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), rather
than normal, to the substrate surface. Surface diffusion and
a
Materials Research Institute and Engineering Science, College of
Engineering, The Pennsylvania State University, University Park, PA,
16802. E-mail: mdemirel@engr.psu.edu
b
Naval Research Laboratory, Code 6910, 4555 Overlook Avenue, S.W.,
Washington, DC, 20375. E-mail: walter.dressick@nrl.navy.mil
Electronic supplementary information (ESI) available: Fig. S1, S2 and
S3. See DOI: 10.1039/b902882j
4796 | J. Mater. Chem., 2009, 19, 47964804 This journal is The Royal Society of Chemistry 2009
PAPER www.rsc.org/materials | Journal of Materials Chemistry
geometric shadowing effects
7,20
occurring during oblique angle
polymerization (OAP) lead to parylene growth as nanostructured
rods onthe substrate, as showninFig. 1C(e.g., a10
; u0s
1
).
19
The inclination, surface density, length, and diameter of the par-
ylene nanorods are determined by the oblique angle (a), as well as
factors suchas the chemical species initially present onthe substrate
surface, substrate and vapor pyrolysis temperatures, deposition
time, and vapor pressure within the deposition chamber. In addi-
tion, rotation of the substrate about the normal (i.e., u > 0 s
1
)
during OAP permits the fabrication of lms exhibiting more
complex morphologies, such as helices or chevrons.
8
Nanostructured parylene lms formed via OAP exhibit excel-
lent biocompatibility and bioactivity, fostering broblast cell
adhesion and proliferation in vitro.
19
The roughened surface
afforded by the nanostructured polymer permits control of lm
wettability
21
and provides a template for the reproducible vapor
phase deposition of adherent Au and Ag metal lms useful as
substrates for surface-enhanced Raman spectroscopy (SERS).
22
Metal adhesion can be further improved by incorporation of
a chemical adhesive component complementing the mechanical
component provided by the nanostructured morphology. For
example, we have recently prepared parylenemetal interfaces
exhibiting enhanced metal adhesion via an electroless process in
which a pyridine ligand is rst physisorbed onto the nano-
structured parylene surface and is stabilized by favorable p and/
or van der Waals interactions with parylene aromatic groups.
23
The adsorbed pyridine covalently and selectively binds colloidal
Pd(II) species
2426
that subsequently catalyze electroless deposi-
tion of adherent, conformal Ni
23
or Co
27
lms onto the nano-
structured surface.
In this work, we generalize our ligand adsorbate concept by
extending it to the fabrication of nanostructured parylenetitania
composites. We describe a liquid phase deposition (LPD)
method for conformal deposition of titania onto a nano-
structured parylene thin lm and characterize various physical
and chemical properties of the resulting composite. Our efforts
constitute a necessary rst step in developing an understanding
of the factors affecting adhesion, wettability, and mechanical
properties of these new composite materials, important for their
subsequent evaluation as potential bioimplant materials and
coatings.
Experimental
Materials and nanostructured lm preparation
Deionized water (18.2 MU cm
1
) from a Barnstead NanoPure II
deionizer was used for all experiments. All materials were used as
received. The ligands phenylphosphonic acid (PPA), thiophenol
(TPH), pyridine (PYR) and the ammonium hexauorotitanate
and boric acid were all ACS reagent grade or better from Aldrich
Chemical Co. Parylene C (i.e., dichloro-[2.2]-p-cyclophane;
Parylene Distribution Services, Inc.; Lot No. 060514; note
Fig. 1A) was used for the preparation of all nanostructured
poly(chloro-p-xylylene) (i.e., PPX-Cl) lms. The OAP process for
the preparation of the PPX-Cl lms has been described in detail
elsewhere.
20
Briey, a 0.3 g portion of dichloro-[2.2]-p-cyclo-
phane, vaporized at 175
C, was subsequently pyrolyzed at 690
).
Titania deposition
PPX-Cl coated Si wafers (OAP and planar methods) were incu-
bated in 0.5 M aqueous phenylphosphonic acid (PPA), 0.5 M
aqueous pyridine (PYR), or 0.5 M thiophenol (TPH) in ethanol
solutions in closed glass containers in a fume hood for 48 h. The
wafers were then rinsed in their respective solvents and trans-
ferred to the titania bath. The LPD bath
29
was prepared imme-
diately prior to use and consisted of an aqueous solution
containing 0.05 M (NH
4
)
2
TiF
6
and 0.15 M H
3
BO
3
. Dilute
aqueous hydrochloric acid, HCl, was added to adjust the pH to
2.88. The PPX-Cl coated wafers were submerged vertically in the
bath held at 50
C for 3 to 24 h to deposit the titania lms. The
wafers were then removed from the bath, sonicated in water for
30 s (VWR Scientic Model 75 HT Aquasonic Bath), rinsed in
fresh water, and dried in a streamof N
2
gas (compressed N
2
tank,
water-pumped). Wafers were stored in sealed Fluoroware
; b 55
).
This journal is The Royal Society of Chemistry 2009 J. Mater. Chem., 2009, 19, 47964804 | 4797
Characterization
An atomic force microscope (AFM, Nanoscope
E, Veeco Inc.)
equipped with an air chamber and silicon nitride cantilevers
operated in contact mode and a JEOL 6700F eld-emission
scanning electron microscope (FESEM) operated at an acceler-
ating voltage of 3 kV were used to characterize the morphology
of the deposited titania lms. Film roughness values were
measured by AFM using methods described previously.
23
The
compositions of the titaniaPPX-Cl composites were determined
using the energy dispersive X-ray (EDX) attachment (Ametex) of
a Philip XL-30 scanning electron microscope (SEM) and an Axis
Ultra XPS X-ray photoelectron spectrophotometer (Kratos)
equipped with a monochromatic Al Ka X-ray source and oper-
ated at a 20 eVpass energy (700 mm300 mmhybrid sample spot
size) under high vacuum conditions (10
9
torr). X-Ray photo-
electron spectra were collected at a take-off angle of 90
and
analyzed using CasaXPS v. 2.312Dev9 spectral tting software
with the C(1s) peak at 284.6 eV taken as the reference. As-
prepared titania samples were subsequently calcined under Ar
atmosphere at 200
C for 24 h and characterized by X-ray
diffraction (XRD). Care was taken to avoid heating the samples
above the PPX-Cl melting temperature of 290
C
30
at any time
during the calcination process. The XRD data were obtained
using a Scintag X2 X-ray diffractometer with a Cu Ka radiation
source and a Si(Li) Peltier cooled detector. The diffraction
patterns were taken using grazing angle incidence (incidence
angle of 2 degrees) while the detector was scanned from 5 to 65
degrees at a rate of 0.02 degree s
1
.
Adhesion tests were performed using the Scotch
tape test.
29
Equal pressure was applied during the attachment and removal
of the tape for all composite lms. Titania coverage was calcu-
lated from 5 low-magnication SEM images taken before and
after the Scotch
/[TiF
5n
(OH)
n+1
]
2
+ F
///[Ti(OH)
6
]
2
(2)
H
3
BO
3
+ 4 HF /HBF
4
+ 3 H
2
O (3)
[Ti(OH)
6
]
2
+ D /TiO
2
(s) + 2 H
2
O + 2 OH
(4)
2 (NH
4
)
2
TiF
6
+ 3 H
3
BO
3
+ HCl /2 TiO
2
(s) + 5 H
2
O
+ NH
4
Cl + 3 NH
4
BF
4
(5)
Under these deposition conditions, the solution is highly
supersaturated and titania nucleation and growth both directly
at the substrate surface and in the solution occur, with subse-
quent incorporation of titania nanoparticles formed in the
solution into the surface titania lm.
29
Fig. 2 depicts the simple two-step scheme used for deposition
of titania lms onto our nanostructured PPX-Cl substrates. In
the rst step, the nanostructured PPX-Cl lm surface is
impregnated with a ligand capable of binding titania or its
precursor species (e.g., eqn. (14)) via simple immersion into
a ligand solution. Ligand physisorption occurs through forma-
tion of favorable p and/or van der Waals interactions between
hydrophobic portions of the ligand structure and aromatic resi-
dues of the parylene chains in a process analogous to that
described for ligand adsorption into solvent-templated nano-
cavities in aromatic organosiloxane SAMs.
4045
For the nano-
structured PPX-Cl lms, however, the corresponding
nanocavities are templated by the anisotropic growth condi-
tions present during the vapor-phase OAP process used to
deposit the parylene, rather than a solvent. Ligand adsorption is
facilitated by the amorphous nature and high curvature of the
parylene nanorods formed, while corresponding planar parylene
lms exhibit negligible ligand binding.
23
The three-dimensional
nature of the parylene polymer chains in nanostructured PPX-Cl
lms provides added conformational exibility in binding ligand
compared to the more rigid two-dimensional aromatic siloxane
SAMs, permitting dissolution and successful binding of a wider
4798 | J. Mater. Chem., 2009, 19, 47964804 This journal is The Royal Society of Chemistry 2009
range of ligands via the use of small hydrophilic alcohols such as
ethanol, in addition to water, as ligand solvents.
We have tested three species, namely phenylphosphonic acid
(PPA), thiophenol (TPH) and pyridine (PYR), which spans
a range of titania binding strengths, as ligands. Because Ti
IV
preferentially binds oxygen-, rather than nitrogen-containing
ligands, it binds strongly to phosphonate-containing species such
as PPA but interacts only weakly with aromatic N-containing
species such as PYR.
46
The selection of TPH represents a ligand
of intermediate binding strength due to the presence of the SH
site, rather than the more strongly interacting OH site of the
PPA. After incorporation of ligand into the nanostructured
PPX-Cl lm, treatment with the aqueous hexauorotitanate-
boric acid LPD bath in the second process step of Fig. 2 initiates
titania lm deposition at the ligand sites.
Table 1 summarizes our titania deposition results as functions
of (1) LPD bath treatment time for PPA-impregnated PPX-Cl
lms, and (2) type of ligand for PPX-Cl lms separately treated
by each ligand (48 h) and the LPD bath (24 h). For the time-
dependent study, SEMs and AFM surface maps are provided in
Fig. 3 as functions of the LPD bath treatment times for the PPA-
impregnated nanostructured PPX-Cl lms. The quantity of
titania deposited onto the PPA-treated PPX-Cl surface increases
monotonically with time, as shown by the decreasing C and
increasing Ti EDX signals in Table 1. Only traces of titania are
observed on the PPX-Cl surface in the absence of ligand treat-
ment, as expected for the model of Fig. 2.
Titania initially deposits as a conformal lm onto the PPA-
impregnated PPX-Cl nanorods, as shown in Fig. 3A, covering
50% of the substrate surface after only 3 h of deposition. After
longer times, however, the distinct PPX-Cl nanorods are
increasingly covered as fronts of growing titania lms merge,
lling the pores between the PPX-Cl nanorods. At the same time,
titania nodules appear and persist on the surface as shown in the
SEM images of Fig. 3B and 3C for 6 h and 24 h LPD bath
treatments, respectively. Signicant changes in surface roughness
simultaneously occur, as shown by the AFM maps in Fig. 3 and
summarized in Table 1. Initial PPX-Cl lm roughness (i.e., 46.3
5.0 nm) decreases markedly during the rst 3 h of titania
deposition (i.e., 19.5 1.2 nm), followed by a slower increase to
31.6 1.9 nm after 24 h. The changes in morphology shown in
the SEMs of Fig. 3, together with the roughness variations
documented in Table 1, are consistent with a model in which
initial nucleation and conformal growth of titania on the PPA-
treated PPX-Cl nanorods is supplemented at longer times by
incorporation of titania nanoparticles nucleated in the solution
into the growing titania lm, as expected for LPD from
a supersaturated solution under our conditions (note experi-
mental section).
29,31
Ligand type also signicantly affects the deposition of titania
onto the PPX-Cl lm. Titania coverage decreases from >95%
when PPA ligand is present to 5090% for TPH and <1020%
for PYR in Table 1. The Ti EDX signal of 19.8% noted for PPA
is reduced to 14.7% for TPH and just 1% for PYR. Both trends
correspond to the expected titanialigand binding strength of
PPA > TPH [PYR. Although PYR adsorbs well to the PPX-
Cl nanostructures,
23
its weaker interactions with Ti
IV
species
severely limits titania deposition. However, adsorbed pyridyl N
sites typically exhibit surface pK
a
s of 3.35.9
47,48
and will be
substantially protonated under our titania deposition conditions
(i.e., 72.599.9% protonation, respectively, at pH 2.88). There-
fore, the minimal titania deposition observed in this case more
likely results from weaker electrostatic, rather than covalent,
interactions between anionic titania precursors shown in eqn. (1
3) and accessible protonated pyridyl sites on the PPX-Cl surface.
The growth of titania is summarized in Table 1 (thickness
column) and depends on the type of ligand present in the PPX-Cl
lm. While PPA and TPH treated PPX-Cl lms show the highest
growth rates, the PYR treated PPX-Cl lm shows sluggish
growth. The growth of the untreated PPX-Cl lm is extremely
poor and takes place primarily due to the physical entrapment of
the titania nanoparticles in the porous PPX-Cl. The initial rapid
titania growth rate eventually slows at longer bath treatment
times, as shown in Fig. 3D for the PPA-impregnated PPX-Cl
lm. This behavior reects the diminished surface area available
for titania deposition as lling of the interstitial regions between
the PPX-Cl nanorods by titania is completed and the titania
completely covers the PPX-Cl lm (note Fig. 3B and 3C).
The corresponding contact angles of the titaniaPPX-Cl
composites from Table 1 also drop steadily as the deposition
proceeds. The PPX-Cl lm possesses a hydrophobic surface with
a contact angle of 124 5
and 37