COMMUNICATION
org/chemcomm | ChemComm
Sacrificial layer electrophoretic deposition of free-standing multilayered
nanoparticle filmsw
Saad A. Hasan,a Dustin W. Kavichb and James H. Dickerson*b
Received (in Berkeley, CA, USA) 10th February 2009, Accepted 4th May 2009
First published as an Advance Article on the web 27th May 2009
DOI: 10.1039/b902622c
Sacrificial layer electrophoretic deposition (SLED) is a
technique to assemble nanoparticles that yields free-standing,
multilayered nanoparticle films with macroscopic lateral
dimensions after the sacrificial layer is dissolved.
Colloidal nanoparticles (NPs) have been the focus of
far-reaching research pursuits due to their attractive material-
dependent and size-dependent electronic, optical and magnetic
properties. The NPs typically comprise an inorganic core
material coated with surface-passivating organic ligand
molecules that, in part, determine their solubility in a given
solvent. Solution-phase NPs have been targeted for applications
such as fluorescent tagging of cells, drug delivery, and
magnetic recording media.1–3 Further applications may be
accessed by forming dry casts of the NPs. Multilayered thin
films of NPs have been featured in solid-state lighting,
magnetic storage, and catalytic devices.4–7 Harnessing
colloidal NPs to produce new electronic devices is desired
because they can be deposited into solid thin films using
wet processes,8 which offer significant cost advantages over
conventional semiconductor fabrication processes. Many of
these wet processes, however, have acknowledged shortcomings,
such as imposing requirements on the film deposition surface
and offering limited capacity to pattern films laterally.9 With a
technique to assemble NPs into free-standing films that are
robust enough to be transferred to arbitrary substrates, the
barriers to using NPs in engineered devices would be lowered
significantly.
The preparation of free-standing, transferable NP assemblies
has progressed along two fronts. In the first approach, macro-
scopic assemblies are achieved by encasing or interspersing the
NPs in a polymer.10–13 The second approach also yields
macroscopic structures of NPs, but only with the introduction
of chemical crosslinkers, molecules added to the system
that bond to adjacent NPs after they achieve proximity and
that hold the assembly together.14,15 In this communication,
we extend the work on NP assemblies by presenting a
straightforward technique to prepare free-standing NP films,
with macroscopic lateral dimensions, that solely comprise the
a
Interdisciplinary Graduate Program in Materials Science, Vanderbilt
University, Nashville, Tennessee, USA.
E-mail: x.hasan@vanderbilt.edu; Fax: +1-615-343-1708;
Tel: +1-615-343-7758
b
Department of Physics and Astronomy, Vanderbilt University,
Nashville, Tennessee, USA.
E-mail: james.h.dickerson@vanderbilt.edu; Fax: +1-615-343-1708;
Tel: +1-615-343-2957
w Electronic supplementary information (ESI) available: Synthesis
and electrophoretic mobility of iron oxide NPs, electrode preparation,
and EPD current. See DOI: 10.1039/b902622c
This journal is
c The Royal Society of Chemistry 2009
www.rsc.
NPs and their native ligand molecules and are entirely free of
crosslinking or encasing agents. A two-step process, depicted
in Fig. 1a, is employed: (a) using electrophoretic deposition
(EPD), NPs are assembled from suspension into a film over a
thin spun cast polymer layer, which serves as a sacrificial layer
and (b) the copolymer, poly(lactic-co-glycolic acid) (PLGA), is
then dissolved to liberate the NP film from the substrate. This
sequence is the sacrificial layer electrophoretic deposition
(SLED) technique.
The efficacy of PLGA as a sacrificial layer to release the NP
film is facilitated by favorable solvent chemistry. PLGA was
selected, in part, because it experiences minimal swelling and
degradation in hexane, the NP suspension liquid. Its tolerance
to hexane provides a stable surface for NP assembly. When we
probed the polymer sacrifice step with the same solvent that
was used initially to dispense the PLGA, chloroform, we
obtained highly fragmented NP film pieces (area o 5 mm2)
because polymer solvation occurs rapidly and because
chloroform interacts with oleic acid ligands on the NPs,
upsetting the integrity of the film. Consequently, we used
deionized water to liberate the NP film from the substrate.
When exposed to water, PLGA is not initially solvated, but
instead is cleaved by hydrolysis of its ester linkages, reducing
the PLGA to its water-soluble monomers, lactic acid and
glycolic acid.16 An added benefit of using water is that the
NP film is unperturbed since the hydrophobic end of oleic acid
faces outward from the NPs. Submerging the substrate-bound
NP film in water triggers breakdown of the PLGA, and
within minutes yields freely floating macroscopic NP film
(area 4 5 mm2, Fig. 1b).
EPD is used to assemble NPs because the process rapidly
deposits dense films, whose thickness may be tuned by altering
Fig. 1 (a) Schematic of the SLED technique to prepare free-standing
NP films. A representative TEM image of the iron oxide NPs is shown.
Photographs of iron oxide NP films (b) floating on water after
liberation, casting tinted shadows and (c) captured inside a pipette tip.
Chem. Commun., 2009, 3723–3725 | 3723
parameters such as deposition time and electric field strength.
Of the various solution-phase NP assembly techniques, EPD
alone provides enhanced deposition rates and produces films
with low surface roughness as well as long-range consistency in
morphology and thickness.8,17 For readers unacquainted with
the EPD technique, a broad selection of literature reviews the
deposition of nanomaterials18–20 and, specifically, the deposition
of colloidal NPs suspended in non-polar solvents.21–26 Deposition
of NP films via EPD requires the NPs to be charged or dipolar;
thus, an immense selection of NPs is eligible. Solution-phase
cleaning and room temperature thermal effects modify the
attachment of ligand molecules, engendering surface charges
on the NPs that facilitate their locomotion by applied electric
fields.21,25,27 The use of a polymer for the sacrificial layer on
the EPD substrate was motivated by our previous work,26 in
which high quality NP films were cast on a polystyrene layer.
Developing the SLED technique required a model NP
system for EPD. For our purposes, a model NP system for
EPD is characterized by monodisperse NPs whose surface
charge and solubility can be tuned by controlling the type and
amount of organic ligand in the system. We synthesized iron
oxide NPs with oleic acid ligands (total diameter B17 nm)
from an iron oleate precursor in 1-octadecene using the
method of Park et al.28 After precipitating the NPs from the
reaction product and suspending them in hexane, we found
that the distribution of surface charges in this NP system can
be tuned via titration with the organic ligand, oleic acid.29
The electrophoretic mobility distribution of the NPs, which
corresponds to their charge states, revealed NPs with positive
charge and with negative charge. The NP mobility distribution
and details of the EPD suspension preparation are presented
in the ESI.w
EPD was performed in a concentrated hexane suspension of
the NPs (B2.5  1013 mL 1) using two inward-facing parallel
electrodes spaced 2 mm. The electrodes, prepared by spin
casting a B75 nm thick layer of PLGA onto Au-covered Si,
were roughly 1.5 cm  3 cm in dimension. We deposited NP
films using 600 V applied dc voltage for B25 min. The NPs are
driven to the electrode’s surface, where they aggregate to
form a tightly packed, solid film with homogeneity on the
centimetre scale (Fig. 2a). The electrodes were withdrawn from
suspension and dried as the field remained on, enabling
densification of the deposit.20 Profilometry showed that the
NP films possessed thicknesses ranging from 300 to 400 nm.
Energy dispersive X-ray spectroscopy (EDS) confirmed the
NP deposition (Fig. 2b).
Once liberated from the Au substrate, the NP films can be
manipulated in several ways. Large pieces (area Z 10 mm2)
were extracted from the water directly onto SU-8 scaffolds
patterned on Si substrates (Fig. 2c), while smaller sections
were captured and dispensed onto TEM grids by pipette.
Films of all dimensions can be inverted while in the water,
allowing subsequent examination of the substrate-facing sur-
face. Fig. 2d and e show representative scanning electron and
optical micrographs, respectively, of NP films sitting on SU-8
scaffolds. The NP films have smooth edges and the iron oxide
NPs give rise to the brown hue of these films. Thin film
interference is responsible for their multicolored translucence.
The glassy appearance is due to the random close packing of
3724 | Chem. Commun., 2009, 3723–3725
Fig. 2 (a) Iron oxide NP film deposited on PLGA-coated Au
substrate. (b) EDS spectra of film bound to substrate in (a) and of
film resting on SU-8 scaffold in (d). (c) Schematic of film on scaffold.
(d) High magnification SEM image of iron oxide NP film resting on
the SU-8 scaffold; the inset shows same film at lower magnification.
(e) Optical micrograph of NP film atop the SU-8 scaffold. Both the
scaffold height and the scaffold pitch are B50 mm. Scaffold labelled
‘‘SF’’ in (d, e).
the constituents in assemblies of spherical sub-micron particles
with packing fraction 0.49–0.64.30 Atomic force microscopy
(AFM) verified NP packing in this range for our films.
Because no matrix material or external crosslinkers are
used to bind NPs together, the stand-alone films rely on
particle–particle interactions to remain intact. In a film
produced by EPD, the constituent NPs nominally possess
the same charge polarity. Thus, the Coulomb interaction does
not favor strong binding of the NPs. It is possible that
interactions of the ligands on adjacent NPs aid in holding
the film together, but the primary function of ligand molecules
is to prevent agglomeration of suspended NPs. We conclude
that significant van der Waals forces, resulting from the NPs
being tightly packed, keep the film intact. EPD is effective
in producing tightly packed films because the process is
comparable to gravity-driven sedimentation; a NP is
compelled to settle close to its neighbor in the direction normal
to the electrode surface due to the electric field-driven NPs
arriving after it. Lateral proximity is achieved as well, likely via
electroosmotic flow.31,32
After the NP films were released from the substrate, some
PLGA could have remained on the films, bridging adjacent
NPs and helping to hold them together. A chemical analysis
of the substrate-facing interface is insufficient to verify the
complete removal of PLGA because the NPs have their own
organic coating, the ligands. Using AFM, we verified that
PLGA was not acting to bind adjacent NPs. Fig. 3 presents
representative AFM scans of the top and bottom surfaces,
revealing well-delineated NP edges in both scans. An extant
PLGA layer, spanning multiple NPs, would have concealed
these edges.
During further probing of the films, still afloat after
liberation from the substrate, we discovered the films to be
extremely flexible. Fig. 1c shows a section of NP film captured
This journal is
c The Royal Society of Chemistry 2009

Fig. 3 Atomic force micrographs of top and bottom surfaces of NP
film with discrete NPs visible, indicating removal of sacrificial polymer
layer. The horizontal scale bars correspond to 30 nm.
inside a pipette tip, with the film adapting to the tip’s curvature
and narrowing profile. Examination of the films revealed no
fractures as a result of bending them, suggesting that NP films
can be prepared initially on a flat surface and then be delivered
intact onto a surface with arbitrary, non-planar contour. The
observed flexibility of these films is attributed to two factors.
First, NPs are not rigidly bonded to each other via added
crosslinker molecules. Second, the interaction of overlapping
ligands attached to adjacent NPs may give rise to elastic
behavior, due to the relatively long chain length of these
molecules.33 The unanticipated flexibility of the films
contributes to their robustness once they are isolated from
the substrate.
Having demonstrated, using iron oxide NPs, the capacity of
the SLED technique to produce free-standing NP films that
can be transferred to arbitrary substrates, e.g. SU-8 scaffolds,
we explored the employment of SLED to produce films of
other NPs. Using cadmium selenide34 NPs provided by our
collaborators, we manually fashioned a doughnut-shaped
section from a NP film that was transferred to a glass slide
(Fig. 4). The cadmium selenide NPs were B6.5 nm in total
diameter, which included their dodecylphosphonic acid
ligands. Thus, through the SLED technique, it is possible to
obtain patternable, free-standing films comprising NPs of
differing composition, size, and ligand coating. While this
technique may facilitate the use of colloidal NPs as thin
film layers in engineered devices, the ability to isolate NP
ensembles as solids also permits measurement of their intrinsic
properties without the effects of substrate interactions. At a
minimum, our findings suggest a need to catalogue the
mechanical properties of these flexible films, as a function of
film thickness, of NP size, and of ligand composition.
Moreover, the opportunity to examine the back face of an
already-deposited film, as demonstrated in Fig. 3, presents
an alternate perspective to the study of particle aggregation at
an electrode surface, a topic historically studied by observing
the dynamics of a low number of particles in the early stages of
assembly.31,32
Fig. 4 (a) TEM image of CdSe NPs. Optical micrographs of CdSe
NP film section on glass slide captured (b) without and (c) with
fluorescent excitation.
This journal is
c The Royal Society of Chemistry 2009
The authors thank Ron Reiserer and VIIBRE for the SU-8
scaffolds, Prof. Sandra Rosenthal for the CdSe NPs, Sameer
Mahajan for the CdSe TEM image and Ash Jayagopal for
assistance with fluorescent microscopy.
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