene glycol) undecanethiol
was then mixed with a hexane solution of gold nanowires (EG6OH) gold nanorods and dropped onto a silicon wafer
and deposited onto a substrate and dried to remove and dried at 25 °C. SEM images showed ordered circular and
the solvent. TEM images showed binary assembly of semicircular superlattices driven by the altering repulsive

FIG. 8. TEM images of CdS nanorods with concentration (a) 8  10 7 mol/L, (b) 1.4  10 6 mol/L, (c) 2.1  10 6 mol/L, and (d) 3.2  10 6 mol/L.
The optimum concentration was found to be 2.1  10 6 mol/L where closed-packed 2D superlattice of CdS nanorods with inset HRTEM image in
(c) shows the monodispersity of nanorods. (e–f) HRSEM images showing monolayer and multilayer, vertically oriented CdS nanrods. (g) Schematic
representation shows the progression of the nanorod assembly in different stages of droplet drying for different concentrations, the nucleation of the
assemblies in the droplet for optimum concentration and further growth process of nanorod assembly is shown in gIII. Reprinted with permission from
Singh et al.,79 copyright 2012 Royal Society of Chemistry.

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1773
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

interaction among the gold nanorods. This was achieved by nanorod-ligand interaction, chemical and biochemical
replacement of surfactant CTAB with (EG6OH). Solvent- strategies and physical forces. While the field is still in
induced nanorod assembly was achieved by treating the its infancy, significant progress has been made in the
nanorods with chloroform and adding isopropanol and assembly of nanorods–particularly gold nanorods–and
allowed to react in nitrogen atmosphere. The nanorod understanding some of the self-directing assembly mech-
assembly was analyzed with TEM and STEM, which anisms. The work thus far has resulted in the development
indicated that the semiconductor nanorods were assembled of a number of well-established protocols with the intent
into flat sheets of the order of a few micrometer through of creating novel architectures utilizing nanorods as
solvophobic effect.77 primary building blocks. Nevertheless, there are only
Ng et al.78 reported treating CTAB-modified gold limited reports on the large-scale assembly of nanorods,
nanorods with a polystyrene-thiol-THF solution with which is essential for practical applications. For expanding
vigorous agitation to obtain PS-modified gold nanorods the development of assembly over large areas, the intrinsic
and then resuspended in chloroform. Horizontal sheets interaction properties of nanorods need to be investigated
were fabricated by adding the chloroform solution of gold and exploited. Further in-depth studies of the available
nanorods into a beaker containing water and covered to surface chemistry are necessary to explore routes for more
prevent rapid evaporation. The solidified monolayers efficient self-assembly. Ligands with specific binding sites
present in the water subphase were transferred to TEM have to be developed that can selectively link nanorods in
lacey grids by a horizontal liftoff technique. Vertical a controlled manner. Better understanding of the drying
sheets were achieved by a similar procedure with anneal- kinetics and solvent evaporation phenomena can also open
ing at 60 °C in a water bath. The method resulted in up new avenues for the development of more controlled
H-sheets and V-sheets of plasmonic ordered superlattices. assembly. Although the assembly of nanorods has seen
In more recent studies, semiconductor nanorods such as remarkable progress, there is still much to be discovered
CdSe were assembled as ordered 3D structures, 2D closed and developed, and with many challenges to overcome.
packing perpendicular arrays, or 1D rail tracks.79 The
ordering was dependent on a number of factors, such as net
charge, dipole moments, nanorod concentration, surface ACKNOWLEDGMENT
charge, and nature of the solvent. The study revealed that This work was supported by the National Science
optimization of these factors facilitated assembly with Foundation under Grant No. CHE-1012850.
high reproducibility. Figures 8(a)–8(f) show TEM and
SEM images of CdSe nanorod assembly at various
concentrations. Figure 8(g) shows schematic representa- REFERENCES
tions of the drying-mediated nanorod assembly at different
1. Y. Xia and P. Yang: Chemistry and physics of nanowires. Adv.
concentration. CdSe nanorods with smectic superstruc- Mater. 15, 351 (2003).
tures over millimeter scale were produced by use of 2. Y. Xia, P. Yang, Y. Sun, Y. Wu, B. Mayers, B. Gates, Y. Yin, F. Kim,
capillary flow in drying the droplet of solution. TEM and H. Yan: One-dimensional nanostructures: Synthesis, character-
analysis showed the semiconductor nanorods assembled ization and applications. Adv. Mater. 15, 353 (2003).
with lamellar-like superstructures and nanorods were 3. R.H. Baughman, A.A. Zakhidov, and W.A. de Heer: Carbon
nanotubes–the route towards applications. Science 292, 787 (2002).
aligned side-to-side forming numerous lm-long tracks 4. Z. Yao, C.L. Kane, and C. Dekker: High-field electrical transport in
giving rise to the smectic superstructure.80 Zanella et al.81 single-wall carbon nanotubes. Phys. Rev. Lett. 84, 2941 (2000).
achieved CdSe nanorod self-assembly over device-scale 5. B. Sun and H. Sirringhaus: Solution-processed zinc oxide field-
areas as multilayer vertical nanorod arrangements. CdSe effect transistors based on self-assembly of colloidal nanorods.
nanorods were precipitated in methanol and redispersed in Nano Lett. 5, 2408 (2005).
6. J. Hu, L-S. Li, W. Yang, L. Manna, L-W. Wang, and A.P. Alivisatos:
xylene or orthodichlorobenzene. The substrates were Linearly polarized emission from colloidal semiconductor quantum
placed on a glass slide inside a petri dish with xylene or rods. Science 292, 2060 (2001).
orthodichlorobenzene and the sample solution was placed 7. I. Gonzalez-Valls and M. Lira-Cantu: Vertically-aligned nano-
as a drop on the substrate and allowed to dry. SEM images structures of ZnO for excitonic solar cells: A review. Energy
showed multilayer close packing of the nanorods and Environ. Sci. 2, 19 (2009).
8. K. Matsui, T. Kyotanni, and A. Tomita: Hydrothermal synthesis of
TEM images confirmed the increasing density of multi- single-crystal Ni(OH)2 nanorods in a carbon-coated anodic alumina
layer assembly with increase in concentration. film. Adv. Mater. 14, 1216 (2002).
9. L. Shi, C. Pei, Y. Xu, and Q. Li: Template-directed synthesis of
ordered single-crystalline nanowires arrays of Cu2ZnSnS4 and
III. CONCLUSIONS Cu2ZnSnSe4. J. Am. Chem. Soc. 133, 10328 (2011).
10. A.J. Wooten, D.J. Werder, D.J. Williams, J.L. Casson, and
In this review we have highlighted various nanorods J.A. Hollingsworth: Solution-liquid-solid growth of ternary
assembly methods that have been demonstrated in recent Cu-In-Se semiconductor nanowires from multiple and single-source
years by manipulating the nanorods surface chemistry, precursors. J. Am. Chem. Soc. 131, 16177 (2009).

1774 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

11. H. Peng, C. Xie, D.T. Schoen, K. Mcllwrath, X.F. Zhang, and 34. T.S. Sreeprasad, A.K. Samal, and T. Pradeep: One-, two-, and three-
Y. Cui: Ordered vacancy compounds and nanotube formation in dimensional superstructures of gold nanorods induced by dimer-
CuInSe2-CdS core-shell nanowires. Nano Lett. 7, 3734 (2007). captosuccinic acid. Langmuir 24, 4589 (2008).
12. C. Steinhagen, V.A. Akhavan, B.W. Goodfellow, M.G. Panthani, 35. G. Kawamura, Y. Yang, and M. Nogami: End-to-end assembly
J.T. Harris, V.C. Holmberg, and B.A. Korgel: Solution-liquid-solid of CTAB-stabilized gold nanorods by citrate anions. J. Phys.
synthesis of CuInSe2 nanowires and their implementation in Chem. C 112, 10632 (2008).
photovoltaic devices. ACS Appl. Mater. Interfaces 3, 1781 (2011). 36. P.R. Selvakannan, E. Dumas, F. Dumur, C. Pechoux, P. Beaunier,
13. X. Wang and Y. Li: Selected-control hydrothermal synthesis of A. Etcheberry, F. Secheresse, H. Remita, and C.R. Mayer: Co-
a- and b-MnO2 single crystal nanowires. J. Am. Chem. Soc. ordination chemistry approach for the end-to-end assembly of gold
124, 2880 (2002). nanorods. J. Colloid Interface Sci. 349, 93 (2010).
14. L. Whittaker, C. Jaye, Z. Fu, D.A. Fischer, and S. Banerjee: 37. N. Zhao, K. Liu, J. Greener, Z. Nie, and E. Kumacheva: Close-
Depressed phase transition in solution-grown VO2 nanostructures. packed superlattices of side-by-side assembled Au-CdSe nanorods.
J. Am. Chem. Soc. 131, 8884 (2009). Nano Lett. 9, 3077 (2009).
15. S.G. Kwon and T. Hyeon: Colloidal chemical synthesis and 38. N. Zhao, J. Vickery, G. Guerin, J.I. Park, M.A. Winnik, and
formation kinetics of uniformly sized nanocrystals of metals, E. Kumacheva: Self-assembly of single-tip metal-semiconductor
oxides, and chalcogenides. Acc. Chem. Res. 41, 1696 (2008). nanorods in selective solvents. Angew. Chem. Int. Ed. 50, 4606 (2011).
16. L. Manna, E.C. Scher, and A.P. Alivisatos: Synthesis of soluble and 39. Y. Nagaoka, T. Wang, J. Lynch, D. LaMontagne, and Y.C. Cao:
processable rod-, arrow-, teardrop-, and tetrapod-shaped CdSe Binary assembly of colloidal semiconductor nanorods with spher-
nanocrystals. J. Am. Chem. Soc. 122, 12700 (2000). ical metal nanoparticles. Small 8, 843 (2012).
17. D. Baranov, L. Manna, and A.G. Kanaras: Chemically induced self- 40. C-C. Kang, C-W. Lai, H-C. Peng, J-J. Shyue, and P-T. Chou: 2D
assembly of spherical and anisotropic inorganic nanocrystals. self-bundled CdS nanorods with micrometer dimension in the
J. Mater. Chem. 21, 16694 (2011). absence of an external directing process. ACS Nano 2, 750 (2008).
18. P.R. Sajanlal, T.S. Sreeprasad, A.K. Samal, and T. Pradeep: 41. C. Xue, O. Birel, M. Gao, S. Zhang, L. Dai, A. Urbas, and Q. Li:
Anisotropic nanomaterials: Structure, growth, assembly, and func- Perylene monolayer protected gold nanorods: Unique optical,
tions. Nano Rev. 2, 5883 (2011). electronic properties and self-assemblies. J. Phys. Chem. C 116,
19. M. Grzelczak, J. Vermant, E.M. Furst, and L.M. Liz-Marzan: 10396 (2012).
Directed self-assembly of nanoparticles. ACS Nano 4, 3591 (2010). 42. F. Kim, S. Kwan, J. Akana, and P. Yang: Langmuir-Blodgett
20. K. Liu, N. Zhao, and E. Kumacheva: Self-assembly of inorganic nanorod assembly. J. Am. Chem. Soc. 123, 4360 (2001).
nanorods. Chem. Soc. Rev. 40, 656 (2011). 43. D. Barano, A. Fiore, M.V. Huis, C. Giannini, A. Falqui, U. Lafont,
21. L-S. Li and A.P. Alivisatos: Origin and scaling of the permanent H. Zandbergen, M. Zanella, R. Cingolani, and L. Manna: Assembly
dipole moment in CdSe nanorods. Phys. Rev. Lett. 90, 97402– of colloidal semiconductor nanorods in solution by depletion
97411 (2003). attraction. Nano Lett. 10, 743 (2010).
22. K.M. Ryan, A. Mastroianni, K.A. Stancil, H. Liu, and A.P. Alivisatos: 44. P. Melby, A. Prevost, D.A. Egolf, and J.S. Urbach: Depletion force
Electric-field-assisted assembly of perpendicularly oriented nanorod in a bidisperse granular layer. Phys. Rev. E 76, 051307 (2007).
superlattices. Nano Lett. 6, 1479 (2006). 45. F. Oosawa and S. Asakua: Surface tension of high-polymer
23. S. Gupta, Q. Zhang, T. Emrick, and T.P. Russell: Self-corralling solutions. J. Chem. Phys. 22, 1255 (1954).
nanorods under an applied electric field. Nano Lett. 6, 2066 (2006). 46. K. Ramasamy, X. Zhang, R.D. Bennett, and A. Gupta: Synthesis,
24. E. Saeedi, C. Marcheselli, A. Shum, and B.A. Parviz: Inertially photoconductivity and self-assembly of wurtzite phase Cu2CdxZn1-x
assisted nanoscale self-assembly. Nanotechnology 21, 375604 (2010). SnS4 nanorods. RSC Adv. 3, 1186 (2013).
25. S. Park, J-H. Lim, S-W. Chung, and C.A. Mirkin: Self-assembly of 47. J.Q. Zhung, H.M. Wu, Y.G. Yang, and Y.C. Cao: Controlling
mesoscopic metal-polymer amphiphiles. Science 303, 348 (2004). colloidal superparticle growth through solvophobic interactions.
26. J-H. Lim, J.W. Ciszek, F. Huo, J-W. Jang, S. Hwang, and Angew. Chem. Int. Ed. 47, 2208 (2008).
C.A. Mirkin: Actuation of self-assembled two-component rod like 48. T. Wang, D. LaMontagne, J. Lynch, J. Zhuang, and Y.C. Cao:
nanostructures. Nano Lett. 8, 4441 (2008). Colloidal superparticles from nanoparticles assembly. Chem. Soc.
27. J.W. Ciszek, L. Huang, S. Tsonchev, Y.H. Wang, K.R. Shull, Rev. doi: 10.1039/c2cs35318k.
M.A. Ratner, G.C. Schatz, and C.A. Mirkin: Assembly of nanorods 49. J. Zhung, A.D. Shaller, J. Lynch, H. Wu, O. Chen, A.D.Q. Li, and
into designer superstructures: The role of templating, capillary Y.C. Cao: Cylindrical superparticles from semiconductor nanorods.
forces, adhesion, and polymer hydration. ACS Nano 4, 259 (2010). J. Am. Chem. Soc. 131, 6084 (2009).
28. B.D. Smith, D.J. Kirby, and C.D. Keating: Vertical arrays of anisotropic 50. T. Wang, J. Zhuang, J. Lynch, O. Chen, Z. Wang, X. Wang,
particles by gravity-driven self-assembly. Small 7, 781 (2011). D. LaMontagne, H. Wu, Z. Wang, and Y.C. Cao: Self-assembled
29. C.J. Orendorf, P.L. Hankins, and C.J. Murphy: pH-triggered colloidal superparticles from nanorods. Science 338, 358 (2012).
assembly of gold nanorods. Langmuir 21, 2022 (2005). 51. E. Dujardin, L-B. Hsin, C.R.C. Wang, and S. Mann: DNA-driven
30. D. Fava, M.A. Winnik, and E. Kumacheva: Photothermally- self-assembly of gold nanorods. Chem. Commun. 1264 (2001).
triggered self-assembly of gold nanorods. Chem. Commun. 2571 52. N.M. Green: Avidin. Adv. Protein Chem. 29, 85 (1975).
(2009). 53. K.K. Caswell, J.N. Wilson, U.H.F. Bunz, and C.J. Murphy:
31. K.G. Thomas, S. Barazzouk, B.I. Ipe, S.T.S. Joseph, and Preferential end-to-end assembly of gold nanorods by biotin-
P.V. Kamat: Uniaxial plasmon coupling through longitudinal self- streptavidin connectors. J. Am. Chem. Soc. 125, 13914 (2003).
assembly of gold nanorods. J. Phys. Chem. B 108, 13066 (2004). 54. J-Y. Chang, H. Wu, H. Chen, Y-C. Ling, and W. Tan: Oriented
32. W. Ni, R.A. Mosquera, J. Perez-Juste, and L.M. Liz-Marzan: assembly of Au nanorods using biorecognition system. Chem.
Evidence for hydrogen-bonding-directed assembly of gold nano- Commun. 1092 (2005).
rods in aqueous solution. J. Phys. Chem. Lett. 1, 1181 (2010). 55. C. Wang, Y. Chen, T. Wang, Z. Ma, and Z. Su: Biorecognition-
33. S.T.S. Joseph, B.I. Ipe, P. Pramod, and K.G. Thomas: Gold driven self-assembly of gold nanorods: A rapid and sensitive
nanorods to nanochains: Mechanistic investigations on their longi- approach toward antibody sensing. Chem. Mater. 19, 5809 (2007).
tudinal assembly using a, x-alkanedithiols and interplasmon 56. B. Pan, L. Ao, F. Gao, H. Tian, R. He, and D. Cui: End-to-end self-
coupling. J. Phys. Chem. B 110, 150 (2006). assembly and colorimetric characterization of gold nanorods and

J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013 1775
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52
K. Ramasamy et al.: Routes to self-assembly of nanorods

nanospheres via oligonucleotide hybridization. Nanotechnology evaporation-induced self-assembling. J. Phys. Chem. C 113, 5947
16, 1776 (2005). (2009).
57. A. Salant, E. Amitay-Sadovsky, and U. Banin: Directed self- 71. B. Pietrobon, M. McEachran, and V. Kitaev: Synthesis of size-
assembly of gold-tipped CdSe nanorods. J. Am. Chem. Soc. 128, controlled faceted pentagonal silver nanorods with tunable plas-
10006 (2006). monic properties and self-assembly of these nanorods. ACS Nano
58. H. Nakashima, K. Furukawa, Y. Kashimura, and K. Torimitsu: 3(1), 21 (2009).
Self-assembly of gold nanorods induced by intermolecular inter- 72. C. Nobile, L. Carbonel, A. Fiore, R. Cingolani, L. Manna, and
actions of surface-anchored lipids. Langmuir 24, 5654 (2008). R. Krahne: Self-assembly of highly fluorescent semiconductor
59. Y. Wang, Y.F. Li, J. Wang, Y. Sanga, and C.Z. Huang: End-to-end nanorods into large scale smectic liquid crystal structures by coffee
assembly of gold nanorods by means of oligonucleotide–mercury stain evaporation dynamics. J. Phys. Condens. Matter 21, 264013
(II) molecular recognition. Chem. Commun. 46, 1332 (2010). (2009).
60. D.A. Walker and V.K. Gupta: Reversible end-to-end assembly of 73. A. Singh, R.D. Gunning, A. Sanyala, and K.M. Ryan: Directing
gold nanorods using a disulfide-modified polypeptide. Nanotech- semiconductor nanorod assembly into 1D or 2D supercrystals by
nology 19, 435603 (2008). altering the surface charge. Chem. Commun. 46, 7193 (2010).
61. T. Jain, R. Roodbeen, N.E.A. Reeler, T. Vosch, K.J. Jensen, 74. L. Yi, A. Tang, M. Niu, W. Han, Y. Houb, and M. Gao: Synthesis
T. Bjørnholm, and K. Nørgaard: End-to-end assembly of gold and self-assembly of Cu1.94S–ZnS heterostructured nanorods.
nanorods via oligopeptide linking and surfactant control. J. Colloid Cryst. Eng. Comm. 12, 4124 (2010).
Interface Sci. 376, 83 (2012). 75. A. Sánchez-Iglesias, M. Grzelczak, J. Pérez-Juste, and
62. B. Nikoobakht, Z.L. Wang, and M.A. El-Sayed: Self-assembly of L.M. Liz-Marzán. Binary self-assembly of gold nanowires with
gold nanorods. J. Phys. Chem. B 104, 8635 (2000). nanospheres and nanorods. Angew. Chem. Int. Ed. 49, 9985 (2010).
63. L. Li, J. Walda, L. Manna, and A.P. Alivisatos: Semiconductor 76. Y. Xie, S. Guo, Y. Ji, C. Guo, X. Liu, Z. Chen, X. Wu, and Q. Liu:
nanorod liquid crystals. Nano Lett. 2(6), 557 (2002). Self-assembly of gold nanorods into symmetric superlattices di-
64. L-S. Li and A.P. Alivisatos: Semiconductor nanorod liquid crystals rected by OH-terminated hexa(ethylene glycol) alkanethiol. Lang-
and their assembly on a substrate. Adv. Mater. 15(5), 408 (2003). muir 27, 11394 (2011).
65. Y. Li, X. Li, C. Yang, and Y. Li: Ligand-controlling synthesis and 77. A.M. Hung, N.A. Konopliv, and J.N. Cha: Solvent-based assembly
ordered assembly of ZnS nanorods and nanodots. J. Phys. Chem. B of CdSe nanorods in solution. Langmuir 27, 12322 (2011).
108, 16002 (2004). 78. K.C. Ng, I.B. Udagedara, I.D. Rukhlenko, Y. Chen, Y. Tang,
66. D.V. Talapin, E.V. Shevchenko, C.B. Murray, A. Kornowski, M. Premaratne, and W. Cheng: Free-standing plasmonic-nanorod
S. Förster, and H. Weller: CdSe and CdSe/CdS nanorod solids. superlattice sheets. ACS Nano 6(1), 925 (2012).
J. Am. Chem. Soc. 126, 12984 (2004). 79. A. Singh, R.D. Gunning, S. Ahmed, C.A. Barrett, N.J. English,
67. A. Ghezelbash, B. Koo, and B.A. Korgel: Self-assembled stripe J-A. Garate, and K.M. Ryan: Controlled semiconductor nanorod
patterns of CdS nanorods. Nano Lett. 6(8), 1832 (2006). assembly from solution: influence of concentration, charge and
68. S. Ahmed and K.M. Ryan: Self-assembly of vertically aligned solvent nature. J. Mater. Chem. 22, 1562 (2012).
nanorod supercrystals using highly oriented pyrolytic graphite. 80. C. Querner, M.D. Fischbein, P.A. Heiney, and M. Drndic:
Nano Lett. 7(8), 2480 (2007). Millimeter-scale assembly of CdSe nanorods into smectic super-
69. J. Wang, E. Khoo, P.S. Lee, and J. Ma: Synthesis, assembly, and structures by solvent drying kinetics. Adv. Mater. 20, 2308 (2008).
electrochromic properties of uniform crystalline WO3 nanorods. 81. M. Zanella, R. Gomes, M. Povia, C. Giannini, Y. Zhang, A. Riskin,
J. Phys. Chem. C 112, 14306 (2008). M.V. Bael, Z. Hens, and L. Manna: Self-assembled multilayers of
70. X. Zhang and T. Imae: Perpendicular superlattice growth of vertically aligned semiconductor nanorods on device-scale areas.
hydrophobic gold nanorods on patterned silicon substrates via Adv. Mater. 23, 2205 (2011).

1776 J. Mater. Res., Vol. 28, No. 13, Jul 14, 2013
http://journals.cambridge.org Downloaded: 02 Aug 2013 IP address: 130.160.40.52

Vous aimerez peut-être aussi