Hybridized Conducting Polymer Chemiresis

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Nano Today (2013) xxx, xxx—xxx

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REVIEW

Hybridized conducting polymer chemiresistive


nano-sensors
Carlos M. Hangarter a, Nicha Chartuprayoona ,Sandra C. Hernández a,
Yongho Choa b,ÿ
, Nosang V. Myung a,ÿÿ

a Chemical and Environmental Engineering, University of California-Riverside, Riverside, CA 92521, United States
b
Department of Fine Chemical Engineering, Hanyang University, Ansan 426-791, Republic of Korea

Received 13 June 2012; received in revised form 13 November 2012; accepted 26 December 2012

KEYWORDS Summary Conducting polymers, or conjugated polymers, are a class of polymers containing
a sp2 structure that permits delocalized transport of charge carriers. Here these polymers are
Gas sensors;
examined in the context of nanoscale hybridization with carbon nanotubes, graphene, metal
Conducting polymers;
nanoparticles or metal oxide nanoparticles, to harness or amplify adsorption, catalytic
Hybrid
reaction and transport behavior of additional material systems. The basis for enhancement in these
nanostructures;
hybrid nanostructures reside in four general structures in which conjugated polymers act as
Chemiresistor
conduits that interface and respond to nanoparticle interactions or conversely play the role of
the sensitizing agent to enhance sensitivity, lower detection limit, response time or selectivity
of relatively inert substances, ultimately giving rise to high performance sensors. This review
is focused on chemiresistive hybrid conducting polymer sensors for detection of gaseous
chem-icals discussing several recent reports along with strategies for further development of hybrid
sensors.
© 2013 Elsevier Ltd. All rights reserved.

Introduction toxins, ensure homeland security, maintain operations and


emission control in the industrial and automobile sectors,
The need for chemical detection and quantification is an and diagnose health problems. Nanosensors, in particular,
increasingly important component of our daily lives, providing have gained attention as a means to increase performance
the means to monitor the environment for pollutants or while reducing the cost and footprint with compact, highly
deployable designs. Among the different sensing modalities,
conductometric configurations (eg, chemiresistive, chemical
field effect transistor (chemFET), chemi-capacitive,
ÿ Corresponding author. Tel.: +82 31 400 5650;
fax: +82 31 418 6490. etc.) have demonstrated some of the most drastic gains due
ÿÿ Corresponding author. Tel.: +1 951 827 7710; to the augmented effect of catalytic and adsorption processes
fax: +1 951 827 5696. on charge transport behavior. This includes reducing
E-mail addresses: choa15@hanyang.ac.kr (Y. Choa), energy consumption and lower operating temperature while
myung@engr.ucr.edu (NV Myung). drastically increasing sensing performance. The diminutive

1748-0132/$ — see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.nantod.2012.12.005

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Figure 1 Chemical structures of several conducting polymers. Note the alternating double bond structure.
Reproduced from Ref. [4] with permission from WILEY-VCH Verlag GmbH & Co.

sizes of nanosensor elements are also conducive to smart advanced sensor systems as the monomeric chemical
sensor platforms that exploit massive parallelism to structure alone presents a veritable database to tailor chemical
determine multiple analysts and their concentrations in complex affinity interactions (Fig. 1) [5—10]. Additionally, the
mixtures [1,2]. secondary and tertiary structures as well as the dopant type and
Conducting polymers (CPs) are attractive sensing concentration can be used to tune the selectivity and
materials because they exhibit electronic, magnetic and optical sensitivity of conjugated polymer sensors [11]. For example, the
properties of metals and semiconductors while retaining the conductivity of conducting polymers ranges from metallic
attractive mechanical properties and processing advantages to near insulating, introducing a number of different
of polymers [3,4]. In this regard conducting polymers that conduction mechanisms just based on the conductivity level,
contains conjugated backbones are particularly suitable for Fig. 2. Conducting polymers (CPs) also operate at near room

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Hybridized conducting polymer chemiresistive nano-sensors 3

temperature drastically increasing efficiency over traditional


semiconducting metal oxide based sensors which
typically operated around 200—400 ÿC [12]. Unlike inorganic
materials, CPs are inherently porous and the sorption
process for these polymers is often more similar to absorption
Rather than adsorption, providing additional benefits in
sensitivity.
Within the realm of chemical sensing, chemiresistive
based devices, which interpret chemical information by
means of two point contact electrical resistance changes,
are among the most studied and promising transduction
mechanisms for conducting polymer based systems.
This is largely due to the fact that current or electrical
resistance is one of the simplest of electric signals to
analyze, requiring minimal supporting electronics, for com-
pact, deployable, self-contained systems. In context
of conducting polymers, this mode of operation is highly
amenable to nanostructuring and exploits the composition
and structure dependent charge transport and adsorption
behavior to fine tune the performance of these materi- als.

Nanostructural hybridization of CPs with inorganic and


graphitic nanoscale building blocks offer further advantages
in polymer processing, device performance and/or further
tunability over standalone polymeric based sensors as well
as traditional metal oxides [13,14]. These nanoscale con-
Figure 2 Conductivity range of conjugated polymers.
stituents can serve as conduits for charge transport with
conjugated polymers behaving as sensitizing agents
or the CPs can be functionalized introducing specificity Conducting polymers
for targeted analytics. Quite often, rapid deposition
technology such as drop-casting, inkjet or electrodeposition The discovery of conducting polymers is often attributed to
can be utilized without the need for more cumbersome
Heeger, MacDiarmid and Shirakawa who first demonstrated
template approaches since the newly introduced the highly conductive and tunable nature of polyacety-lene
nanostructure imparts the benefits of nanoscale dimensions [15].(PA) doped with halogens in the late 1970s [16—18].
In some cases these nanoparticles may act as nanoelectrodes These works along with significant development in numer-
that create a matrix of nanoscale CP sensors to
ous aspects of these polymers by the trio would merit the
enhance sensitivity and decrease electrical resistance of 2000 Nobel Prize in chemistry [3,4]. In this regard, one
device, offering gains in price and size reduction of of their most important contribution was identification of
chemiresistors due to fewer and less complex electronics the conjugated backbone or alternating -bonds along with
components. doping as the culprit for conduction. This work is allowed for
These advantages have spurred interest in chemiresistive quick identification of conducting polymers from existing
based conducting polymer hybrid nanosensors for chemical chemistries, several of which are shown in Fig. 1.
analysis. In particular, the focus of this review will Ascertained from this list, aromatic cyclic monomers, many of
be conducting polymer hybrid sensors containing metals, which are heterocyclic, provided a first cut at stabilizing the
metal oxides, or graphitic materials (ie, carbon nano-tubes bare conjugated backbone of PA and practically introduced
and graphene) in the form of nanostructures (ie, application in sensing.
nanoparticles, nanowires, nanotubes, etc.). Due to the
inherent porosity, conducting polymer thin films or nano-
structures that are either surface functionalized or contained Synthesis
nanoparticles incorporated into the polymer matrix are
relevant to this review. Several significant contributions to the The synthesis of these hybrid devices is critical as it is
field are examined to describe recent progress and identify affects the conformational and tertiary structure of the
practical challenges associated with these hybrids CP (described below) critically impacting transport charges
structures. In addition to surveying recent literature for and sensing mechanisms [19,20]. While specific descriptions
experimental demonstrations of such sensor systems we of hybrid material synthesis will accompany reports
discuss the sensing mechanisms of these hybrid materials, below, a general description of CP synthesis techniques
as they can be significantly different than traditional is included here to facilitate understanding in the hybrid
CP sensors. A brief background of conducting polymers context. In terms of polymerization, chemical, electro-
in the context of sensing is first given to describe the chemical, plasma, enzymatic and photochemical techniques
breadth of work undertaken in developing our current have been used to assemble polymer chains from monomer
understanding of conducting polymer behavior in chemistry precursors [21—23], with chemical synthesis being the
environments. dominant route in literature reports followed by electrochemistry

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polymerization. Chemical routes have been extensively due to chain stacking, polydispersity and potential for side
studied with a number of polymer specific catalysts to reactions while inkjet printed or spin coated films utilize
attain proper bonding for conjugation and high region, chemically synthesized chains with greater chain length and
where applicable, typically giving better control over limited defects to produce better crystallinity by self-assembly.
molecular weight than other synthetic approaches. Chem- Although electrodeposition is typically more disordered,
ically synthesized CPs generally require solubilization of choice of solvent and deposition conditions can be used to
the polymers and further processing by drop-casting, inkjet tune defect density, chain orientation and crystallinity. In
coating, or electrospinning for fabrication, enabling more terms of self-assembly, alkyl side chains may also be utilized
crystalline tertiary structures by self-assembly of deposited to generate highly crystalline films due to steric hindrance
chains [24—29]. conversely, electrochemical polymerization between chains. These side groups facilitate a coplanar
of CPs allows for rapid, site-specific deposition that packing arrangement with interlocking side groups between
circumvents additional processing, but with polymer chains that adjacent chains and are the source for increased conduction
are generally less pristine than those synthesized by and highly regionally dependent transport properties
chemical means [30—32]. of P3HT [38,39].

Conducting polymer structure Transport charges

The utility of conducting polymers for chemical and bio- In the case of conductometric sensing the nature of the
chemical detection can be strongly attributed to them charge carrier and transport are essential for optimization. In
multilevel chemical structure. In terms of their primary this regard, conducting polymers are diverse materials for
structure, different functional groups and cyclic moieties sensing as conduction occurs by two different mechanisms,
can strongly influence chemical affinity for analytes and intra- and inter-chain transport, that can each be affected
consequently adsorption. One can imagine that these inter- by multiple variables. Intra-chain, or localized, transport
actions can be manipulated to target specific molecules by is highly anisotropic as it occurs along the unidirectional
modification of the monomer chemical structure or cova- pristine conjugated backbone proceeding at very fast rates
lent attachment of synthetic receptors. Although beyond [40—42]. The nature of the charge carrier is dependent on
the scope of this paper, this approach has been proven quite the exact polymer and can include solitons, polarons and
potent demonstrating isomer and even enantiomeric bipolarons, all of which introduce energy states between
chemical selectivity and readers are referred to McQuade et al. the highest occupied molecular orbital and lowest
for a comprehensive review of work in the field [5]. unoccupied molecular orbital. Although charge carriers can be
Like any polymer, CP properties, particularly charge induced by other mechanisms such as photons, the breadth
transport and sensing behavior, are also dependent on of work with sensors includes those imposed by chemicals
defects, chain length and polydispersity. Branching or dopants. These dopants are typically anions and therefore most
monomer coupling defects, which are typically highly syn- CPs are generally p-type semiconductors. The charge of the
thesis dependent but are also a contributing factor to dopant is balanced by the charge carrier that is generally
polymer aging, disrupt the -conjugated backbone creating distributed over several mononers by inducing slight
a distinction between chain length and conjugation deformation of the conjugated backbone. When polarized charge
length. Chain length is critical in dictating orientation carriers, which include both the charge and deformation,
and tertiary structure with longer chain lengths exhibiting can also be injected and physically translated along the
greater order or crystallinity, particularly in confined spaces polymer chain with doping facilitating hopping to a neighbor-
where longer chain lengths induced uniaxial orientation. boring chain [43]. Since most chains do not extend from
Additionally, conformational and linkage defects can electrode to electrode, their transport properties are
significantly alter the tertiary structure by introducing disorder orsensitive to chain length and they require inter-chain transport
microdomains within the polymer and many CP derivatives to migrate across a device [44—46].
has been designed to mitigate these deleterious reactions. Inter-chain charge transport requires hopping or tuning
The most successful examples to counter these aberrations of the charge carrier and is the bottleneck in CP
include alkyl chains and the dioxy group demonstrated with conduction that is dependent on the conformation, tertiary
poly-3hexylthiophene (P3HT) and poly-3,4-dioxythiophene structure and dopant of the polymer. Hopping of charge
(PEDOT), respectively [10,20,33—37]. In the case of small carriers is a thermally activated process that is dictated by
alkyl chain asymmetry is introduced into the monomer and the inter-chain distance is largely determined by the packing
head to tail linkages are required for extended conjugation, arrangement [40]. Since most CP thin films and nano-
while head to head and tail to tail linkages serve to decrease structures reside between crystalline and amorphous with
conductivity. The extent of proper head to tail linkage is polymer chains that do not extend across contacts, a mixture
referred to as regioregularity while the inverse, head to of hopping and intra-chain transport is present in practical
head and tail to tail, is referred to as regioirrgularity. systems. The degree of crystallinity will determine the inter-
The tertiary structure, including chain packing, chain transport behavior, however, even in highly crystalline
orientation, disorder and conformation, can range from single films the orientation of the polymer chains is critical as CP
crystalline to amorphous although for most their CP sensors chains in the transverse direction of charge transport will
structure falls somewhere between these two extremes. be dominated by hopping while those aligned parallel
The crystallinity is highly dependent on the synthesis route maximize intra-chain transport [47]. To further complicate the
with electropolymerized films being more disordered in part picture of CPs, structural inhomogeneities at interfaces and

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Hybridized conducting polymer chemiresistive nano-sensors 5

also heterogeneous disorder within the bulk, can create disparate molecules can cause permanent conformation changes and
behavior from idealized systems [48—50]. The sheer Likewise some analytes can sweep away dopants by solvation
of the tertiary structures complexity has been produced an active [65]. Due to the unique proton dependent transport properties of
area or research in charge transport of CPs and led to the PANI, several sensing mechanisms unique to PANI have
development of several models, generally based on physi- cal has also been reported [66].
tertiary structure as well as the doping level; hopping in Electrical contact between CP and electrode is critically
disordered CPs, quasi one-dimensional transport, tunneling important in understanding overall sensor behavior
between metallic regions, etc. [42,48,50—56]. The readers as the contribution to chemiresistive devices is known to
are referred to a couple of reviews addressing the topic in range from negligible to dominant over bulk behavior. For
greater detail including polymer specific behavior [48,57]. example, the more reduced forms of CPs are also subject to work
function dependent chemical interactions. In
these polymers, the VOCs act similar to polar molecules but
Conducting polymer sensors impose only partial charges that collectively act to shift the
CP work function [67—70]. These CP sensors are usually
CP responses to chemical species include changes in energy dominated by a Schottky barrier at the metal/CP contact where
bands, optical, piezoelectric, and charge transport properties, the work function modulation can generate significant sensitivity
each of which has been explored for CP chemistry and very low detection limits [68,69,71,72]. However
sensors [58]. We will focus on chemiresistors in a two the converse of this is also true, and thus polymers with bulk
point contact configuration with simple supporting electronics to responses may exhibit reduced sensitivity due to contact
measure changes in electric resistance, current, resistance by poor design of contacts or improper selection of
or potential. The defining attributes of these sensors materials. consequently, these devices should be
include sensitivity, selectivity, dynamic range, lower detection thought of as series circuits with a bulk sandwiched resistor
limit, upper detection limit, and response/recovery between two contact resistors. The effect of contact resist-
time. The sensitivity is generally defined as the change tance is typically exacerbated as dimensions decrease and
in electrical resistance over the change in concentration novel approaches are typically required to facilitate contact
and is typically derived from a calibration curve of time to nanostructured CP devices [73].
exposures to several different concentrations of the target In regards to stability, aging of polymers in the environment,
analyte. The selectivity is determined by comparison of sensor similar to that required for gas sensing, is known to decrease
response to target analyte and interfering chemicals, the conductivity of CPs. These changes are related to both
which is a common background analyzer for a specific system changes in the conjugation length and doping concentration.
of interest, typically by separate exposures. For the purposes of While accelerated aging studies with light, moisture or heat
this review, selectivity is conservatively utilized in paint a bleak picture for these materials, non-accelerated
a qualitative manner. The lower and upper detection limits studies in a dark ambient environment displayed less than
indicates the minimum and maximum concentrations of an one order of magnitude drop in conductivity after twenty
analyze that a sensor can detect. The lower detection limit years, suggest these materials are more stable than previously
is commonly limited by the most dilute concentration exam-ined believed [74,75]. Strategies for imposing stability upon
or a response that is three times the noise level of the the conjugated backbone has been described above and
baseline resistance. The response time is generally defined primarily consist of introducing alkyl chains or other chemical
as the time required achieving 90% of the total change in groups to stabilize carbon positions most susceptible
resistance for a specific analyte and concentration, with the to oxidation. On the doping side, a number of studies have
recovery time being that required to drop back to 10% of the suggested that dopant size is inversely proportional to the
response value after the exposure ends. mobility of dopant species and hence larger dopants may
In the chemiresistive arena, CPs are well-suited material as alleviate dedoping degradation [75,76]. In terms of sensing,
their range of electrical conductivity, encompassing these aging effects have not been thoroughly explored,
near metallic to insulate behavior, permit a host of well- but one would anticipate the latter effect is minimal for
documented sensing mechanisms [59]. Some of the earliest near intrinsic CP materials utilized in Schottky diode sensors.
studies utilized a chemiresistive modality, typically synthesized Conversely, highly doped CP sensors are vulnerable to
by electropolymerization, to detect volatile organics considerable modulation in performance, but be careful
compounds (VOCs) by a swelling mechanism. In this case, selection of materials may mitigate dedoping consequences
the CP is well-doped and the VOC is absorbed causing the of aging [75].
polymer chains to separate, increasing the hopping distance As nanostructured devices, conducting polymers have
for charge transport creating an increase in electrical resistance several documented advantages for sensors [77,78]. The
[60,61]. Alternatively, chain induced alignment, in small sizes permit refined spatial resolution and have also
which analyte solvated polymer chains are aligned by polarization Has been shown to produce enhanced response/recovery times
of the applied potential, can occur for CPs containing due to a two-dimensional analytical diffusion profile [79].
smaller chains [62]. Polar molecules such as NH3 or NO2 Although porous, CP density will still impart a bulk diffusion
behave as electron acceptors or donors contributing a charge ultimately dictating response and recovery time, which
carrier to the polymer and subsequently participating as can be circumvented by nanostructuring [80—82]. Like any
dopants that increase or decrease carrier concentration, plastic, the porosity of CPs is dependent on a multilevel
respectively [63,64]. While most of these interactions are structure and synthetic therefore dependent variation in
generally reversible, the exception being the inherent Bulk diffusion is a practical feature that should be considered.
irreversible chain alignment mechanism, highly reactive Some synthesis approaches also permit increased

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Figure 3 Schematic of four different hybrid conducting polymer structures: (i) CP structure surface decorated with discrete
nanoparticles, (ii) conducting polymer with embedded nanoparticles, (iii) nanostructures coated with a thin sheath of conducting
polymer, and (iv) nanostructures containing discrete conducting polymer sites.

order, typically as a result of confinement, with small fibers interfacial structure, which can strongly influence the electronic
similar to their inorganic counterparts, however clear cor- properties of these materials, as is often the intent
relation between tertiary structure and sensor performance of hybridization, and worthy discussion. Within the framework
has yet to be demonstrated with nanostructured CP sensors of hybridization, many of the interfacial properties are
[83,84]. dependent on the fabrication approach, which is typical
described by a sequence of synthesis, blending and deposition
Hybrid nano-sensors procedures [72,85,86]. Most approaches will either
synthesize one material in the presence of the other or uti-lize
separate synthesis procedures with subsequent blending
Structure
and deposition. In situ hybridization by synthesis of one
materials in the presence of the other can generate non-
The hybrid CP sensor can be practically represented by covalent interfaces as well as covalently bonded hybrids
four different configurations that shift the primary sensor materials in which the polymers are generally aligned normal
functions, transducer and sensitizing element, between to the surface. In the case of the latter the two materials
the two materials shown in Fig. 3. Devices that have the may be deposited sequentially by a number of different
CPs sensitized with nanostructures include surface
approach or they may be blended together in solution and
functionalized devices as well as composite structures or those then recast by spin-coating, drop-cast, or inkjet deposition.
with nanoparticles embedded throughout the bulk of the Non-covalent interactions may be classified by hybrid
polymer. In these structures the conducting polymer is trans- material, for example many metal oxides generate electrostatic
ducing the electronic response of the nanoparticle as well as interactions with CPs while the graphitic surfaces
direct interaction between CP and analyte. Since the parties (ie, graphene and CNT) are functionalized by -stacking
have an active electronic role in these devices, features van der Waals forces [87—89]. Some synthesis approaches
such as loading, dispersion and particle size are important are known to exhibit certain interfacial traits as in the
design considerations. Furthermore, the CP porosity and case of electrodeposition, which has been shown to produce
characteristic length will also dictate the trade-off between shorter oligomers at interfaces and in specific instances
surface and bulk hybridization, with a convergence in both highly ordered epitaxial interfacial layers distinct from the
sensitivity and response/recovery time expected at smaller bulk structure [90]. While a number of different scenarios
length scales where processing advantages are likely to can unfold at the interface, many of which are incommensu-
dictate the final structure. The inverse configuration of these rate with the bulk and hinder interpretation, these features
devices employs conducting polymers as discrete entities, are critically important for device behavior and should be considered
particles or covalently bonded molecules, or thin films to the forefront of thought in design of experiments, executing
increase selectivity and/or sensitivity of a non-polymeric experiments and evaluating reports.
nanostructure, typically a wire or tube (Fig. 3, iii and iv).
For decorated materials the polymer may screen out certain,
molecules, increase chemical affinity or impose modulation Hybrid conducting polymer sensors
in charge transport in response to adsorbate interactions.
In the case of CP sensitized nanoparticles such as single- Metal/conducting polymer
walled carbon nanotubes (SWNTs), the SWNTs transduce the Hybrid CP/metal sensors include both thin film and nano-
analyte—CP interactions. structured CPs containing either surface decoration or bulk
In addition to the bulk structure, the performance of inclusions of metal nanoparticles. A number of studies have
these hybrid sensors are intimately tied to the physical focused on detection of VOCs or other gaseous molecules

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Figure 4 (a) Scheme of synthesis route for Ag nanoparticles/PEDOT nanotubes. TEM images of Ag NPs/PEDOT NTs with increasing
concentration of AgNO3: (b) 5 wt.%, (c) 10 wt.%, (d) 30 wt.% and (e) FE-SEM image of PEDOT NTs containing Ag NPs on an electrodes.
(f) The sensing performances of pristine PEDOT NTs and Ag NPs/PEDOT NTs with 5, 10, and 30 wt.% Ag to several concentrations of
NH3.
Reproduced from Ref. [104] with permission from The Royal Society of Chemistry.

primarily using precious metals including Au, Ag, and Pt also shown to increase with increasing Ag loading up to
as the work function of these metals are sensitive to ana- 30 wt.% (Fig. 4c), thereafter particle coalescence decreased
lyte interactions, however studies with other metals such as the role of the CP in the device leading to slight drop in
Ni and Cu are also reported [14,91—99]. In these studies, sensitivity. The rapid response times, minimized at 30 wt.% and
the nanoparticle coverage, dispersion, surface chemistry believed to be related to the reduction of charge traps, suf-fered
and size can be highly dependent on the synthesis route slightly at higher Ag loadings as the surface coverage
and may even prelude significant gains in sensing performance. hindered transport of the analyte into the CP.
Indeed a number of studies have been dedicated A significant contribution using metallic nanoparti-cles as the
to the synthesis of these hybrid materials for sensing as sensitizing agent was demonstrated with an
well as other applications but few have observed significant Au/PANI system for H2S detection by Shirsat et al. [105].
improvement in sensitivity or lower detection limit In this work, a PANI nanowire network was electropolymer-ized
to gas analytes [14,21,69,100—103]. Part of the challenge using a two-step approach for nucleation and growth
is the entanglement of charge transport pathways and physical to attain 250—350 nm ligaments. Following polymerization
structure of the composite which blurs the exact sensing of the PANI network was electrochemically functionalized
mechanisms and routes to rationally enhance performance. with Au nanoparticles of 70—120 nm in diameter. This route
Here a couple of well-controlled systems with specific attention led to good nanoparticle dispersion as depicted in Fig. 6a.
to the sensing mechanisms and structure are described The Au/PANI devices demonstrated superior sensing performance
as they provide direction with these hybrid systems. with a sub-ppbv lower detection limit for H2S at room
Nanoparticles that act as nanoelectrodes have been temperature (Fig. 5b) while the unfunctionalized PANI net-work
demonstrated by Park et al. with Ag/PEDOT nanotubes lower detection limit was four orders of magnitude
[104]. For these devices, the Ag nanoparticle decorated higher, showing almost no response to 50 ppmv H2S (Fig. 5c).
PEDOT nanotubes were synthesized by metal ion reduction Although the sensing mechanism was not described in detail,
mediated vapor deposition polymerization in templates the high work function of the AuS adlayer (6.18 eV) has been achieved
coated with both an initiator (Fe3+) and nanoparticle precursor shown to result in charge transfer of electrons from Au to AuS
(Ag+ ), depicted by the schematic in Fig. 4a. By varying [106]. In this case, the transfer of electrons from PANI to AuS
the silver ion loading in the template the authors could modify would also occur, but a substantial Schottky barrier would
the size and density of nanoparticles on the tubes, prevent electron transfer from the particle to the PANI. The
as verified by transmission electron microscopy in Fig. 4b. resulting surface charge of the nanoparticle behaves as a
These devices demonstrated increased electrical conduct- nano-gate significantly increasing conduction in the particle-
tivity with Ag nanoparticle loading, perceptibly permitting localized region, similar to a way that a negative gate bias
charge transport across the PEDOT/Ag/PEDOT interfaces can be used to switch a p-type field effect transistor to an
and likely reducing the density of charge traps that would 'on' state with higher conductivity.
not typically contribute to charge transport and analyzer These two reports highlight the CP/metal relationship in
response. In terms of charge transport across the PEDOT/Ag two different, promising scenarios; the conducting polymer
and Ag/PEDOT interfaces the lower work function of Ag acting as the sensory material with the nanoparticles behaving
(4.7 eV) with respect to PEDOT (ÿ5.0 eV) would create a as nanoelectrodes to decrease overall device electrical
slight barrier to charge transport that is likely mitigated by resistance and the conducting polymer behaving as a trans-
the applied potential thus results in a tenfold decrease ducer for sorption reactions occurring at the nanoparticle
in resistivity for 30 wt.% Ag. As NH3 sensors, the devices (Fig. 6). In the former, the particles are dispersed in a sufficiently
demonstrated very rapid responses and the sensitivity was doped CP material that ideally results in the same

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Figure 6 Schematic of hybrid inorganic/CP sensing


mechanisms. (a) Dispersed metallic electrodes in a doped conductor
polymer: (i) The doped conducting polymer device in carrier gas
Figure 5 (a) SEM image of functionalized gold nanoparticles is dominated by several resistive regions and (ii) upon exposure
PANI nanowires network across gold microelectrodes. (b) to the analyst exhibits a higher bulk resistance. (iii) The cor-
Response and recovery transients (solid line) of gold responding metal nanoparticle decorated CP exhibits a lower
initial resistance due to the role of the dispersed
nanoparti-cles functionalized PANI nanowire network based chemiresistive
sensors toward 0.1 ppb, 1 ppb, 10 ppb, 100 ppb, 500 ppb, and nanoelectrodes, (iv) while still exhibiting the same overall resistance
1 ppm. Dashed line indicates concentrations of H2S gas. Inset upon exposure. (b) Dispersed nanogates in an intrinsic
shows linear calibration curve for these concentrations. (c) conducting polymer: (i) The intrinsic CP exhibits higher resistance in
Response of unfunctionalized PANI nanowire network toward the bulk and at the contact due to a Schottky junction, (ii) with
50 ppm of H2S gas. Dashed line indicates carrier gas and arrows subsequent exposure of the analyte exacerbating the Schottky
indicates analyte exposure. junctions. (iii) Introduction of the nanogates generating similar
Reproduced from Ref. [105] with permission from American resistive behavior in the carrier gas; (iv) exposure to the
Institute of Physics. ana-lyte augments the electrostatic gate or depletion/accumulation
layer, indicated by the red shaded region surrounding the
par-ticle, which influences charge transport. The resistors are used
to illustrate the general sensor signal before and after sensing
R response to the analyte (Fig. 6a, iv) as the stand alone
and as a consequence of hybridization.
CP device (Fig. 6a, ii), ultimately driving up the sensitivity
by virtue of the baseline drop (Fig. 6a, iii) with respect to
unfunctionalized material (Fig. 6a, i). The second report is Metal oxide/conducting polymer
akin to the dispersed nano-gate scenario (Fig. 6b), in which Metal oxides (eg, SnO2, In2O3, TiO2, ZnO, and WO3) are
an intrinsic polymer that typically forms a Schottky junction the most commonly used materials for gas sensing and
at the contact in the unfunctionalized state (Fig. 6b, has been used for several decades in smoke alarms and a
ii) is now subject to significant bulk contribution by growth number of common commercial and residential early
of the accumulation/depletion layer (Fig. 6b, iv). Since warning systems. However, several disadvantages, such as poor
these devices contain undoped or intrinsic CPs one must be selectivity, high operating temperatures (eg, 200—400 ÿC),
cognoscente of the potential for Schottky junction formation and baseline drift, plague this family of material sensors.
at the contacts and rational strategies to incorporate Metal oxide structures with reduced dimensionality
or exclude their behavior [72]. and increased crystallinity can enhance binding energies

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Hybridized conducting polymer chemiresistive nano-sensors 9

leading to significant electronic shifts to small concentrations and TiO2 exhibiting a well-defined response to CO
of gases at low temperatures. For hybrid configurations concentrations below the ppmv threshold, which is an impressive
containing the intrinsic polymer, the metal oxide/CP inter- lower detection limit for CO particularly at room temperature.
face forms a heterojunction that can be very sensitive to The sensing mechanism of these devices is similar
analytes, particularly with those containing the intrinsic that described with hollow metal oxide particles, however
or lightly doped form of the polymer, similar to Fig. 6b. the heterojunctions are formed with a reduced CP (dedoped)
Although a number of studies have examined the utility of and hence the depletion region is larger (Fig. 8b), consistent
metal oxide/CP materials [15,107—113], most studies fall with Fig. 6b. Exposure to NO2 decreases the depletion
short of capturing synergistic behavior that leads to region at the CP/SnO2 interface behaving as a nanostructured
significant gains for gas sensing in a chemiresistive mode as point FET, effectively increasing the conductivity.
the quality of both the CP and metal oxide as well as the The PANI/SnO2 response to CO perceptibly forms a similar
composite structures are critical. nanoparticle p—n junction FET sensor. The chemical
One attempt to incorporate metal oxides with CP sen- selectivity of the sensors to the two different analytes was not
sors utilized hollow SnO2 spheres coated with a thin CP elaborated upon but likely resides in affinity interactions
film [114,115], the synthesis scheme entailed coating the between the analyte and thiol or amine group and inter-
n-type metal oxide spheres with the monomer in solution facial structure as RRP3HT/TiO2 was sensitive to 10 ppm
followed by introduction of the oxidizing agent for NO2 with no response to 10 ppm CO while only PANI/SnO2
polymerization, shown in Fig. 7. The spheres served to augment showed a greater response to 1 ppm CO than 1000 ppm
the CP surface area and were believed to create sensi- SO2.
tive junctions between spheres. The SnO2 particles comprise
the bulk of the volume, as shown by TEM images of SnO2
nanoparticles without (Fig. 7a and b) and with (Fig. 7c and Carbon nanotubes/conducting polymers
d) a CP coating, but still behaves as a sensitizing agent The CNT/CP materials are perhaps the most widespread
with charge transport believed to occur primarily through explored hybrid CP gas sensors largely due to interest in
the thin CP coating. The role of the SnO2 hollow spheres developing SWNT based devices. In these sensors the limited
was not fully clarified but the CP coating was shown to specificity of SWNTs, low analyte affinity, and irreversibility
limit metal oxide—analyte interactions. These devices were adsorption with SWNTs confines their role primarily to
thought to be dominated by the depletion region formed at transducing elements with the CP imparting sensitivity,
the interface of the CP/metal oxide interface due to the selectivity, and reversibility. Although composites in which
p—n junction. The depletion region contains a reduced the CNT and CP are fully intermixed have been pursued by
carrier concentration and is suspected of being more sensitive some groups, the structure does not optimize the role of
to analyze interactions. These sensors demonstrate promise both the SWNT transducer and CP sensitizing element and
with NO2 and NH3, showing improvement over stand-alone little gain has been seen with these devices. This approach
CP devices, but were limited to ppmv lower detection limits, was taken by An and co-workers, in which SWNT were
which may have resulted from the doping level of the incorporated during the chemical polymerization process [118].
CP. While little was given in terms of the polymer The SWNTs did provide an enhancement to fairly
conformation and structure, the CP was shown to be more concentrated NO2, 3000 ppmv, but the lower detection limits
amorphous in structure due to the in situ polymerization were not reported and are suspected of being less
approach, with the rough morphology of the metal oxide consequential, a likely feature of having the SWNTs fully embedded
assemblies likely having a significant impact on the in PPy. Similarly structured SWNT/CP composites were
structure. fabricated by inkjet printing also demonstrated enhancement
The most successful metal oxide hybrid demonstrations in lower detection limit to percent range concentration of
to date utilized ultrathin films of several conducting VOCs [119]. These inkjet processed hybrid films were shown
polymers, including PEDOT, P3HT, PANI, RR-P3HT, and a to have the added advantage of transparency and flexibility
copolymer of PEDOT-P3HT, with either SnO2 and TiO2 with a polyimide support.
nanoparticles [116,117]. The key to these sensors was the The transition to a more ideal configuration for hybrid
use of layer by layer assembly with Langmuir—Blodgett (LB) SWNT/CP devices actually developed first with polymers
or self-assembled layers of conducting polymers with the that lacks a fully conjugated backbone. This was demon-
metal oxide nanoparticles to achieve fine control over film strated early on by Qi and co-workers in which CVD grew
thickness. The films were de-doped by washing with ammo- SWNT's grown in place were non-covalently decorated with
nia followed by EDTA to produce intrinsically conducting polymer thin films to achieve high selectivity and sensitivity
polymers film composites. Although the tertiary structure for both NO2 and NH3 [120]. A perm-selective polymer,
was not elaborated upon in these reports the LB process is Nafion, was used to impart selectivity for NH3 while poly-
associated with more crystalline films and the nanoparticles mer binding affinity enabled high selectivity and sensitivity
incorporation is expected to be within the film as well as for NO2. One critical feature of their process was sequential
on the surface due to the LB assembly process. PEDOT/SnO2 fabrication; initialized by stand-alone SWNT devices, and
and RR-P3HT/SnO2 (Fig. 8a) were shown to achieve lower in this case with a high yield of semiconducting SWNTs as
detection limits <100 ppbv for NO2 with PEDOT/SnO2 an added benefit to the in situ synthesis, followed by
demonstrating a ppbv level low detection limit. Just as significantfunctionalization with a thin film of the polymer. The fabrication
is that fact that these composites displayed a response time sequence ensured that the SWNTs or SWNT network provides
of <1 s, suggests the nanometers thin film is more easily CP independent paths for charge transport while the thin
penetrated by gaseous species. PANI composites with SnO2 polymer layer imparts sensitization without bulk coverage

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Figure 7 (top) Schematic illustration for synthesizing polypyrrole-coated SnO2 hollow spheres. TEM images of (a, b) pristine SnO2
hollow spheres and (c, d) polypyrrole-coated SnO2 hollow spheres.
Reproduced with Ref. [115] with permission from The American Chemical Society.

that dissociates polymer—analyte interactions from SWNT sensitize the SWNT but was localized to carboxyl groups,
transport charges. suggests covalent bonding is particularly effective at sen-
The early efforts with CPs utilized SWNT networks with sitizing SWNT to the electronic interactions of PABS chemical
covalently bonded PABS to demonstrate two orders of switches. In fact, the COOH functional group may be a
magnitude improvement in NH3 detection [121]. The enhancementcritical feature of these sensitive systems and COOH density
was attributed to modulation of the charge carrier may be a fruitful parameter to explore further. Although one
concentration due to a deprotonation reaction of the PABS might think the structure does not fully capture the potential
functional group (Fig. 9a). The enhancement with these of the hybrid sensor due to incomplete coverage of the
hybrid networks are significant as the CP did not fully SWNT, a more optimized SWNT—PABS networks later yielded

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Hybridized conducting polymer chemiresistive nano-sensors 11

Figure 9 (a) The interaction of SWNT—PABS with NH3. (b) Real


response time of the SWNT—PABS sensors to NH3.
Figure 8 (a) Resistance change of RRPHTh—SnO2 nanocom- (a) Reproduced from Ref. [121] with permission from American
posite vs. NO2 gas concentration. (b) Energy-band of hetero Chemical Society. (b) Reproduced from Ref. [122] with
pn-junction. Dashed lines show energy levels under NO2 expo- permission from IOP Publishing Ltd.
sure.
Reproduced from Ref. [116] with permission from Elsevier
but may also have electronic origins as decreased
Publishing.
conductivity has been shown to increase sensitivity.
The concept of the parallel CP and SWNT sensing
elements was taken a step further in a complimentary study
100 ppbv and 20 ppbv lower detection limits for NH3, shown that explored humidity tolerance with camphor sulfonic-
in Fig. 9b, and NO2, respectively [122]. acid (CSA) doped PANI [124]. A careful balance of contrasting
Similar work by Zhang et al. also explored the use of conductivity responses to humidity for the SWNT network
electrification to functionalize SWNT—COOH networks with and PANI—CSA was shown to enable highly sensitive and
chloride doped PANI for gas sensing [123]. Electrodeposition reproducible detection of ammonia over relative humidity
provides the advantage of coating all electrically conducting concentrations ranging from 0—60%. In these hybrid materials,
surfaces in the network with lower nucleation potentials Humidity behaves as an electron donor for SWNTs,
on defect sites, ensuring the most sensitive spots are effectively decreasing the conductivity. on the other hand the PANI—CSA
functionalized. Their results showed a 60-fold improvement in interaction with humidity can be described by a proton
sensitivity at room temperature, 2.44% R/R per ppmv, over exchange-assisted conduction of electrons. In this scheme
that of unfunctionalized SWNT—COOH networks with a lower adsorbed H2O increases the probability of proton exchange,
detection limit of 50 ppbv for NH3. In this configuration, the along with the redox reaction, thereby oxidizing the PANI
CP was continuous and shown to have a strong impact on and increasing the conductivity upon exposure to humidity.
device conductivity. The added complexity of active charge These CSA doped PANI functionalized SWNT networks were
transport through the CP was indicated to convolute also shown to exhibit a lower detection limit of 10 ppbv for
contributions to device sensitivity and the sensing mechanism, NH3 at room temperature.
which was believed to be a combined response of both PANI In one of the few studies that utilized synthetic chemistry
and the SWNT network in a parallel circuit. These are PANI of conducting polymers in a hybrid setting, Wang et al.
decorated SWNT networks were shown to be sensitive to demonstrated calixarene-substituted polythiophene coated
temperature as well. The resistance was shown to decrease SWNT sensors for differentiation of xylene isomers [125].
with an increase in temperature, as expected for In this work the calixarene groups were attached to the
semiconductor SWNTs and PANI, however the sensitivity decreasedhexane tails in P3HT and then chemically polymerized to
with higher temperatures. This was explained as an increase create the isomer selective CP. The CP was then mixed
in the gas/PANI partition of NH3 with respect to temperature with SWNTs and spin coated on electrodes to create hybrid

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sensor devices. Although not extreme, these sensors were particular interest as polymeric residue during lithographic
shown to have increased sensitivity to p-xylene by virtue of patterning of electrodes was recently shown to impart
the calixarene shape selective hydrophobic pocket, while significant sensitivity gains for several different analytes.
unmodified SWNT/P3HT devices displayed no difference in Initial studies with graphene/CP hybrid materials can be
response to individual xylene isomers. classified by one of two geometries, composite films in
Beyond analyte specific studies the electropolymerization which the polymers are polymerized in situ with exfoliated
platform for SWNT/CP gas sensors was subsequently graphene sheets and CP functionalized graphene sheets.
extended to several different CPs to differentiate a number Although the latter may hold greater potential for sensors,
of analytes. In this study, SWNTs films were fabricated by efforts to date have focused on the composite films to
vacuum filtration, followed by shadow mask contact and CP bypass the challenge of making single graphene sheet devices.
electropolymerization. The SWNT loading was optimized for Since composite films to date are solution processed,
dynamic range and lower detection limit by exposure to only graphene oxide has been used as a precursor or directly
DMMP and NH3, both of which converged on 1 mg/L, and for graphene/CP sensors. While this route has enabled facile
applied to the synthesis of all sensors. Numerous devices synthesis, it also undermines the potential of this system
with seven varieties of CPs, along with bare SWNTs, were with a fragmented picture of these materials. The chemical
implemented to create unique signatures for six different modifications that permit exfoliation of graphene oxide also
analytes in an e-nose fashion. impart substantial changes in electronic structure with
A recent study of a non-covalently PANI functional-ized strong implications on sensor performance. Although
SWNT system compared the hybrid sensor response to reduced graphene oxide contains pristine grains or regions,
SWNT networks and PANI nanofibers during exposure to but is still a far cry from epitaxial graphene. While these
different analytes to understand the synergistic gains of chemical moieties or defects do not preclude enhanced
SWNT—PANI networks [126] . SWNTs were shown to have a chemical sensitivity they bypass features such as the zero
bipolar response due to a hydrazine induced n-type bandgap of pristine graphene that permits charge transfer
conversion while PANI were irreversibly oxidized, and hence with adsor-bates containing only a slight chemical potential
both were poor hydrazine detectors. In contrast, the hybrid mismatch [136] .
system demonstrated reproducible responses to saturated The composite films to date are still limited to just a
hydrazine vapors but demonstrated poor recovery. Cyclic handful of studies, many of which are solution based.
voltammetry was used to show the oxidation potential for In the realm of gas sensing graphene/PANI sensors have
conversion from emeraldine base to pernigraniline had been recently demonstrated for hydrogen sensing [137]. The
shifted substantially more positive in the presence of the composite was synthesized by in situ addition of graphene
SWNTs. Additionally, UV—vis-NIR spectroscopy showed an during chemical polymerization of PANI, a relatively facile
increase in the S11 band indicating that electron transfer approach to graphene incorporation. The composite, shown
from the SWNT to PANI occurred during exposure to in Fig. 10a and b, outperformed the bare graphene across
hydrazine increasing the energy barrier for oxidation from the H2 concentrations examined, but only provided gains
emeraldine to pernigraniline. While the synergistic sensing against PANI for higher H2 concentrations (ie 0.5% and 1.0%)
mechanism of the PANI—SWNT devices was delicately shown in Fig. 10d. In this system, graphene and PANI were
demonstrated, the practical use of these sensors is not clear shown to have contrasting sensing mechanisms; hydrogen
as sensor performance was not fully examined for hydrazine. acts as a reducing agent for carboxylic groups in graphene
Lastly, as SWNTs are one-dimensional structures, it is depleting the majority hole carriers resulting in an increase
worth mentioning the several studies have explored the in resistance, and for PANI, H2 is believed to hydrogen bond
concept of alignment on device performance [127—130]. to an amine group of the emeraldine salt and dissociates
Laterally configured, AC dielectrophoretically aligned SWNT following the formation of a new NH bonds to the amine.
devices were shown to outperform randomly deposited Graphene was indicated to enhance the porosity of the film
SWNT networks due to a reduction in interconnecting nodes and hence provide an increased response to hydrogen, and
and preferential alignment of semiconducting SWNTs. In a therefore contributed in a limited capacity as no change in
separate effort vertically aligned CNTs were explored as a the electronic structure was described by addition of
way to bypass dispersion and assembly steps, with direct graphene.
integration into devices. Further advantages include ease of In a similar study, pyrene was electropolymerized with
functionalization with CPs, demonstrated robustness in exfoliated graphene oxide, where polypyrene (PPr), 0.2 mg/
terms of contact and low device resistance owing to a L GO/PPr and 1.0 mg/L GO/PPr are shown in Fig . 11a—c
densely populated forest of CNTs. [138]. In these composites the GO was shown to red shift
the UV—vis spectra with respect to PPr. XRD spec-tra
demonstrated the composite had a distinct structure from
Conducting polymer/graphene both PPr and GO. As separate components PPr was
Graphene based CP sensors have just begun to gain amorphous and GO was crystalline, while in the composite
momentum with studies being limited by challenges with crystalline peaks for PPr were present and the GO oxide
graphene processing, both isolation of individual graphene peak disappeared due to dispersion. These results supported
sheets and controlling their surface chemistry [131—135]. an ordered or crystalline arrangement of PPr chains on the
The impetus for functionalization of graphene is similar to GO sheets, which gave rise to synergistic response to VOCs
SWNTs, tuning the selectivity and sensitivity of graphene, not attained with either PPr or GO. Unlike traditional CP
while composites are receiving attention as a means to responses to VOCs that increase in resistance due to
swelling
overcome processing challenges of single layer graphene. Moreover, CPs these
are ofhybrids reacted with a fully reversible increase in

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Hybridized conducting polymer chemiresistive nano-sensors 13

Figure 10 SEM images of graphene/PANI nanocomposite (a) top view, (b) tilted view (45ÿ ). (c) The dynamic responses of
graphene/PANI layer are shown for several H2 concentrations. (d) The sensitivities of the H2 gas sensors with sensitive layers
of (i) graphene/PANI, (ii) PANI nanofibers, and (iii) graphene.
Reproduced from Ref. [137] with permission from The American Chemical Society.

current upon exposure to toluene (Fig. 11d), chloroform and transport due to increased conjugation and sensitivity by
hexane. By consequence of both polarity and chemical virtue of their planar configuration along graphene sheets.
structure the enhanced responses were identified as being due
to partial charge transfer and possible gating, where the - Summary and outlook
electron cloud of toluene may serve to significantly enhance
hole transport. This behavior was facilitated by the highly
Conducting polymers hybrid nanostructures are rich
crystalline PPr structure that likely enhanced intra-chain
materials for chemical detection, providing means to overcome

Figure 11 SEM images of electrosynthesized pure PPr film (a) and GO/PPr composite film deposited from the electrolyte containing
0.2 (b) or 1 (c) mg/mL GO. The deposition charge density was 0.4 C cm2 for each film. (d) The dynamic current responses of the
sensor with a sensitive layer of (i) GO/PPr, (ii) PPr, or (iii) GO to toluene vapor.
Reproduced from Ref. [138] with permission from The Royal Society of Chemistry.

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selectivity and sensitivity limitations of standalone materi- doping levels of CPs can affect electronic energy levels and
als. Conducting polymers can behave as either transducing accordingly intrinsic CPs appear to be better suited for
elements or sensitizing agents in a chemiresistive modality, some of these hybrid devices. This may in fact be an
facilitating cost effective, portable, room temperature, real independent manifestation of the processing pathway, such as is
time monitoring. Several key demonstrations have been capturedthe case for electrodeposited nanoparticles on CPs, which
the potential of these devices but many efforts appear to indirectly dedope the CP by application of a reducing
miss key elements that elevate performance beyond that potential to deposit the nanoparticles. In this particular case of
of standard CP sensors. Indeed the geometry, size, inorganic nanoparticle decoration, the intrinsic behavior of
electronic structure and synthesis protocol for both materials the CP may also impose significant durability due to the
can affect the sensor and must be strategically evaluated in inconsequential effects of age-induced dedoping. However,
the device design. in the case of metal nanoparticles behaving as
The interplay between CPs and nanoparticles includes nanoelectrodes doping may be required to facilitate transport across
sensitization of the conducting polymer due to depletion or the metal/CP interface and is more likely prone to the
accumulation of charge species at the particle/CP interface. detriments of aging. Better understanding of inorganic/CP
These zones can result from either p and n heterojunctions interfacial charge transfer (eg the impact of polymer
or Schottky junctions that act as nano-field effect transistors orientation, localized doping, trap states, etc.) is of strong
to create localized regions of high conductivity or interest for both hybrid material behavior and electricity
resistance. During exposure to specific analytes these contact with only limited work to date.
depletion/accumulation regions can be significantly augmented We have seen an instance where nanoparticles containing
due to work function modulation of either the particle or ohmic or near ohmic contact with the CP behave
CP and appear to be one of the most promising avenues for as nanoelectrodes probing the most conductive and likely
development. However, having said that, early studies most ordered pathway between them to enhance
suggest any synergistic gains in hybrid nano-sensors require a performance. The one demonstration to date on this topic did
careful balance of function and structure. The behavior of show an improvement in performance but the novelty of
each material should be understood independently, along this approach, particular for conducting polymers, leaves
with their contacts and composite form to provide a many questions remaining with an unclear picture on the
meaningful selection of materials for target analysts. Perhaps practical utility of dispersed nanoelectrodes in CPs and the
more important is a solid grasp on synthesis and processing role of the synthesis route. Further studies should examine
conditions and their effect on structure—property relations- nanoelectrode utility in other geometries such as thin
ships. This is significantly lacking in the literature as few films and explore their use in unintuitive settings, such as
studies have demonstrated sensitivity gains by hybridization Schottky junction devices, that may require careful selection
with even fewer probing the interfacial structure of these of materials and processing to probe their utility.
composites. Hybrid structures with carbon allotropes (ie CNTs and
Both the sensitivity and lower detection limits of these graphene) primarily utilize CPs as sensitizing agents owing
sensors have been demonstrated to be intimately tied to the to the excellent transport properties and generally limited
length scales of individual constituents. The CP thickness has chemical affinity and selectivity of SWNTs and graphene.
Been shown to have an optimal thickness indicating that bulk While ease of processing and better understanding of SWNTs
absorption, although permissible with CPs, can be a limiting have accelerated these hybrid devices, significantly slower
factor for devices demonstrating gains by decreasing the progress has been made with graphene due to challenges
film thickness or moving to nanostructured CPs. on the contrary, with isolation of single graphene sheets or dispersion within
as sensitizing agents the CP film thickness has also been used a CP matrix. With graphene, most composite structures
shown to be optimal for very thin films or single adsorbed seems to wash out the impressive sensitivity of stand-alone
layers that augment chemical affinity without compromising graphene devices, suggest hybridization is best pur- sued
transducer sensitivity. In both cases the conformation at the monolayer scale. Advances on this front must
and tertiary structure of the CP, although lacking for many address graphene processing issues, and recent efforts with
reports, appears to be critical to device performance, with graphene sensors are geared toward this direction but many
many of the best performing hybrids having more orders opportunities exist for synthesis, transfer and structural
structures. Further study of the CP structure is warranted implications on device performance [136]. As graphene syn-
but difficult to implement as the conformation and tertiary thesis routes become more mainstream with significant potential
structure are often intimately tied to the synthesis route. is anticipated with CP hybridization, rivaling or possibly sur-
The length scale of inorganic particles used to hybridize passing carbon nanotube based sensors.
CPs are equally important as that of the CP itself. Inorganic Individual SWNT/CP devices have shown surprisingly high
nanoparticles embedded within or decorating the surface of room temperature sensitivities with impressive selectivity
CPs have been on the scale of 10s or <10 nm for the most by polymer choice and array based approaches have been
effective hybrid sensors, however little effort is indicated demonstrated for higher levels of discrimination. From the
toward reporting or controlling size dispersion or character- perspective of transducer development, alignment and chirality
izing size effects. In this context nanoparticles that form strongly influence performance with semiconducting SWNTs
strong Schottky or p and n junctions have the strongest consisting of the most sensitive devices. On that note, in situ
impact on sensitivity and design gains appear to be limited or post synthesis alignment processes selective for semi-
from better understanding of both analyte induced work conducting SWNTs appear most promising as they partition
function modulation of the particle and the electronic inter- the role of SWNT and CP with reduced percolative transport
action between the particle and CP. In this regard, the high contribution from the CP. On the side of the sensitizing

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Hybridized conducting polymer chemiresistive nano-sensors 15

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Hybridized conducting polymer chemiresistive nano-sensors 17

[122] T. Zhang, S. Mubeen, E. Bekyarova, BY Yoo, RC Had-don, NV


Nicha Chartuprayoon received her BS degree
Myung, MA Deshusses, Nanotechnology 18 (2007) 165504.
in Chemical Engineering in 2007 from
University of California, Riverside. She earned
[123] T. Zhang, MB Nix, BY Yoo, MA Deshusses, NV Myung,
her Ph.D. degree in Chemical Engineering in
Electroanalysis 18 (2006) 1153.
2012 from University of California, Riverside
[124] T. Zhang, S. Mubeen, B. Yoo, N.V. Myung, M.A. Deshusses,
under the supervision of Professor Nosang V.
Nanotechnology 20 (2009) 255501.
Myung, with a focus on the electrodeposition
[125] F. Wang, Y. Yang, T. M. Swager, Angew. Chem. Int. Ed. 47 (2008)
8394. and application of organic nanomaterials for
chemical and biological sensors. Her research
[126] MN Ding, YF Tang, PP Gou, MJ Reber, A. Star, Adv. Mater. 23
interests include synthesis and applications
(2011) 536.
of semiconducting nanostructures for electronics
[127] C. Wei, L.M. Dai, A. Roy, T.B. Tolle, J. Amer. Chem. Soc. 128 devices.
(2006) 1412.
[128] XJ Xian, LY Jiao, T. Xue, ZY Wu, ZF Liu, ACS Nano 5 Sandra C. Hernández received her Ph.D.
(2011) 4000. (2010) in Chemical Engineering from the
[129] JH Lim, N. Phiboolsirichit, S. Mubeen, M.A. Deshusses, A. University of California at Riverside under
Mulchandani, NV Myung, Nanotechnology 21 (2010) 075502. the guidance of Profs. Nosang V. Myung and
[130] JH Lim, N. Phiboolsirichit, S. Mubeen, Y. Rheem, M.A. Ashok Mulchandani. She is currently an NRC
Deshusses, A. Mulchandani, N.V. Myung, Electroanalysis 22 Post-doctoral fellow at the Naval Research
(2010) 99. Laboratory in the Plasma Physics Division.
[131] JL Zhang, GX Shen, WJ Wang, XJ Zhou, S W Guo, J. Her work involves the surface modification
Mater. Chem. 20 (2010) 10824. of graphene and related materials by plasma
[132] XH An, TW Butler, M. Washington, SK Nayak, S. Kar, ACS functionalization and electrochemical routes
Nano 5 (2011) 1003. for device and sensor applications.
[133] H. Bai, K. X. Sheng, P. F. Zhang, C. Li, G. Q. Shi, J. Mater.
Chem. 21 (2011) 18653. Yong Ho Choa received his BS in Inorganic
[134] NT Hu, YY Wang, J. Chai, R.G. Gao, Z. Yang, E.S.W. Kong, Materials Engineering from Hanyang
Y.F. Zhang, Sens. Actuators B: Chem. 163 (2012) 107. University in 1989, and MS and Ph.D. in
[135] ZX Zheng, YL Du, QL Feng, ZH Wang, CM Wang, J. Mol. Chemical Process Engineering from Osaka
Catal. A: Chem. 353 (2012) 80. University in 1993 and 1996, respectively.
[136] KR Ratinac, WR Yang, SP Ringer, F. Braet, Environ. Sci. After spending several years as a research
Technol. 44 (2010) 1167. associate at ISIR of Osaka University, he
[137] L. Al-Mashat, K. Shin, K. Kalantar-Zadeh, JD Plessis, SH joined the Department of Materials Science
Han, RW Kojima, R.B. Kaner, D. Li, XL Gou, SJ Ippolito, W. and Engineering at Cheonbuk National
Wlodarski, J. Phys. Chem. C 114 (2010) 16168. University as an assistant professor in 2000.
[138] L. Zhang, C. Li, A. R. Liu, G. Q. Shi, J. Mater. Chem. 22 (2012) In 2002, he moved to Hanyang University,
8438. ERICA campus and became a full professor in 2009. His research
[139] CY Lee, MS Strano, Langmuir 21 (2005) 5192. has focused on the preparation and utilization of nanoengineered
[140] B. Li, G. Sauve, M. C. Iovu, M. Jeffries-EL, R. Zhang, J. Cooper, materials. His publication includes 140+ scientific papers devoted
S. Santhanam, L. Schultz, J. C. Revelli, A. G. to nanosensors, electronics, mechanics, energy harvesting and electromagnetics.
Kusne, T. Kowalewski, JL Snyder, LE Weiss, GK Fed-der, Nosang V. Myung received his MS (1996) and
RD McCullough, DN Lambeth, Nano Lett. 6 (2006) 1598. Ph.D. (1997) in Chemical Engineering from
the University of California at Los Angeles
[141] BJ Doleman, EJ Severin, NS Lewis, Proc. Natl. Acad. Sci. under the guidance of Prof. Ken Nobe.
USA 95 (1998) 5442. Prior to joining UCR in 2003, he worked as an
Carlos M. Hangarter received his BS (2002) engineering staff at JPL MEMS technology
and Ph.D. (2009) in Chemical Engineering group. His work has focused on the synthesis
from the University of California Riverside. of nanoengineered materials and applied
In his graduate work he explored conducting these materials to various applications
polymer nanostructures for gas sensing. including gas and biological sensors,
Carlos is currently a postdoc in the Materials thermoelectrics, spintronics, phase change
Science and Engineering Division at NIST. memories and topological insulators. He is currently serving as the
His research interests are in electrochemical department chair of the UCR Chemical and Environmental
systems and interfacial reactions for sensors, Engineering Department and the founding faculty director for the
electrocatalytic and energy applications. newly formed Winston Chung Global Energy Center (WCGEC).

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