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Annu. Rev. Chem. Biomol. Eng. 2016.7:373-393. Downloaded from www.annualreviews.org
Nan Chen,1,∗ Do Han Kim,1,∗ Peter Kovacik,1

Hossein Sojoudi,1,2 Minghui Wang,1
Access provided by RMIT University on 07/24/17. For personal use only.
and Karen K. Gleason1

1
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139; email: kkg@mit.edu
2
Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139
Annu. Rev. Chem. Biomol. Eng. 2016. 7:373–93 Keywords

The Annual Review of Chemical and Biomolecular CVD, chemical vapor deposition, surface engineering, organic devices,
Engineering is online at chembioeng.annualreviews.org
conformal coating, encapsulation, solvent-free
This article’s doi:
10.1146/annurev-chembioeng-080615-033524 Abstract
Copyright c 2016 by Annual Reviews. Chemical vapor deposition (CVD) polymerization uses vapor phase
All rights reserved
monomeric reactants to synthesize organic thin films directly on substrates.
∗
Authors contributed equally. These thin films are desirable as conformal surface engineering materials
and functional layers. The facile tunability of the films and their surface
properties allow successful integration of CVD thin films into prototypes
for applications in surface modification, device fabrication, and protective
films. CVD polymers also bridge microfabrication technology with chemi-
cal and biological systems. Robust coatings can be achieved via CVD meth-
ods as antifouling, anti-icing, and antihydrate surfaces, as well as stimuli-
responsive or biocompatible polymers and novel nanostructures. Use of
low-energy input, modest vacuum, and room-temperature substrates ren-
ders CVD polymerization compatible with thermally sensitive substrates
and devices. Compared with solution-based methods, CVD is particularly
useful for insoluble materials, such as electrically conductive polymers and
controllably crosslinked networks, and has the potential to reduce environ-
mental, health, and safety impacts associated with solvents. This review dis-
cusses the relevant background and selected applications of recent advances
by two methods that display and use the high retention of the organic func-
tional groups from their respective monomers, initiated CVD (iCVD) and
oxidative CVD (oCVD) polymerization.
373
INTRODUCTION
Chemical vapor deposition (CVD) is a mature and powerful technology in the semiconductor
industry for creating and engineering inorganic surfaces. The CVD method also has been rapidly
expanding for functional organic surfaces and devices (1–3), enabled by the common characteristics
of CVD polymers (Figure 1). For CVD polymers, monomer vapors flow into a vacuum chamber
and undergo polymerization to form a solid organic thin film in a single step (1, 2). The high
degree of purity of the vapor phase reactants eliminates many contaminants, such as salts and
surfactants, producing the high-quality films essential for devices. Unlike conventional solution-
synthesized polymer films, CVD polymers are inherently free of residual solvents and thus do not
typically require additional curing or drying steps. Simple adjustments to the flow rates of the
Flexible
electronics
Low-
temperature
processing
Substrate
independent Solvent-free
Conductive textiles
CVD
polymers
Conformal
Scale-up coating Defect-free,
high-purity films
Fully
functional
group Functional films
– –
–
–
–
Roll-to-roll –
–
– –
+ – + +
N N N
+ + +
N N N
Figure 1
Core features (inner ring) of chemical vapor deposition (CVD) polymers and related exemplar applications
and attributes (outer branches): defect-free, high-purity films (5), functional films for biomass extraction (6),
roll-to-roll web coating system (7), conductive textiles for wearable devices (8), and dielectric polymeric films
on flexible electronics (9). Portions of the figure reprinted with permission from Reference 5, 2014
c Wiley;
from Reference 7, 2009
c Elsevier; from References 6 and 8, 2015
c R. Soc. Chem.; and from Reference 9,
2015
c Nat. Publ. Group.
374 Chen et al.

reactant vapors enable systematic tuning of the thin-film and surface properties (1, 2). In the case
of copolymers, film composition can be readily adjusted via the feed ratio of the monomers. As
a low–surface temperature and solvent-free process, CVD polymerization is compatible with a
wide range of substrates, even materials that are flexible, fragile, and/or difficult to wet. Lack of
surface tension effect also allows CVD polymers to uniformly cover micro- and nanoscale features,
a characteristic known as conformal coverage. Use of CVD also minimizes the environmental,
health, and safety impacts and recycling/disposal cost associated with using solvents. Based on the
well-established fundamentals of chemical kinetics, fluid dynamics, and heat and mass transport,
CVD polymer processes are scalable to large areas and roll-to-roll manufacturing and can be
readily integrated with other types of coating or printing equipment (4).
Several CVD processes have been mechanistically designed to mimic the chain growth and
step growth mechanisms from solution synthesis. For chain growth polymers, a volatile initiator
can be introduced in the vapor phase feed along with the monomer(s). The initiators can be acti-
vated thermally (initiated CVD, iCVD) (2), by UV exposure (photo-iCVD) (10), or by applying
plasma excitation (initiated plasma-enhanced CVD, iPECVD) (11). Alternatively, high–molecular
weight initiators can be preapplied to the substrate [surface-initiated vapor deposition polymeriza-
tion (VDP)] (12). Methods for CVD step growth polymerization include oxidative CVD (oCVD)
(13), vapor phase polymerization (14), molecular layer deposition (15, 16), and oxidative molecular
layer deposition (17). The benign conditions of these mechanistically based processes can achieve
excellent retention of functional groups from the monomers into the films. Recent progress on
CVD polymers is reviewed in three sections. The first focuses on surface engineering designed
to achieve a portfolio of properties, including antibiofouling, ice-/hydrate-phobic surfaces, drop-
wise condensation, biocompatibility, antimicrobials, and stimuli-responsive behavior. The second
section summarizes the device integration of CVD polymers for advancing supercapacitors (18),
sensors (19), transistors (9, 20, 21), photovoltaic cells (22, 23), batteries (24, 25), and other de-
vices. The third section discusses CVD polymeric films as protective layers to prolong the stability
of nanotubes and devices when exposed to external stresses, such as moisture, solvent, and UV
light.
SURFACE ENGINEERING
Antibiofouling iCVD Surfaces: Hydrophilic, Amphiphilic, and Zwitterionic,

Including Durable, Grafted Layers
Surface coatings that resist fouling by biomolecules and microbes are desirable for applications
ranging from marine equipment and membrane desalination systems to food packaging (26, 27).
Classes of antibiofouling CVD polymers include those based on polyethylene oxide (PEO) (28,
29), amphiphilic compositions (28–32), and zwitterionic surfaces (33–35).
Hydrophilic PEO-based coatings have long been considered to be the gold standard for an-
tifouling surfaces (26, 28). By employing iCVD, Bose et al. (29) synthesized antifouling PEO
coatings via a unique ring-opening cationic polymerization mechanism. The silicon substrate was
prefunctionalized with amine groups to achieve high grafting density and polymer formation in
one single step and in a short period (∼27 nm/min). Excellent fouling resistance toward bovine
serum albumin (BSA) was observed, resulting from the large enthalpic penalty for protein to
displace the water molecules adsorbed on EO monomer units via hydrogen bonding (29, 36).
Amphiphilic compositions resist biofouling through molecular-level heterogeneities that
disrupt surface-protein interactions (37). The solvent-free nature of iCVD enabled random
www.annualreviews.org • Chemical Vapor Deposition 375

copolymerization of a hydrogel-forming monomer and a fluoromonomer, hydroxyethyl

methacrylate and (1H,1H,2H,2H-perfluorodecyl)acrylate (pPFDA), respectively. This hy-
drophilic/hydrophobic copolymerization is difficult to realize via other methods. The composition
containing 40% of pPFDA was optimal for resisting fouling by the protein BSA. Images of the
interspersed hydrophilic and hydrophobic nanodomains (1–2 nm2 ) were obtained by amplitude
modulation atomic force microscopy (AFM) (24). Ultrathin (∼38.7-nm) amphiphilic iCVD layers,
directly applied on the commercial reverse osmosis (RO) membranes (38), resisted protein and
bacterial attachment, while yielding a minimal decline in the water flux and salt rejection (38).
Zwitterionic coatings, with permanent cation/anion pairs, strongly bind water via electrostatic
interactions. Analogous to the mechanism discussed above for PEO-based surfaces, hydration
induces high resistance toward nonspecific biofoulant adsorption (36). Although traditional atom
transfer radical polymerization can damage commercial RO membranes, Yang et al. (33–35) di-
rectly applied iCVD followed by an in situ 1,3-propanesultone vapor treatment to synthesize a se-
ries of zwitterionic coatings directly on RO membranes. The first-generation iCVD methacrylate-
based zwitterionic coatings demonstrated nondetectable surface attachment of sodium alginate
and Escherichia coli and minimal adsorption of BSA protein (34, 35). Moreover, the coated RO
membranes showed minimal change in water flux and salt rejection (35). Owing to the pos-
sible degradation of the methacrylate-based coatings in the seawater- and chlorine-containing
environment (39), a second generation of iCVD zwitterionic coatings was synthesized using the
nonacrylate-based monomers 4-vinylpyridine (4VP) and divinylbenzene (DVB) (Figure 2a) (33,
40). The 4VP-co-DVB copolymer-based zwitterionic coatings demonstrated excellent stability in
the chlorine-containing solution. In addition, a synergistic antifouling effect was observed when
combining zwitterionic surface and low-level chlorination. As shown in Figure 2b, the fouling
resistance for zwitterionic coating in the chlorine solution (e.g., Figure 2b, viii ) was much bet-
ter (as much as 10 times) than the multiplicative effects assumed between the chlorination (e.g.,
Figure 2b, ii and vii ) and the coating (e.g., Figure 2b, ii and vi ) (33).
A molecular force probe was used to measure the adhesion force between iCVD surfaces and an
AFM tip functionalized with foulant analogs (41). The molecular force probe force values for the
4VP-co-DVB-based zwitterionic surfaces were lower than for the amphiphilic surfaces (41). The
iCVD zwitterionic coatings also display underwater superoleophobicity, enabling gravity-driven
oil-water separation (42). As shown in Figure 2c, a mineral oil–water mixture was separated by
the iCVD 4VP-co-DVB zwitterion-coated nickel mesh, with mineral oil (red color) accumulated
on the membrane. After filtration, the mineral oil–contaminated nickel mesh was simply cleaned
by water rinsing (42).
Biomass Extraction Using iCVD Coatings

Microalgea is a potential feedstock for renewable biofuels, but the traditional lipid-extraction step is
highly energy intensive (6). As an alternative, Yoo et al. (6) surface modified nylon membranes with
quaternary amine functional groups using iCVD poly(N-4-vinylbenzyl-N,N-dimethyl-amine)
(PDMAMS). As shown in Figure 2d, the negatively charged phospholipid bilayers of the intact
microalgal cells are attracted by the positively charged PDMAMS surface. Direct contact with
the membrane ruptures the microalgal cell membrane and stimulates the release of intracellular
lipid. Improved energy efficiency results from minimizing the dewatering load. The maximal
extraction yield was as high as 25.6%. It should be noted that iCVD PDMAMS can also serve as
an antimicrobial surface with >99.99% efficiency against E. coli and Bacillus subtilis (32). Adding
the crosslinking agent (ethylene glycol diacrylate, EGDA) during synthesis prevents the iCVD
coating from dissolving and/or leaching when immersed in liquid (43).
376 Chen et al.

5 ppm chlorine
i. Bare ii. Coated iii. Bare iv. Coated

a b
5h
F1 ≈ 0.01 F1 ≈ 0.45
+
N
v. Bare vi. Coated vii. Bare viii. Coated
O 12 h
S
O –
O
F1 ≈ 0.14 F1 ≈ 0.58 S ≈ 0.26
50 μm
N
–
c d –
–
–
–
Oil – [ ]n *
Cleaned – *
Ni mesh – –
+ – + +
N N N
+ + +
N N N
Ni Lipid
mesh body
Water
Microalgal cell Contact with functional Cell disruption and

polymeric membrane lipid body release
Figure 2
(a) Molecular structure of copolymer poly(4-vinylpyridine-co-divinylbenzene) (p4VP-co-DVB)-based zwitterionic initiated chemical
vapor deposition (iCVD) coating. (b) Attachment of concentrated suspensions of the marine bacteria Vibrio cyclitrophicus to glass surfaces
with (i,v) no treatment, (ii,vi ) the zwitterionic coating (functionalized copolymer 1), (iii,vii ) chlorination (5 ppm), and (iv, viii ) the
zwitterionic coating plus chlorination (5 ppm), after 5 h (i–iv) and 12 h (v-viii ). Reproduced with permission from Reference 33,
2014
c Wiley. (c) Mineral oil–water separation membranes (with self-cleaning characteristics) fabricated by coating nickel mesh via the
iCVD approach. (inset) Micrographs of the unmodified nickel mesh (diamond pores with diagonal length of 750 μm). Reproduced with
permission from Reference 42, c 2015 Wiley. (d ) Schematic illustration of the proposed mechanism for cell disruption. Intact
microalgal cells (left) enveloped with multiple membrane layers of cell wall (negatively charged at the cell surface) are in contact with
positively charged tert-amine-containing functional coating (middle). The direct contact induces the perturbation of the local
electrostatic equilibrium of the amphiphilic microalgal cell membrane and results in local rearrangement of lipid bilayers of microalgae
(middle), which further leads to the rupture of the cell membrane and the release of intracellular lipid (right). Reproduced with
permission from Reference 6, 2013 c R. Soc. Chem.
Durable Anti-Icing, Anti-Hydrate, and Dropwise Condensation:

Grafted Hydrophobic Surfaces
Surface wettability has emerged as a powerful means to influence phase-change phenomena, such
as the formation, accumulation, and adhesion of ice, snow, frost, rime, glaze, or their mixtures, as
well as condensation of steam (44–46). In particular, icephobic coatings offer promise for saving
energy and enhancing safety when applied to the surfaces of solar panels (47), wind turbines (48),

aircraft (49), heat pumps (50, 51), power lines (52), telecommunication equipment (52, 53), and
submarines (54). Practical adoption of icephobic coatings requires mechanical robustness and
stability under harsh real-world environments.
iCVD offers a unique way to deposit graded, bilayer, or crosslinked polymers of limited-
solubility monomers, such as low–surface energy fluoropolymers, desired for icephobic
applications simply by changing the ratio of reactants fed to the vacuum chamber during the
film growth period (55). In addition, iCVD enables interfacial engineering at the initial growth
interface to promote adhesion of the film to the substrate, enhancing mechanical robustness
(55–58). For example, Sojoudi et al. (55) have developed durable and mechanically robust bilayer
of poly(divinyl benzene) and poly(perfluorodecyl acrylate) (pDVB/pPFDA) coatings using iCVD
to reduce the adhesion strength of ice to underlying silicon and steel substrates (Figure 3). They
designed inherently rough bilayer films deposited on rough steel substrates: a relatively thick (∼1
µm) and highly crosslinked polymer (pDVB) underneath a very thin (10- or 40-nm), fluorine-rich
polymer (pPFDA). The coatings exhibit a receding water contact angle (WCA) higher than
150◦ and WCA hysteresis as low as 4◦ . Finally, the strength of ice adhesion is reduced more
than sixfold when the surfaces are coated with the iCVD bilayer polymer films (Figure 3b). In
addition, crosslinking and grafted gradation of 1H,1H,2H,2H-perfluorooctyl acrylate (PFOA)
film with an ultrafilm pDVB layer reduced the WCA hysteresis to as low as 26.9◦ , resulting in
short chain fluoropolymeric films (59).
Moreover, blockage of pipelines by formation and accumulation of clathrate hydrates of nat-
ural gases (also called gas hydrates) can compromise project safety and economics in oil and gas
operations, particularly at high pressures and low temperatures, such as those found in subsea or
arctic environments (60, 63). In two separate studies, Sojoudi et al. (60, 63) examined their bilayer
polymer coatings to study the formation and adhesion of hydrates. They studied both water-
miscible and water-immiscible hydrates. The strength of water-miscible tetrahydrofuran (THF)
hydrate adhesion experiences a tenfold reduction when substrates are coated with the iCVD bi-
layer polymers: from 1,050 ± 250 kPa on bare silicon to 128 ± 100 kPa on coated silicon and from
1,130 ± 185 kPa on bare steel to 153 ± 86 kPa on coated steel. Likewise, the adhesion strength
of water-immiscible cyclopentane (CyC5) hydrate deposits was reduced from 220 ± 45 kPa
on rough steel substrates to 20 ± 17 kPa on the polymer-coated steel substrates.
Another application of wettability control on surfaces related to the phase-change phenomena
is dropwise condensation of water vapor in power generation and thermal desalination processes.
Maintaining the condensate in droplet form offers an order-of-magnitude improvement in the
heat-transfer coefficient and increased energy efficiency when compared with filmwise condensa-
tion (64–66). However, for efficient dropwise condensation, surface coatings must be ultrathin, as
a thick coating can itself be a thermal insulator. Ultrathin films (∼40 nm) of p(PFDA-co-DVB)
grafted to metal substrates by iCVD resulted in sustained (>48-h) dropwise condensation of steam
under accelerated testing. Under the same conditions, traditionally available fluorosilane coatings
degraded in <30 min (56).
Stimuli-Responsive Polymers
A high retention of functional groups is essential for the synthesis of polymers that exhibit responses
to external stimuli, such as changes in pH, temperature, and UV-light exposure (61, 67–71). For
better sensitivity, iCVD enables integration of the responsive polymer films with high–surface
area nanostructures like nanotubes and membranes. For example, Ye et al. (71) and Armagan
et al. (67) deposited an iCVD pH-responsive hydrogel, poly(methacrylic acid-co-ethylene glycol
dimethacrylate), on carbon nanotubes (CNTs) and anodic aluminum oxide (AAO) while preserving
378 Chen et al.

a DVB PFDA
b
O
H 2C
OCH2CH2(CF2)7CF 3
1 μm 40 nm
10 or
pPFDA
pDVB Bare Coated

BL (40 nm)
O O O O O
Substrate
BL (10 nm)
c d
100 No xPMAA
T < LCST, at 25° T > LCST, at 55° Porous xPMAA
25 °C 55 °C
80
Porous
Transmittance (%)
polymer
60
Transparent Opaque
Ponceau S and 5 mm
40 crystal violet Crystal violet
Ponceau S
20
at λ = 500 nm
0
25 27 29 31 33 35 37 39 41 43 45 47 49 51 53 55
Temperature (°C)
Figure 3
(a) A linker-free grafted bilayer pDVB/pPFDA polymeric network deposited on substrates (silicon or steel) and representative images
of cyclopentane (CyC5)-in-water emulsion droplets captured during contact angle measurements on linker-free grafted bilayer
pDVB/pPFDA with 40-nm pPFDA on Si [denoted as BL (40 nm)] (top) and linker-free grafted bilayer pDVB/pPFDA with 10-nm
pPFDA on Si [BL (10 nm)] (bottom). Reprinted with permission from Reference 55, 2015 c R. Soc. Chem. (b) Microscopic image of the
bare sample that shows crystals of frost formation (left) and initiated chemical vapor deposition (iCVD)-coated sample that shows
formation of only small droplets (right), both of which occur when water vapor condenses at lowered temperatures. (c) UV
transmittance (at the wavelength of 500 nm) of aqueous solution containing 0.25 wt.% PNVCL, measured from 25◦ C to 55◦ C. The
top inset images show the change in contact angle (CA) of iCVD PNVCL coated on a Si wafer. The CA was approximately 25◦ at 25◦ C
(left) and 70◦ at 55◦ C (right). The bottom inset images show the change in optical transparency of PNVCL aqueous solution at 25◦ C
(left) and 55◦ C (right). Reprinted with permission from Reference 61, 2013
c Elsevier. (d ) Mixture of crystal violet and ponceau S
flowing through a paper-based microfluidic device in the absence (left) and presence (right) of a porous xPMAA membrane. Reprinted
with permission from References 62, 2013c Am. Chem. Soc.
the vertical alignment of coated structures and the pendent functional groups of monomers.
Ye et al. (71) observed that the hydrogel coating significantly enhanced the water wettability of
CNTs. Armagan et al. (67) demonstrated that the free-standing pH-responsive iCVD hydrogel
nanotubes templated by AAO are potentially useful for drug-delivery systems.
Temperature-responsive polymers exhibit different contact angles upon the external thermal
stimuli that change intramolecular forces, such as hydrogen bonding and hydrophobic interac-
tions (61, 68–70). iCVD poly(N-vinylcaprolactam) (pNVCL) is an amphiphilic and water-soluble
polymer at ∼31–34◦ C in aqueous medium, but it becomes water insoluble at temperatures higher

than that. In Figure 3c, UV-vis transmittance at a wavelength of 500 nm clearly shows the phase
transition from dissolved pNCVL to the hydrophobic precipitates of pNVCL as temperature
increases (61). With the pNVCL films on a glass substrate, Lee et al. (61) transferred 30- to
100-nm-thick NIH 3T3, mouse fibroblasts attached the pNCVL, to another substrate by con-
trolling the temperature. The iCVD pNCVL film was also found to be biocompatible as tested via
live/dead assay to culture cells on it (61). Other thermoresponsive polymers deposited by iCVD
are poly(N-isopropylacrylamide) (pNIPAAm) and poly(methacrylic acid) (pMAA). Demiryürek
et al. (69) developed highly ordered, well-defined wrinkle structures of pNIPAAm on prestrained
polydimethylsioxane. Seidel et al. (70) synthesized novel pMAA and pNIPAAm membranes with
dual-scale porosity that contain small-size pores within a structure of larger-size pores.
Petruczok et al. (68) reported the iCVD synthesis of the UV-responsive layer poly(vinyl
cinnamate) and demonstrated patterning with 30-µm resolution using 254-nm irradiation. The
copolymer of vinyl cinnamate with N-isopropylacrylamide is also thermoresponsive, which enables

reversible patterning upon submersion of the copolymer films in water. In all cases, the properties
of the coated nanostructures can be tailored by simple adjustments in iCVD process conditions.
Biocompatible Polymers
Biocompatible polymers are broadly used in medicine, medical devices, and tissue engineering.
Key requirements for these polymers are lack of reaction with immune systems and compatibility
with blood. Accordingly, poly(ethylene glycol) (PEG) is a biocompatible polymer well-known to
repel protein and inhibit cell adsorption. However, the coating with PEG is challenging owing to
the high viscosity and water solubility of PEG precursor in solution-based depositions. The im-
mobilization of specific biomolecules on the films is very useful for understanding and controlling
cellular behaviors in biological environments. Bally et al. (72) deposited poly(4-ethyl-p-xylene-
co-p-xylene) through the pyrolysis of 4-ethynyl[2.2]paracyclophane and presented the multiple
types of immobilization in conjunction with microcontact printing. To increase surface area (72)
in order to enhance performance, Ince et al. (73) developed imprinted polymeric nanotubes with a
template of AAO and iCVD poly(2-hydroxyethyl methacrylate), which can specifically recognize
and immobilize immunoglobulin G (IgG).
Novel Nanostructures
Polymer films can be fabricated at a fast deposition rate by controlling the CVD conditions: the
chamber pressure, flow rate, and stage temperature. For example, polymer CVD was employed
successfully to produce thick films or free-standing membranes with unique porous structures.
The Gupta group (62, 70) created novel membranes with highly engineered porous structures
by using iCVD under unconventional CVD processing conditions—they increased the partial
pressure of the monomer above its saturation pressure and decreased the substrate temperature
below the freezing point of the monomer. Then, by removing unreacted monomers from the
partially polymerized thick films, they produced free-standing polymer membranes with dual-
scale porosity, in which the large- and small-size pores coexisted. Control over the pore size and
growth rate was achieved by adjusting deposition time, substrate temperature, and monomer par-
tial pressure (70). In a later work, they deposited crosslinked pMAA, a pH-responsive polymer,
on partially masked paper to create hierarchical porous-on-porous structures (62). The resulting
paper-based microfluidic device, as seen in the right-hand side of Figure 3d, allows the selective
separation of crystal violet, a cationic analyte, from a mixture containing the anionic dye ponceau
380 Chen et al.

S. This was due to the increased electrostatic attractions between pMAA with high surface area
and crystal violet. In Gupta et al.’s (74) recent work, the pMAA membrane was converted to
poly(methacrylic acid-co-methacrylic anhydride) by thermal annealing, which allowed for tuning
of the water-dissolution behavior. In contrast, thin and crosslinked underlayers produced smooth
iCVD films under the supersaturation of monomer vapors. Other macroporous films were syn-
thesized by introducing a porogen (e.g., ethylene glycol) and crosslinker during iCVD and then
removing it, e.g., under vacuum (75). In this process, the inert condensable, for example, leads the
phase separation during vapor deposition polymerization in which the porogen turns into tunable
pores later in the films (76). In addition to the porous structures, polymer nanoparticles, beneficial
to catalysis, photonics, and drug delivery, were produced by iCVD on the liquid (polydimethyl-
siloxane, Krytox) with low vapor pressure (77). It was observed that the different location of the
particles relative to the liquid-vapor interface relies on the surface tension interaction between
the polymer and liquid above or below the interface, wherein the particle diameter is deposition
time and liquid dependent.
Process Studies and Tuning CVD Polymers

As mentioned in the introduction, modified polymer CVD processes have been developed to solve
some challenges of conventional polymer CVD. A variant of plasma-enhanced CVD (PECVD),
initiated PECVD (iPECDV), uses low-power plasma excitation to decompose the volatile ini-
tiator molecules while avoiding the fragmentation of the monomer vapors (10). The resulting
iPECVD films contain comparable retention of monomer functional groups to the iCVD films
(10). In another example, Petruczok et al. (78) modified conventional continuous-flow iCVD to
closed-batch iCVD, which significantly reduced material cost per 100 nm of films by 1–2 orders
of magnitude while yielding conformal, uniform, and smooth polymer films with precise con-
trol over the deposition rate. As regards conjugated polymers, poly(3,4-ethylenedioxythiophene)
(PEDOT), in oxidative molecular-layer deposition, instead of concurrent exposure used in oCVD,
the sequential vapor exposures of monomer and oxidant achieved highly conformal coatings ex-
ceeding 3,000 S cm−1 over deep trench (aspect ratio, 1:40) structures (17, 79). The copolymeriza-
tion of thiophene and pyrrole by oCVD enhanced the electrical conductivity and stability in the
ambient atmosphere in comparison to the respective homopolymers (80).
The characteristic properties of CVD polymer films are tunable based on the process pa-
rameters. For instance, in iCVD poly(4-vinylpyridine-co-divinylbenzene), the ratio of the two
monomers fed to the reactor determined the degree of incorporation of DVB into the copolymer
and thus tuned the mechanical properties of the films (40). The glass-transition temperature, coef-
ficient of thermal expansion, and elastic modulus of iCVD poly(neopentylmethacrylate) films were
controllable and compared with the spun-cast films (81). Thermal reaction of the pendent organic
group of iCVD poly(glycidylmethacrylate) allowed the bonding of two large 300-mm wafers, either
permanently or temporarily depending on the annealing temperature (82). With respect to control
of water wettability, tuning the flow-rate ratios of monomers for the copolymerization of immisci-
ble polymers, such as poly(2,3,4,8-tetramethyl-2,4,5,6-tetravinylcyclotetrasiloxane) (pV4D4) and
poly(4-vinylpyridine), by iCVD provided exquisite control over the surface energy (83). This fine-
tuning capability of iCVD for wettability also enabled the development of novel Janus cylinders
(84). An effective patterning technique was also developed by applying transition metal salts in
selective iCVD processes (85). X-ray spectroscopic investigation revealed that the reduction of
the oxidation state of metals quenches the propagating radicals and therefore inhibits the iCVD
film growth.

DEVICE INTEGRATION
Polymer films will play an important role in next-generation electronics (86). Novel technologies
based on thin-film architectures expose unique potential benefits over their rigid counterparts,
such as lower cost, lightness, and flexibility, as well as improved performance and new func-
tionality. For example, conjugated polymers have already demonstrated technological shifts in
multiple established areas of electronics, in pace with the emergence of organic light-emitting
diodes (OLEDs), organic photovoltaics (OPVs), and organic field-effect transistors (OTFTs).
Simultaneously, dielectric and ion-conducting polymers have been shaping the fields of battery
and supercapacitor energy storage, fuel cells, and electrochromic devices. Here, we review progress
in these device areas in the context of CVD polymer thin films.
Conducting and semiconducting conjugated polymers have been a key material platform for
organic electronics (87). One of the most prominent representatives is PEDOT, a transparent
polymer with excellent electrical conductivity (88). These properties have predetermined its main
application as a transparent electrode in OPVs and OLEDs, but also as an interface layer in organic
optoelectronics in general. PEDOT produced by oCVD has demonstrated excellent performance

and stability, compared with solution-processed PEDOT:PSS, and a unique applicability in differ-
ent device architectures (89). This comes as a result of the solvent-free and substrate-independent
character of the CVD deposition process. Recently, several studies have examined the fundamental
structure-property relationships behind its properties. Improvements in conductivity of PEDOT
owing to an elevated substrate temperature were shown to arise from increased growth and inter-
connectivity of the polymer crystals within the film (Figure 4a–e) (90). Postdeposition acid doping
with HBr led to a better molecular alignment as well as improved counteranion doping (91, 91a).
However, the resulting high doping densities (∼1021 cm−3 ) were found to limit the carrier mo-
bility of the polymer, which suggests that no significant enhancement in charge transport would
likely come from an additional doping of PEDOT (91). Another study on oCVD and vapor phase
polymerization PEDOT films showed that introducing additional water vapor into the process
increases the doping level and crystallinity of the films without the need for acid rinsing (92).
As regards the performance, the combination of high-temperature deposition and postdeposition
doping of ultrathin PEDOT films has demonstrated conductivities of >3,000 S cm−1 and an op-
tical figure of merit of >30 (90). These values warrant further investigation of oCVD PEDOT
and indicate a potential for the future low-cost replacement of indium tin oxide (93).
PEDOT electrodes can be coated or printed onto unconventional substrates. These include
not only flexible plastic foils but also paper, elastomers, and textiles. The conformal and substrate-
independent character of oCVD has already contributed to novel technologies, such as paper solar
cells (94) and conductive textiles (8). For example, lightweight paper OPV could significantly
reduce system costs associated with standard photovoltaic technologies [balance of system can
reach up to ∼5× the module price (23)], facilitating deployment of low-cost solar cells in the
developing world. Electronic textiles, however, could open up a new innovation frontier, ranging
from functionalized, everyday fabrics for energy generation/storage to intelligent clothing for
health monitoring. Kovacik et al. (8) recently explored oCVD printing of large-area patterned
PEDOT textiles, as shown in Figure 4f,g. Although the conductivity of these textiles was among
the highest for polymer-based imprints, the unique conformality of the coatings did not alter
the textile microstructure and fully preserved its original functionality. The excellent coating
durability was demonstrated through a test in which the conductive textile resisted severe twisting
and stretching cycles without deterioration of the performance. This work illustrated low-cost
printing of conductive patterns across large textile areas, providing another example of CVD
polymers contributing to the development of future electronics.
382 Chen et al.

a b c
20 nm 20 nm
Silicon PEDOT Cap PEDOT

10 nm
40
e d
High temperature
Distribution (%)
30 Low temerature
20
10
0
1 2 3 4 5 6 7 8 9 10
Domain size (nm)
5 nm
f g
Figure 4
High-angle annular dark field (HAADF) images with scanning transmission electron microscopy (STEM) of
cross-sections of PEDOT films grown at (a) 100◦ C and (b) 200◦ C. The top halves of both images are color
enhanced to emphasize the crystalline domains surrounded by an amorphous matrix. (c–d ) High-resolution
images for the film synthesized at 200◦ C. (e) Histogram of statistical domain size distribution obtained from
images a and b. ( f,g) Patterning and modification of imprint coverage of conductive PEDOT on a t-shirt
demonstrating the suitability of oxidative chemical vapor deposition (oCVD) in smart clothing. (a–e)
Reprinted with permission from Reference 90, 2015
c Wiley. ( f,g) Reprinted with permission from
Reference 8, 2015
c R. Soc. Chem.
oCVD semiconductors form another class of attractive conjugated polymers. In the past few
years, different research groups have demonstrated synthesis of light-absorbing polymer films and
their application as active layers in solar cells (95, 96) and electrochromic windows (97). These
polymers, such as polythiophene (PT) and polyselenophene, are interesting primarily owing to
their unsubstituted character. The oCVD process allows their transformation into functional thin
films without the need for soluble side groups and thus provides a unique opportunity for study of
their fundamental backbone properties. For instance, Borrelli et al. (21) fabricated OTFTs with
PT as the active channel layer to explore its charge transport properties and potential in micro-
electronic applications. Moderate mobilities (µFET < 4 × 10−3 cm2 V−1 s−1 ) indicated structural
defects, likely coming from irregular monomer linkages. Although this made the PT OTFT
performance comparable to that of their regiorandom solution-processed poly(3-hexylthiophene)
(P3HT) counterparts, the device characteristics were inferior to those based on regioregular P3HT
(mobilities up to 10−1 cm2 V−1 s−1 ) (98). To note, the oCVD polymers are synthesized in a highly
doped state; hence, a dedoping step (rinsing with methanol) was necessary to reduce the carrier
density in PT to suitable OTFT levels (1016 –1017 cm−3 ).
Microelectronic devices and their performance are also defined by the thin-film interfaces and
dielectric layers separating different conducting parts from one another. iCVD has demonstrated
excellent potential in this area, allowing for the deposition of extremely thin films of low-k di-
electrics (k ∼ 2.2) with desirable uniformity and conformality (99). Moon et al. (9) applied thin
layers of poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane) (pV3D3) across different device ar-
chitectures to illustrate its deposition versatility and good insulating properties (Figure 5a). For
example, thin (∼10-nm) layers of pV3D3 sandwiched between Al electrodes exhibited current leak-
age densities as low as 10−8 –10−9 A cm−2 , showing their suitability for low-power electronics. Such
insulating properties and sub-10-nm-thickness control render this polymer deposition competitive
even to thermally grown SiO2 or atomic layer deposition–grown separators. This likely comes as a
result of the solvent-free character of iCVD and consequential low density of defects and pinholes.
To demonstrate the feasibility of pV3D3 as a gate dielectric, Moon et al. fabricated bottom-
gate OTFTs with ideal hysteresis-free transfer characteristics (with µFET = 1.3 cm2 V−1 s−1
and on/off ratios >105 , using C60 as a channel layer). Moreover, low-temperature growth and
substrate independence allowed for fabrication of top-gate OTFTs onto various channel materi-
als, including process-sensitive indium gallium zinc oxide. Finally, mechanical flexibility is one of
the key advantages of polymer-based dielectrics—here, the pV3D3 film withstood tensile strain up
to 4% (bending radius ∼1.5 mm), confirming its compatibility with soft electronics. Seong et al.
showed in the follow-up study that a brief oxygen plasma treatment turns the surface of pV3D3 into
a capping SiOx layer, improving the thermal stability and applicability of the dielectric layer (20).
The ubiquitous character of CVD polymer films also has been used in sensing technologies.
Different mechanisms have been explored in recent years, such as resistive sensing of volatile
organic compounds (100) or swelling response to nitroaromatics (101). Mehrabani et al. (102)
employed a moisture-sensitive iCVD film of pNIPAAm to enhance response of a microcavity op-
tical humidity sensor. Such optical sensors are preferred in industrial environments owing to their
immunity to electrical and vibrational noise. The polymer coating of the optical cavity underwent
conformal change upon exposure to humidity, resulting in a change in refracting index and in
the cavity’s diameter. This led to a significantly increased optical response (∼ ×102 ) for coatings
only ∼50 nm thick. The substrate (or shape) independence of iCVD/oCVD deposition thus holds
a potential for improving already-established technologies, especially those incompatible with
solvent-based thin-film deposition.
Charge storage has become one of the most prominent areas of CVD polymer application. For
example, iCVD films with ion-conduction capability have been proposed as solid-state electrolytes
384 Chen et al.

a
Al
pV3D3 ~11 nm
Al
20 nm 100 nm
R = 2.0 mm
R = 1.5 mm
dsub = 125 μm
b 2,000
C
Li+
Rs
1,500 ClO4–
Li+
ClO4–
–Z'' (Ω)
Rp ClO4–
1,000
Li+
500
0
0 500 1,000 1,500 2,000
Z' (Ω)
Figure 5
(a, top) Cross-sectional HRTEM image of Al/pV3D3/Al metal-insulator-metal (MIM) device with
11-nm-thick layer of dielectric pV3D3. (bottom) Al/pV3D3/Al MIM devices (PV3D3 ∼20 nm) fabricated on
PET substrates during tensile (left) and compressive (right) bending tests. Reprinted with permission from
Reference 9, 2015
c Nat. Publ. Group. (b) Electrochemical impedance spectra of lithiated 25-nm pV4D4
films, with the semicircles indicating ionic conduction in pV4D4. The frequency range was 100 kHz–
100 Hz, with a 10-mV (RMS) potential. The circuits used for equivalent circuit fitting are also shown. (inset)
pV4D4 structure after lithiation. Reprinted with permission from Reference 24, 2015
c R. Soc. Chem.

for electrochemical storage, particularly batteries. In the first such demonstration, Chen et al. (24)
showed that pV4D4 thin films (20–40 nm) can be doped with Li+ to achieve ionic conductivities up
to 10−8 S cm−1 (Figure 5b). This polymer electrolyte can be coated onto complex 3D electrodes,
allowing for an increased energy density of storage, compared with conventional planar battery
designs. Meanwhile, a thin, conformal, and uniform pV4D4 layer maintains short ionic transport
distances necessary for high power densities. The iCVD electrolytes could therefore be a suitable
strategy for fabrication of these challenging 3D-battery architectures.
Supercapacitors are an alternative technology to batteries, attractive mainly owing to rapid
charging rates as well as high-capacity storage and improved cycle stability (103). In a standard
electric double-layer capacitor, charges are stored at the surface of the electrode in the form of a
charge double layer. Such electrodes consist preferentially of highly porous materials, often CNTs
or graphene flakes, which can store a high density of charges. However, the electric double-layer
capacitor storage capacity of the electrode-electrolyte interface can be further enhanced by a layer
of conductive polymer, allowing pseudocapacitive charge storage throughout its volume. Lachman
et al. (103a) demonstrated such enhancement, coating CNT-forest electrodes with conductive
oCVD PEDOT. The specific capacitance increased with increasing thickness of the PEDOT
coating (0–10 nm), and so did the energy and power density. The same approach was used in full
device configurations with graphene flakes (105) and CNTs as positive electrodes (104). Nejati
et al. (106) used the concept simultaneously, using oCVD PT coatings for conformal treatment
of nanoporous electrodes based on activated C, AAO, and TiO2 .
PROTECTIVE LAYERS
As a versatile tool CVD provides functional and conformal coatings on various substrates, including
surfaces with complex geometries (e.g., arrays of high aspect ratio) (2, 24). Thus, CVD thin films
can be used as protective layers for surfaces and devices (107–109).
In the recent progress of protective films, inorganic-organic hybrid encapsulations using iCVD
polymers have been applied to OPV devices (107) and other organic devices (110). As shown in
Figure 6a,b, the bilayer encapsulation containing UV-screening inorganic layer of CeO2 and
iCVD pDVB significantly reduced the degradation of top-illuminated OPV devices (107). Also,
Chen et al. (109) showed that iCVD polymers can be applied alone as a fast protection method
for flexible organic electrodes like PEDOT (Figure 6c). Kim et al. (110) showed a combination
of iCVD pV4D4 and ALD Al2 O3 can reduce water vapor transmission rate (WVTR) as low
as 1.29 × 10−5 g (m2 · day) in ambient conditions, which is sufficient to extend the lifetime of
organic devices. By PECVD, Qi et al. (108) used a SiOx /PET encapsulation layer to protect OPV
devices and achieved a half-life of more than 500 h (Figure 6d,e). iCVD polymers also show good
water resistance and stability. In a recent study of iCVD polymer-intercalated resistive random
access memory (i-RRAM), highly crosslinked poly(ethylene glycol dimethacrylate) (pEGDMA)
was applied as a resistive switching layer. Owing to the high water stability of the pEGDMA,
the iCVD-fabricated i-RRAM showed robust flexibility and stable operation, even under water
(111). Besides encapsulation, CVD-based protective films were also used in the passivation of
silicon. In fabrication of silicon solar cells, passivation of silicon to reduce the recombination of
minority carriers is very important to improve photovoltaic efficiency. Silicon nitride (SiNx ), a
SiO2 /SiNx combination, and iCVD organic vapors have been explored recently in this area (57,
112, 113). Figure 6f shows a room-temperature passivation method of silicon achieved by Yang
et al. (57) using iCVD organic vapors. Using tert-butyl peroxide and 1,9-decadiene vapors, this
novel organic iCVD passivation achieved a surface recombination velocity less than 10 cm s−1 while
retaining the substrate temperature at room temperature, which is highly desired in fabrication
386 Chen et al.

Figure 6
a b
1.0 PDVB/CeO2 Recent chemical vapor
CeO2 500 nm/0
Encapsulation deposited (CVD)
250 nm/25 nm
PDVB encapsulations.
PDVB/MoO3
PEDOT 500 nm/50 nm (a,b) Initiated CVD
Normalized PCE
No encapsulation (iCVD) bilayer
MoO3
encapsulation on
DBP
Device organic photovoltaic
C60 0.5 (OPV) devices, which
Ag extends the lifetime of
Glass the device up to five
times. Reprinted with
permission from
c Reference 105, 2015
c
0.0 Wiley. (c) Fast iCVD

0.23 µm 0.23 µm
0 100 200 conformal
20 50 65 96 encapsulation for
Time (h) flexible electrodes.

Reprinted with
0.22 µm
permission from
e Reference 107, 2014
c
1.0
Elsevier. (d,e) SiOx
0.21 µm encapsulation by
Normalized values
0.8 Plasma enhanced

1 µm
CVD (PECVD) on
0.6 OPVs. The half-life of
the encapsulated
d 0.4 device exceeded 500 h.
JSC
PET + barrier
VOC Reprinted with
Ag FF permission from
0.2
PEDOT Eff Reference 106, 2014
c
P3HT: PCBM Elsevier. ( f ) Room-
Glue Glue 0.0
Al2O3 0 100 200 300 400 500 600 temperature iCVD
ITO Aging period (h) passivation of silicon
Glass using organic vapors
PET + barrier instead of silicon
nitride or oxide.
TBPO Reprinted with
Decadiene
O permission from
O
f Reference 54, 2013
c
iCVD chamber
Transfer Wiley.
SiO4 H H H H into iCVD Pump Pump
HF chamber down down Repeat × 5
Si Si ...
Process A
TBPO O EGDA
O
O O
O O
iCVD chamber PEGDA
PEGDA
Si Si
Traditional iCVD Si
polymerization
Process B

of temperature-sensitive devices. SiNx films have been a dominant surface passivation method in
the photovoltaics industry (114). Recently, Bonilla et al. (113) applied a SiO2 /SiNx double-layer
passivation and achieved a surface recombination velocity of less than 2 cm/s. This work also
provides direct measurements of the location and concentration of charge in the double-layer
structure, suggesting a strategy to achieve charge engineering (115, 116).
CONCLUSION
In summary, CVD methods enable direct chemical synthesis and thin-film formation in a single
step. Unlike solution-based methods, monomeric reactants in the CVD process do not need to be
soluble, and impacts associated with using solvents are avoided. Among different CVD methods,
the full-degree retention of the organic functional group in the iCVD process is highly desired in
many applications, such as surface modification and device fabrication. The chemical and biological
specificity imparted by these organic functional groups differentiates iCVD polymers from their
inorganic CVD counterparts.
In CVD processes, contiguous films can be obtained with controlled thickness as low as
<10 nm, and high-growth-rate conditions (>1 µm/min) can be achieved to deposit films with
micrometer thickness. Also, CVD films can be deposited in a uniform and conformal manner,
even on a substrate with complicated geometry. The facile tunability of the film and surface prop-
erties has allowed the successful integration of CVD polymers into prototypes for applications
including, but not limited to, surface engineering, device fabrication, and protective films. In this
review, we summarized recent progress in the use of iCVD thin films on antifouling, anti-icing, an-
tihydrate, dropwise, and biomass extraction coatings, as well as the synthesis of stimuli-responsive
and biocompatible polymers. We also reviewed the recent development of conducting and semi-
conducting polymers, which can be used in electronics, including low-k dielectrics and electrolytes
in batteries. Finally, we discussed CVD thin films used as device/surface protection and silicon
passivation layers. Ultimately, the precisely controlled vacuum deposition and the potential for
reproducible processing and scale-up are keys to the commercial success of CVD technologies
and will be essential to their further development.
DISCLOSURE STATEMENT
One author, K.K. Gleason, has financial interests in GVD Corporation and Dropwise Technology
Corporation, both of which utilize CVD polymer technology.
ACKNOWLEDGMENTS
The authors acknowledge financial support from the National Science Foundation under Grant
No. 1344891, MIT Institute for Soldier Nanotechnologies (ISN) under Contract DAAD-19-
02D-0002 with the U.S. Army Research Office, the Office of Naval Research under Contract
N00014-13-1-0466, the Chevron-MIT Energy Initiative Program, Eni S.p.A. under the Eni-
MIT Alliance Solar Frontiers Program, and Kuwait-MIT Center for Natural Resources and the
Environment (CNRE).
LITERATURE CITED
1. Alf ME, Asatekin A, Barr MC, Baxamusa SH, Chelawat H, et al. 2010. Chemical vapor deposition of
conformal, functional, and responsive polymer films. Adv. Mater. 22:1993–2027
388 Chen et al.

2. Coclite AM, Howden RM, Borrelli DC, Petruczok CD, Yang R, et al. 2013. 25th anniversary article:
CVD polymers: a new paradigm for surface modification and device fabrication. Adv. Mater. 25:5392–
423
3. Reeja-Jayan B, Kovacik P, Yang R, Sojoudi H, Ugur A, et al. 2014. A route towards sustainability
through engineered polymeric interfaces. Adv. Mater. Interfaces 1:1400117
4. Gupta M, Gleason KK. 2006. Large-scale initiated chemical vapor deposition of poly(glycidyl methacry-
late) thin films. Thin Solid Films 515:1579–84
5. Baxamusa SH, Gleason KK. 2008. Thin polymer films with high step coverage in microtrenches by
initiated CVD. Chem. Vap. Depos. 14:313–18
6. Yoo G, Yoo Y, Kwon J-H, Darpito C, Mishra SK, et al. 2013. An effective, cost-efficient extraction
method of biomass from wet microalgae with a functional polymeric membrane. Green Chem. 16:312–19
7. Lewis HGP, Bansal NP, White AJ, Handy ES. 2009. HWCVD of polymers: commercialization and
scale-up. Thin Solid Films 517:3551–54
8. Kovacik P, del Hierro G, Livernois W, Gleason KK. 2015. Scale-up of oCVD: large-area conductive
polymer thin films for next-generation electronics. Mater. Horiz. 2:221–27
9. Moon H, Seong H, Shin WC, Park W-T, Kim M, et al. 2015. Synthesis of ultrathin polymer insulating
layers by initiated chemical vapour deposition for low-power soft electronics. Nat. Mater. 14:628–35
10. Coclite AM, Gleason KK. 2012. Initiated PECVD of organosilicon coatings: a new strategy to enhance
monomer structure retention. Plasma Process. Polym. 9:425–34
11. Pfluger CA, Carrier RL, Sun B, Ziemer KS, Burkey DD. 2009. Cross-linking and degradation proper-
ties of plasma enhanced chemical vapor deposited poly(2-hydroxyethyl methacrylate). Macromol. Rapid
Commun. 30:126–32
12. Chang Y-C, Frank CW. 1998. Vapor deposition–polymerization of α-amino acid N-carboxy anhydride
on the silicon (100) native oxide surface. Langmuir 14:326–34
13. Lock JP, Im SG, Gleason KK. 2006. Oxidative chemical vapor deposition of electrically conducting
poly(3,4-ethylenedioxythiophene) films. Macromolecules 39:5326–29
14. Winther-Jensen B, West K. 2004. Vapor-phase polymerization of 3,4-ethylenedioxythiophene: a route
to highly conducting polymer surface layers. Macromolecules 37:4538–43
15. George SM, Yoon B, Hall RA, Abdulagatov AI, Gibbs ZM, et al. 2011. Molecular layer deposition of
hybrid organic–inorganic films. In Atomic Layer Deposition of Nanostructured Materials, ed. N Pinna, M
Knez, pp. 83–107. Weinheim, Ger.: Wiley-VCH Verlag GmbH & Co. KGaA
16. Zhou H, Bent SF. 2013. Fabrication of organic interfacial layers by molecular layer deposition: present
status and future opportunities. J. Vac. Sci. Technol. A 31:040801
17. Atanasov SE, Losego MD, Gong B, Sachet E, Maria J-P, et al. 2014. Highly conductive and conformal
poly(3,4-ethylenedioxythiophene) (PEDOT) thin films via oxidative molecular layer deposition. Chem.
Mater. 26:3471–78
18. Zhou Y, Xu H, Lachman N, Ghaffari M, Wu S, et al. 2014. Advanced asymmetric supercapacitor based
on conducting polymer and aligned carbon nanotubes with controlled nanomorphology. Nano Energy
9:176–85
19. Ozaydin-Ince G, Coclite AM, Gleason KK. 2012. CVD of polymeric thin films: applications in sen-
sors, biotechnology, microelectronics/organic electronics, microfluidics, MEMS, composites and mem-
branes. Rep. Prog. Phys. 75:016501
20. Seong H, Baek J, Pak K, Im SG. 2015. A surface tailoring method of ultrathin polymer gate dielectrics
for organic transistors: improved device performance and the thermal stability thereof. Adv. Funct.
Mater. 25:4462–69
21. Borrelli DC, Lee S, Gleason KK. 2014. Optoelectronic properties of polythiophene thin films and
organic TFTs fabricated by oxidative chemical vapor deposition. J. Mater. Chem. C 2:7223–31
22. Wang F, Kozawa D, Miyauchi Y, Hiraoka K, Mouri S, et al. 2015. Considerably improved photovoltaic
performance of carbon nanotube-based solar cells using metal oxide layers. Nat. Commun. 6:6305
23. Jean J, Brown PR, Jaffe RL, Buonassisi T, Bulovic V. 2015. Pathways for solar photovoltaics. Energy
Environ. Sci. 8:1200–19
24. Chen N, Reeja-Jayan B, Lau J, Moni P, Liu AD, et al. 2015. Nanoscale, conformal polysiloxane thin
film electrolytes for three-dimensional battery architectures. Mater. Horiz. 2:309–14

25. Zamfir MR, Hung Tran N, Moyen E, Lee YH, Pribat D. 2013. Silicon nanowires for Li-based battery
anodes: a review. J. Mater. Chem. A 1:9566–86
26. Banerjee I, Pangule RC, Kane RS. 2011. Antifouling coatings: recent developments in the design of
surfaces that prevent fouling by proteins, bacteria, and marine organisms. Adv. Mater. 23:690–718
27. Elimelech M, Phillip WA. 2011. The future of seawater desalination: energy, technology, and the
environment. Science 333:712–17
28. Tsai MY, Chen YC, Lin TJ, Hsu YC, Lin CY, et al. 2014. Vapor-based multicomponent coatings for
antifouling and biofunctional synergic modifications. Adv. Funct. Mater. 24:2281–87
29. Bose RK, Nejati S, Stufflet DR, Lau KKS. 2012. Graft polymerization of anti-fouling PEO surfaces by
liquid-free initiated chemical vapor deposition. Macromolecules 45:6915–22
30. Amadei CA, Yang R, Chiesa M, Gleason KK, Santos S. 2014. Revealing amphiphilic nanodomains of
anti-biofouling polymer coatings. ACS Appl. Mater. Interfaces 6:4705–12
31. Baxamusa SH, Gleason KK. 2009. Random copolymer films with molecular-scale compositional het-
erogeneities that interfere with protein adsorption. Adv. Funct. Mater. 19:3489–96
32. Martin TP, Kooi SE, Chang SH, Sedransk KL, Gleason KK. 2007. Initiated chemical vapor deposition
of antimicrobial polymer coatings. Biomaterials 28:909–15
33. Yang R, Jang H, Stocker R, Gleason KK. 2014. Synergistic prevention of biofouling in seawater desali-
nation by zwitterionic surfaces and low-level chlorination. Adv. Mater. 26:1711–18
34. Yang R, Gleason KK. 2012. Ultrathin antifouling coatings with stable surface zwitterionic functionality
by initiated chemical vapor deposition (iCVD). Langmuir 28:12266–74
35. Yang R, Xu J, Ozaydin-Ince G, Wong SY, Gleason KK. 2011. Surface-tethered zwitterionic ultrathin
antifouling coatings on reverse osmosis membranes by initiated chemical vapor deposition. Chem. Mater.
23:1263–72
36. Jiang S, Cao Z. 2010. Ultralow-fouling, functionalizable, and hydrolyzable zwitterionic materials and
their derivatives for biological applications. Adv. Mater. 22:920–32
37. Baxamusa SH, Im SG, Gleason KK. 2009. Initiated and oxidative chemical vapor deposition: a scalable
method for conformal and functional polymer films on real substrates. Phys. Chem. Chem. Phys. 11:5227–
40
38. Shafi HZ, Khan Z, Yang R, Gleason KK. 2015. Surface modification of reverse osmosis membranes
with zwitterionic coating for improved resistance to fouling. Desalination 362:93–103
39. Quintana R, Gosa M, Jańczewski D, Kutnyanszky E, Vancso GJ. 2013. Enhanced stability of low fouling
zwitterionic polymer brushes in seawater with diblock architecture. Langmuir 29:10859–67
40. Petruczok CD, Yang R, Gleason KK. 2013. Controllable cross-linking of vapor-deposited polymer thin
films and impact on material properties. Macromolecules 46:1832–40
41. Yang R, Goktekin E, Wang MH, Gleason KK. 2014. Molecular fouling resistance of zwitterionic
and amphiphilic initiated chemically vapor-deposited (iCVD) thin films. J. Biomater. Sci. Polym. Ed.
25:1687–702
42. Yang R, Moni P, Gleason KK. 2015. Ultrathin zwitterionic coatings for roughness-independent un-
derwater superoleophobicity and gravity-driven oil-water separation. Adv. Mater. Interfaces 2:1400489
43. Ye Y, Song Q, Mao Y. 2011. Single-step fabrication of non-leaching antibacterial surfaces using vapor
crosslinking. J. Mater. Chem. 21:257–62
44. Alizadeh A, Bahadur V, Kulkarni A, Yamada M, Ruud JA. 2013. Hydrophobic surfaces for control and
enhancement of water phase transitions. MRS Bull. 38:407–11
45. Kim P, Wong T-S, Alvarenga J, Kreder MJ, Adorno-Martinez WE, Aizenberg J. 2012. Liquid-infused
nanostructured surfaces with extreme anti-ice and anti-frost performance. ACS Nano 6:6569–77
46. Liu Z, Gou Y, Wang J, Cheng S. 2008. Frost formation on a super-hydrophobic surface under natural
convection conditions. Int. J. Heat Mass Transf. 51:5975–82
47. Andrews RW, Pollard A, Pearce JM. 2013. A new method to determine the effects of hydrodynamic
surface coatings on the snow shedding effectiveness of solar photovoltaic modules. Sol. Energy Mater.
Sol. Cells 113:71–78
48. Dalili N, Edrisy A, Carriveau R. 2009. A review of surface engineering issues critical to wind turbine
performance. Renew. Sustain. Energy Rev. 13:428–38
390 Chen et al.

49. Menini R, Ghalmi Z, Farzaneh M. 2011. Highly resistant icephobic coatings on aluminum alloys. Cold
Reg. Sci. Technol. 65:65–69
50. Parent O, Ilinca A. 2011. Anti-icing and de-icing techniques for wind turbines: critical review. Cold Reg.
Sci. Technol. 65:88–96
51. Lai JX, Liu C, Gong CB. 2011. Research situation and prospect for highway snowmelt deicing tech-
nology with electric heat tracing. In Frontiers of Green Building, Materials and Civil Engineering, Parts
1–8, ed. D Sun, WP Sung, R Chen, pp. 1865–69. Stäfa-Zurich: Trans Tech Publ. Ltd.
52. Laforte JL, Allaire MA, Laflamme J. 1998. State-of-the-art on power line de-icing. Atmos. Res. 46:143–58
53. Frankenstein S, Tuthill AM. 2002. Ice adhesion to locks and dams: past work; future directions? J. Cold
Reg. Eng. 16:83–96
54. Alizadeh A, Yamada M, Li R, Shang W, Otta S, et al. 2012. Dynamics of ice nucleation on water
repellent surfaces. Langmuir 28:3180–86
55. Sojoudi H, McKinley GH, Gleason KK. 2015. Linker-free grafting of fluorinated polymeric cross-
linked network bilayers for durable reduction of ice adhesion. Mater. Horiz. 2:91–99
56. Paxson AT, Yaguee JL, Gleason KK, Varanasi KK. 2014. Stable dropwise condensation for enhancing
heat transfer via the initiated chemical vapor deposition (iCVD) of grafted polymer films. Adv. Mater.
26:418–23
57. Yang R, Buonassisi T, Gleason KK. 2013. Organic vapor passivation of silicon at room temperature.
Adv. Mater. 25:2078–83
58. Coclite AM, Shi YJ, Gleason KK. 2012. Grafted crystalline poly-perfluoroacrylate structures for super-
hydrophobic and oleophobic functional coatings. Adv. Mater. 24:4534–39
59. Liu A, Goktekin E, Gleason KK. 2014. Cross-linking and ultrathin grafted gradation of fluorinated
polymers synthesized via initiated chemical vapor deposition to prevent surface reconstruction. Lang-
muir 30:14189–94
60. Sojoudi H, Walsh MR, Gleason KK, McKinley GH. 2015. Investigation into the formation and adhesion
of cyclopentane hydrates on mechanically robust vapor-deposited polymeric coatings. Langmuir ACS
J. Surf. Colloids 31:6186–96
61. Lee B, Jiao A, Yu S, You JB, Kim D-H, Im SG. 2013. Initiated chemical vapor deposition of thermore-
sponsive poly(N-vinylcaprolactam) thin films for cell sheet engineering. Acta Biomaterialia 9:7691–98
62. Kwong P, Seidel S, Gupta M. 2013. Solventless fabrication of porous-on-porous materials. ACS Appl.
Mater. Interfaces 5:9714–18
63. Sojoudi H, Walsh MR, Gleason KK, McKinley GH. 2015. Designing durable vapor-deposited surfaces
for reduced hydrate adhesion. Adv. Mater. Interfaces 2:1500003
64. Zhang Q, He M, Zeng X, Li K, Cui D, et al. 2012. Condensation mode determines the freezing of
condensed water on solid surfaces. Soft Matter 8:8285–88
65. Dorrer C, Ruehe J. 2007. Condensation and wetting transitions on microstructured ultrahydrophobic
surfaces. Langmuir 23:3820–24
66. Wier KA, McCarthy TJ. 2006. Condensation on ultrahydrophobic surfaces and its effect on droplet
mobility: Ultrahydrophobic surfaces are not always water repellant. Langmuir 22:2433–36
67. Armagan E, Qureshi P, Ince GO. 2015. Functional nanotubes for triggered release of molecules. Nanosci.
Nanotechnol. Lett. 7:79–83
68. Petruczok CD, Armagan E, Ince GO, Gleason KK. 2014. Initiated chemical vapor deposition and light-
responsive cross-linking of poly(vinyl cinnamate) thin films. Macromol. Rapid Commun. 35:1345–50
69. Demiryürek R, Ali MK, Ince GO. 2014. A facile method for fabrication of responsive micropatterned
surfaces. Smart Mater. Struct. 23:095020
70. Seidel S, Kwong P, Gupta M. 2013. Simultaneous polymerization and solid monomer deposition for
the fabrication of polymer membranes with dual-scale porosity. Macromolecules 46:2976–83
71. Ye Y, Mao Y, Wang H, Ren Z. 2012. Hybrid structure of pH-responsive hydrogel and carbon nanotube
array with superwettability. J. Mater. Chem. 22:2449–55
72. Bally F, Cheng K, Nandivada H, Deng X, Ross AM, et al. 2013. Co-immobilization of biomolecules
on ultrathin reactive chemical vapor deposition coatings using multiple click chemistry strategies.
ACS Appl. Mater. Interfaces 5:9262–68

73. Ince GO, Armagan E, Erdogan H, Buyukserin F, Uzun L, Demirel G. 2013. One-dimensional surface-
imprinted polymeric nanotubes for specific biorecognition by initiated chemical vapor deposition
(iCVD). ACS Appl. Mater. Interfaces 5:6447–52
74. Seidel S, Cheong CC, Kwong P, Gupta M. 2015. All-dry fabrication of poly(methacrylic acid)-based
membranes with controlled dissolution behavior. Macromol. Mater. Eng. 300:1079–84
75. Tao R, Anthamatten M. 2013. Porous polymers by controlling phase separation during vapor deposition
polymerization. Macromol. Rapid Commun. 34:1755–60
76. Tao R, Anthamatten M. 2012. Condensation and polymerization of supersaturated monomer vapor.
Langmuir 28:16580–87
77. Haller PD, Gupta M. 2014. Synthesis of polymer nanoparticles via vapor phase deposition onto liquid
substrates. Macromol. Rapid Commun. 35:2000–4
78. Petruczok CD, Chen N, Gleason KK. 2014. Closed batch initiated chemical vapor deposition of ultra-
thin, functional, and conformal polymer films. Langmuir 30:4830–37
79. Kim DH, Atanasov SE, Lemaire P, Lee K, Parsons GN. 2015. Platinum-free cathode for dye-sensitized
solar cells using poly(3,4-ethylenedioxythiophene) (PEDOT) formed via oxidative molecular layer de-
position. ACS Appl. Mater. Interfaces 7:3866–70
80. Nejati S, Patel A, Wallowitch GR, Lau KKS. 2015. Electrical conductivity and stability of oxidative
chemical vapor deposition copolymer thin films of thiophene and pyrrole. Nanosci. Nanotechnol. Lett.
7:50–55
81. Bharamaiah Jeevendrakumar VJ, Altemus BA, Gildea AJ, Bergkvist M. 2013. Thermal properties of
poly(neopentylmethacrylate) thin films deposited via solventless, radical initiated chemical vapor depo-
sition. Thin Solid Films 542:81–86
82. Jeevendrakumar VJB, Pascual DN, Bergkvist M. 2015. Wafer scale solventless adhesive bonding with
iCVD polyglycidylmethacrylate: effects of bonding parameters on adhesion energies. Adv. Mater. In-
terfaces 2:1500076
83. Kwak MJ, Oh MS, Yoo Y, You JB, Kim J, et al. 2015. Series of liquid separation system made of
homogeneous copolymer films with controlled surface wettability. Chem. Mater. 27:3441–49
84. Kim J, Oh MS, Choi C-H, Kang S-M, Kwak MJ, et al. 2015. Three-dimensional clustering of Janus
cylinders by convex curvature and hydrophobic interactions. Soft Matter 11:4952–61
85. Kwong P, Seidel S, Gupta M. 2015. Effect of transition metal salts on the initiated chemical vapor
deposition of polymer thin films. J. Vac. Sci. Technol. A 33:031504
86. Cicoira F, Santato C. 2013. Organic Electronics: Emerging Concepts and Technologies. Hoboken, NJ: John
Wiley & Sons
87. So F. 2009. Organic Electronics: Materials, Processing, Devices and Applications. Boca Raton, FL: CRC
Press
88. Elschner A, Kirchmeyer S, Lovenich W, Merker U, Reuter K. 2010. PEDOT: Principles and Applications
of an Intrinsically Conductive Polymer. Boca Raton, FL: CRC Press
89. Bhattacharyya D, Howden RM, Borrelli DC, Gleason KK. 2012. Vapor phase oxidative synthesis of
conjugated polymers and applications. J. Polym. Sci. B Polym. Phys. 50:1329–51
90. Ugur A, Katmis F, Li M, Wu L, Zhu Y, et al. 2015. Low-dimensional conduction mechanisms in highly
conductive and transparent conjugated polymers. Adv. Mater. 27:4604–10
91. Lee S, Paine DC, Gleason KK. 2014. Heavily doped poly(3,4-ethylenedioxythiophene) thin films with
high carrier mobility deposited using oxidative CVD: conductivity stability and carrier transport. Adv.
Funct. Mater. 24:7187–96
91a. Howden RM, McVay ED, Gleason KK. 2013. oCVD poly(3,4-ethylenedioxythiophene) conductivity
and lifetime enhancement via acid rinse dopant exchange. J. Mater. Chem. A 1:1334–40
92. Goktas H, Wang X, Ugur A, Gleason KK. 2015. Water-assisted vapor deposition of PEDOT thin film.
Macromol. Rapid Commun. 36:1283–89
93. Ellmer K. 2012. Past achievements and future challenges in the development of optically transparent
electrodes. Nat. Photonics 6:808–16
94. Barr MC, Rowehl JA, Lunt RR, Xu JJ, Wang AN, et al. 2011. Direct monolithic integration of organic
photovoltaic circuits on unmodified paper. Adv. Mater. 23:3500–5
392 Chen et al.

95. Borrelli DC, Barr MC, Bulovic V, Gleason KK. 2012. Bilayer heterojunction polymer solar cells us-
ing unsubstituted polythiophene via oxidative chemical vapor deposition. Sol. Energy Mater. Sol. Cells
99:190–96
96. Jo WJ, Borrelli DC, Gleason KK. 2015. Photovoltaic effect by vapor-printed polyselenophene. Org.
Electron. 26:55–60
97. Nejati S, Lau KKS. 2011. Chemical vapor deposition synthesis of tunable unsubstituted polythiophene.
Langmuir 27:15223–29
98. Zaumseil J. 2014. P3HT and other polythiophene field-effect transistors. In P3HT Revisited—From
Molecular Scale to Solar Cell Devices, ed. S Ludwigs, pp. 107–37. Berlin: Springer-Verlag
99. Trujillo NJ, Wu QG, Gleason KK. 2010. Ultralow dielectric constant tetravinyltetramethylcyclote-
trasiloxane films deposited by initiated chemical vapor deposition (iCVD). Adv. Funct. Mater. 20:607–16
100. Vaddiraju S, Gleason KK. 2010. Selective sensing of volatile organic compounds using novel conducting
polymer-metal nanoparticle hybrids. Nanotechnology 21:125503
101. Petruczok CD, Choi HJ, Yang SY, Asatekin A, Gleason KK, Barbastathis G. 2013. Fabrication of a
microscale device for detection of nitroaromatic compounds. J. Microelectromech. Syst. 22:54–61
102. Mehrabani S, Kwong P, Gupta M, Armani AM. 2013. Hybrid microcavity humidity sensor. Appl. Phys.
Lett. 102:241101
103. Yang PH, Mai WJ. 2014. Flexible solid-state electrochemical supercapacitors. Nano Energy 8:274–90
103a. Lachman N, Xu H, Zhou Y, Ghaffari M, Lin M, et al. 2014. Tailoring thickness of conformal conduct-
ing polymer decorated aligned carbon nanotube electrodes for energy storage. Adv. Mater. Interfaces
1:1400076
104. Zhou Y, Xu HP, Lachman N, Ghaffari M, Wu S, et al. 2014. Advanced asymmetric supercapacitor
based on conducting polymer and aligned carbon nanotubes with controlled nanomorphology. Nano
Energy 9:176–85
105. Zhou Y, Lachman N, Ghaffari M, Xu HP, Bhattacharya D, et al. 2014. A high performance hybrid
asymmetric supercapacitor via nano-scale morphology control of graphene, conducting polymer, and
carbon nanotube electrodes. J. Mater. Chem. A 2:9964–69
106. Nejati S, Minford TE, Smolin YY, Lau KKS. 2014. Enhanced charge storage of ultrathin polythiophene
films within porous nanostructures. ACS Nano 8:5413–22
107. Chen N, Kovacik P, Howden RM, Wang X, Lee S, Gleason KK. 2015. Low substrate temperature
encapsulation for flexible electrodes and organic photovoltaics. Adv. Energy Mater. 5:1401442
108. Qi L, Zhang C, Chen Q. 2014. Performance improvement of inverted organic solar cells by adding
ultrathin Al2 O3 as an electron selective layer and a plasma enhanced chemical vapor deposition of SiOx
encapsulating layer. Thin Solid Films 567:1–7
109. Chen N, Wang X, Gleason KK. 2014. Conformal single-layer encapsulation of PEDOT at low substrate
temperature. Appl. Surface Sci. 323:2–6
110. Kim BJ, Kim DH, Kang SY, Ahn SD, Im SG. 2014. A thin film encapsulation layer fabricated via
initiated chemical vapor deposition and atomic layer deposition. J. Appl. Polym. Sci. 131:40974
111. Lee B-H, Bae H, Seong H, Lee D-I, Park H, et al. 2015. Direct observation of a carbon filament in
water-resistant organic memory. ACS Nano 9:7306–13
112. Chu Y-H, Lee C-C, Chang T-H, Chang S-Y, Chang J-Y, et al. 2014. Investigation of hydrogenated
amorphous silicon as passivation layer by high density plasma. Thin Solid Films 570(B):591–94
113. Bonilla RS, Reichel C, Hermle M, Wilshaw PR. 2014. On the location and stability of charge in
SiO2 /SiNx dielectric double layers used for silicon surface passivation. J. Appl. Phys. 115:144105
114. Soppe W, Rieffe H, Weeber A. 2005. Bulk and surface passivation of silicon solar cells accomplished
by silicon nitride deposited on industrial scale by microwave PECVD. Prog. Photovolt. 13:551–69
115. Spee DA, Rath JK, Schropp REI. 2015. Using hot wire and initiated chemical vapor deposition for gas
barrier thin film encapsulation. Thin Solid Films 575:67–71
116. Spee DA, Rath JK, Schropp REI. 2013. Polymer layers by initiated CVD for thin film gas barrier
encapsulation. In Encapsulation Nanotechnologies, ed. V Mittal, pp. 255–89. Hoboken, NJ: John Wiley &
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Contents Volume 7, 2016

Neutron Scattering from Polymers: Five Decades of Developing

Possibilities
J.S. Higgins p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Membrane Desalination: Where Are We, and What Can We Learn
from Fundamentals?
Joseph Imbrogno and Georges Belfort p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p29
Multiscale Materials Modeling in an Industrial Environment
Horst Weiß, Peter Deglmann, Pieter J. in ‘t Veld, Murat Cetinkaya,
and Eduard Schreiner p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p65
The Modern Temperature-Accelerated Dynamics Approach
Richard J. Zamora, Blas P. Uberuaga, Danny Perez, and Arthur F. Voter p p p p p p p p p p p p p p87
Charged Polymer Membranes for Environmental/Energy Applications
Jovan Kamcev and Benny D. Freeman p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 111
The Evolution of Process Safety: Current Status and Future Direction
M. Sam Mannan, Olga Reyes-Valdes, Prerna Jain, Nafiz Tamim,
and Monir Ahammad p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 135
Design of Responsive and Active (Soft) Materials Using Liquid Crystals
Emre Bukusoglu, Marco Bedolla Pantoja, Peter C. Mushenheim,
Xiaoguang Wang, and Nicholas L. Abbott p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 163
Thiol-Disulfide Exchange Reactions in the Mammalian Extracellular
Environment
Michael C. Yi and Chaitan Khosla p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 197
A Selection of Recent Advances in C1 Chemistry
Carl Mesters p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 223
The Energy-Water-Food Nexus
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vii
Status of Solid State Lighting Product Development and Future Trends

for General Illumination
Thomas M. Katona, P. Morgan Pattison, and Steve Paolini p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 263
Switchable Materials for Smart Windows
Yang Wang, Evan L. Runnerstrom, and Delia J. Milliron p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 283
Nanoparticle-Based Modulation of the Immune System
Ronnie H. Fang and Liangfang Zhang p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 305
Shape-Controlled Metal Nanocrystals for Heterogeneous Catalysis
Aleksey Ruditskiy, Hsin-Chieh Peng, and Younan Xia p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 327
Computer Simulations of Ion Transport in Polymer Electrolyte

Membranes
Santosh Mogurampelly, Oleg Borodin, and Venkat Ganesan p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 349
Polymer Thin Films and Surface Modification by Chemical Vapor

Deposition: Recent Progress
Nan Chen, Do Han Kim, Peter Kovacik, Hossein Sojoudi, Minghui Wang,
and Karen K. Gleason p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 373
Thermodynamics of Bioreactions
Christoph Held and Gabriele Sadowski p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 395
Complex Fluids and Hydraulic Fracturing
Alexander C. Barbati, Jean Desroches, Agathe Robisson, and Gareth H. McKinley p p p p 415
Biomanufacturing of Therapeutic Cells: State of the Art, Current
Challenges, and Future Perspectives
Kyung-Ho Roh, Robert M. Nerem, and Krishnendu Roy p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 455
Polymer Fluid Dynamics: Continuum and Molecular Approaches
R.B. Bird and A.J. Giacomin p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 479
Progress in the Development of Oxygen Reduction Reaction Catalysts for
Low-Temperature Fuel Cells
Dongguo Li, Haifeng Lv, Yijin Kang, Nenad M. Markovic,
and Vojislav R. Stamenkovic p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 509
The Carbon-Water Interface: Modeling Challenges and Opportunities
for the Water-Energy Nexus
Alberto Striolo, Angelos Michaelides, and Laurent Joly p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 533
New Vistas in Chemical Product and Process Design
Lei Zhang, Deenesh K. Babi, and Rafiqul Gani p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 557
Advances in Nanoimprint Lithography
Matthew C. Traub, Whitney Longsine, and Van N. Truskett p p p p p p p p p p p p p p p p p p p p p p p p p p p 583
viii Contents
Theoretical Heterogeneous Catalysis: Scaling Relationships

and Computational Catalyst Design
Jeffrey Greeley p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 605
Engineering Delivery Vehicles for Genome Editing
Christopher E. Nelson and Charles A. Gersbach p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 637
Lewis Acid Zeolites for Biomass Conversion: Perspectives and Challenges
on Reactivity, Synthesis, and Stability
Helen Y. Luo, Jennifer D. Lewis, and Yuriy Román-Leshkov p p p p p p p p p p p p p p p p p p p p p p p p p p p p 663
Indexes
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Annu. Rev. Chem. Biomol. Eng. 2016. 7:373–93 Keywords

374 Chen et al.

Antibiofouling iCVD Surfaces: Hydrophilic, Amphiphilic, and Zwitterionic,

www.annualreviews.org • Chemical Vapor Deposition 375

copolymerization of a hydrogel-forming monomer and a fluoromonomer, hydroxyethyl

Biomass Extraction Using iCVD Coatings

376 Chen et al.

i. Bare ii. Coated iii. Bare iv. Coated

Microalgal cell Contact with functional Cell disruption and

Durable Anti-Icing, Anti-Hydrate, and Dropwise Condensation:

www.annualreviews.org • Chemical Vapor Deposition 377

378 Chen et al.

pDVB Bare Coated

www.annualreviews.org • Chemical Vapor Deposition 379

copolymer of vinyl cinnamate with N-isopropylacrylamide is also thermoresponsive, which enables

380 Chen et al.

Process Studies and Tuning CVD Polymers

www.annualreviews.org • Chemical Vapor Deposition 381

optoelectronics in general. PEDOT produced by oCVD has demonstrated excellent performance

382 Chen et al.

Silicon PEDOT Cap PEDOT

384 Chen et al.

www.annualreviews.org • Chemical Vapor Deposition 385

386 Chen et al.

0.0 Wiley. (c) Fast iCVD

Time (h) flexible electrodes.

0.8 Plasma enhanced

www.annualreviews.org • Chemical Vapor Deposition 387

388 Chen et al.

www.annualreviews.org • Chemical Vapor Deposition 389

390 Chen et al.

www.annualreviews.org • Chemical Vapor Deposition 391

392 Chen et al.

www.annualreviews.org • Chemical Vapor Deposition 393

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Contents Volume 7, 2016

Neutron Scattering from Polymers: Five Decades of Developing

Status of Solid State Lighting Product Development and Future Trends

Computer Simulations of Ion Transport in Polymer Electrolyte

Polymer Thin Films and Surface Modification by Chemical Vapor

Theoretical Heterogeneous Catalysis: Scaling Relationships

Cumulative Index of Contributing Authors, Volumes 3–7 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 693

Cumulative Index of Article Titles, Volumes 3–7 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 696

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