Fh

ANa

b

c

d

a

ARRAA

KAPOPHA

1

psatedTocnpctcIPn

0d

Synthetic Metals 159 (2009) 2253–2258

Contents lists available at ScienceDirect

Synthetic Metals

journa l homepage: www.e lsev ier .com/ locate /synmet

ormation and properties of nano- and micro-structured conducting polymerost–guest composites

.A. Puda,∗, Yu.V. Noskova, N.A. Ogurtsova, O.P. Dimitrievb, Yu.P. Piryatinski c,.M. Osipyonokb, P.S. Smertenkob, A. Kassibad, K.Yu. Fatyeyevaa, G.S. Shapovala

Institute of Bioorganic Chemistry and Petrochemistry of NASU, 50 Kharkivske shose, 02160 Kyiv, UkraineInstitute of Semiconductor Physics of NASU, 45 pr. Nauki, Kyiv 03028, UkraineInstitute of Physics of NASU, 46 pr. Nauki, Kyiv 03028, UkraineLaboratoire de Physique de l’Etat Condensé, UMR CNRS 6087, Université du Maine, 72085, Le Mans Cedex 9, France

r t i c l e i n f o

rticle history:eceived 25 July 2008eceived in revised form 17 August 2009ccepted 21 August 2009vailable online 17 September 2009

a b s t r a c t

Process of formation of polyaniline (PANI) at the surface of SiC and CdS nanoparticles or submicron- andmicron-sized particles of poly(vinylidene fluoride) (PVDF), polycarbonate and polyamides-11, 12 andproperties of the prepared composites are considered. Beginning of the formation of the PANI shell atthe particle surface was evaluated. This important result opens the possibility to control properties ofthe final hybrid composite. In case of CdS nanoparticles PANI was synthesized in the form of nanofibers

eywords:nilineolymerizationCP monitoringolyanilineybrid nanocomposites

embedding these nanoparticles. Films of the PANI–polymer composites showed the conductivity of up to∼0.4 S/cm. The planar heterojunction of the compression molded PVDF/PANI–DBSA film with bulk CdSdisplayed photovoltaic activity.

© 2009 Elsevier B.V. All rights reserved.

pplications

. Introduction

The ability of hybrid composites of intrinsically conductingolymers with common polymers or inorganic nanoparticles toynergistically combine properties of their components is, prob-bly, the main reason of their diverse applications [1–5]. Due tohis ability unprocessible materials become processible, their prop-rties are changed in the required direction, their stability andurability are increased, the cost problem is resolved, etc. [6,7].he composite materials can replace bulk materials in photovoltaic,ptoelectronic and sensor devices, antistatic protection, catalysis,orrosion protection, etc. [5,8–16]. Among these materials a sig-ificant attention is paid to polyaniline (PANI) based compositesrobably due to interesting chemical properties of PANI, its goodonductivity, higher stability and low cost [6,17,18]. At the sameime, poor mechanical properties, meltability and solubility of PANI

ause difficulties in its processibility and producing its composites.t is well known that the situation can be improved when usingANI doped with some functionalized protonic acids being simulta-eously dopants and plasticizers [19,20]. However, a simple mixing

∗ Corresponding author. Tel.: +380 44 503 3110; fax: +380 44 573 2552.E-mail address: alexander.pud@gmail.com (A.A. Pud).

379-6779/$ – see front matter © 2009 Elsevier B.V. All rights reserved.oi:10.1016/j.synthmet.2009.08.043

of previously synthesized conducting PANI with other componentsof the composite in solution or extruder not always results in goodconductivity.

At the same time, there is a known alternative to that mixingapproach. This is aniline polymerization in a presence of other com-ponent of the composite [6]. Specifically, such polymerization canproceed in water dispersion of this component [21–23]. Effective-ness of that way stems probably from the fact that during PANIsynthesis an intimate contact appears between all participants ofthe system. Frequently, in this case, hybrid particles with PANIshell and a core of other material are formed due to precipita-tion of a thin PANI layer at any surface being in contact with thereaction medium [21–26]. The presence of a nonionic steric stabi-lizer, e.g. poly(N-vinylpyrrolidone), poly(vinyl alcohol) or colloidalsilica, etc., is important here to keep the dispersion (latex) stabil-ity and to allow the formation of the conducting polymer shell[21–24,27]. In turn, thickness, morphology and composition of theshell both depend on the polymerization conditions (temperature,pH, reagents loading and nature) [21,28] and obviously have a cru-

cial importance for properties of the hybrid composite material incase of its treatments by melting or solution techniques. Duringthe treatments these factors can, obviously, affect shell transfor-mations into PANI clusters of different size, shape and qualityand, thus, indirectly influence properties of the PANI percolation

2 Metal

ndot

fidmdpiaopmaatctbft

sscepoc

2

uan(sC(((E

iab

wtn0cr

fbtscpwm

254 A.A. Pud et al. / Synthetic

etwork formed inside the final material. Therefore understandingifferent aspects of formation of the PANI overlayer at the surfacef other component of the composite is a necessary step to develophe methods allowing controlling the composite properties.

Useful information about thickness and quality of the formednal shell has been obtained with dynamic light scattering,isk centrifuge photosedimentometry, and scanning electronicroscopy allowing evaluation of size and surface perfection

egree of the core–shell particles formed in the polymerizationrocess [21,28]. X-ray photoelectron spectroscopy (XPS) provided

nformation on the homogeneity of the PANI coatings formedt polystyrene latex particles that was confirmed by hot-stageptical microscopy study [21b]. These investigations evidencedroperties of the final core–shell particles. Physical–chemical andechanistic aspects of the process of formation of PANI shell

t the particles of the dispersion phase in situ can be prob-bly understood better when using continuous monitoring ofhe aniline polymerization process with measurements of openircuit potential (OCP), pH, temperature of the reaction mix-ure and its spectral changes [22,26a]. These methods discoveroth a development of electronic structure of PANI during itsormation and chemical changes in the reaction medium composi-ion.

Using combination of UV–vis spectroscopy and OCP mea-urements, we consider in this report formation of differenttates of PANI at different stages of aniline polymerization pro-ess in solution and in the presence of a disperse phase. Theffect of the reagents nature on the development of open circuitotential (OCP) of this process is demonstrated. Some propertiesf prepared hybrid host–guest (core–shell) composites are dis-ussed.

. Experimental

Aniline and o-metoxyaniline (Merck) were distilled under vac-um before use. Oxidants (NH4)S2O8, K2S2O8, KIO3, K2Cr2O7, H2O2;nd acids-dopants p-toluenesulfonic acid (TSA), camphorsulfor-ic acid (CSA) (Aldrich) and dodecylbenzenesulfonic acid (DBSA)Acros) were of reagent grade. As disperse phase we used nano-ized powders of inorganic semiconductors SiC (∼20 nm) anddS (∼4–5 nm) as well as submicron poly(vinylidene fluoride)PVDF) particles (∼200 nm) in a latex form, micron-sized powders∼100 mkm) of PVDF (“Kynar 1000”, Arkema), polyamides-11,12PA-11, PA-12) (Arkema), and polycarbonate (“Lexan”, Generallectric).

Polymerizations in water media and their UV–vis and OCP mon-toring were performed in a presence of the above sulfonic acids inccord with refs. [25,26] and with aniline:oxidant ratios calculatedy the known normalized aniline/oxidant ratio [20].

Hybrid SiC nanocomposites with PANI–CSA were synthesizedith weight ratios of the inorganic phase to the polymer one in

he range from 0.66:1 till 5.75:1. The weight ratios in the CdSanocomposites with PANI–CSA and PANI–DBSA were 4.5:1 and.8:1, respectively. In case of the polymer–polymer composites theonducting PANI–DBSA(TSA) phase content was changed in theange from 0.5 till 20 wt.%.

Prepared PANI containing composite powders were used bothor preparation of films by compression molding and for studiesy transmission electron and optical microscopy (TEM and OM),hermogravimetry (TG), tensile strength and conductivity mea-

urements. TG measurements were used to determine the ultimateontent of the PANI phase in the inorganic–polymer nanocom-osites. In case of the polymer–polymer composites this contentas found when analyzing their solutions by UV–vis spectroscopyethod [29].

s 159 (2009) 2253–2258

3. Results and discussion

Formation of quite stable colloidal dispersions of PANI nanopar-ticles (nanofibers, nanotubes) or hybrid core–shell structures withPANI shell [30–34] during aniline polymerization opens a goodpossibility to watch changes in chemical structure of the formingpolymer by UV–vis spectroscopy [35]. These spectral observationscan be supplemented with independent OCP measurements atPt electrode placed in the polymerization mixture [26a,c]. Suchthe combination is effective due to the fact that OCP profile ofthe aniline polymerization process displays a development of dif-ferent oxidation states of growing chains of PANI [36,37] thatshould, obviously, correlate with changes in electronic spectra.Indeed, monitoring in situ aniline polymerization under the actionof the persulfate oxidants at low reagent concentrations (dilutedaniline polymerization conditions [26a,30,31]) by UV–vis spec-troscopy and OCP measurements without additional dispersionphase allowed us to estimate moments of formation of differ-ent states of PANI. This became possible due to the low rate ofthe process and to proximity in time of changes in spectra of theforming PANI and characteristic points in OCP profile of the poly-merization mixture. Specifically, from the spectra (not shown) wedistinguished an induction period (IP), appearance and growth ofpernigraniline chain by increase and displacements of the longwave band, and by appearance of pernigraniline insoluble phasefollowed by its transformation to emeraldine state. As in the case ofsynthesis of PANI–DBSA suspensions in water or 2-propanol–watermedia [35,38], we found that spectral and visual (color) changesappeared in the polymerization mixture after IP had finished. Onlythe spectrum of the anilinium salt was observed during IP that tes-tified to the fact that aniline oligomers did not appear at this stageunder the polymerization conditions [35]. At the same time, weshould mention here that there were a lot of publications, in whichformation of aniline oligomers during IP was described (e.g. seereview [39]). The discrepancy can be connected with the fact thatother authors used experimental conditions, which differed fromthe low concentrated polymerization conditions used in this work.

These spectral manifestations of the aniline polymerization arenearly synchronous to changes of the OCP profile and to color tran-sitions of the reaction mixture (Fig. 1a). Here we also distinguishIP (t1), where OCP very hardly grows from the level obtained afteraddition of (NH4)S2O8, testifying obviously to very weak changesin the mixture. This OCP behavior and absence of changes in thespectra during IP suggest that in the system under investigationnot chemical but some physical–chemical changes proceed thatresult probably in formation of a transition state, which includesmain participants of the process. Specifically, the charged nature ofthe monomer (anilinium cations) and the oxidant anions (S2O8

2−)allow us to presume their association into some intermediates like[(PhNH3)+· · ·S2O8

2−· · ·+(NH3Ph)] [26a]. Existence of such dianilin-ium peroxydisulfate intermediate clusters was earlier postulatedby Manohar and co-workers [40]. These clusters can subsequentlydevelop with formation of soluble colorless rodlike aggregatesproved by light-scattering measurements in combination with OCPmesurements and being probably able, in their turn, act as seedsthat promote formation of PANI nanofibrils [40].

At the second stage t2 OCP becomes to grow due to appearanceof aniline oligomers in pernigraniline state having oxidative abil-ity [17] and presenting in the solution in the form of nanofibrills,in line with [40]. These OCP changes correspond both with syn-chronous appearance of blue coloring and the oligomers absorption

in the UV–vis spectra (not shown) of the polymerization mixture. Atthe end of this stage insoluble pernigraniline particles appear andcatalyze the aniline polymerization [26a] that enhances the OCPgrowth during the stage t3 (Fig. 1). Interestingly that, in the middleof this stage t3, in the UV–vis spectra of the forming pernigraniline

A.A. Pud et al. / Synthetic Metals 159 (2009) 2253–2258 2255

F ) presA meriz

a[Ocbatwaomb

acoloOc

dappalatnt

m

ig. 1. Comparison of OCP profiles of the aniline polymerization in (a) absence and (bn:(NH4)2S2O8 = 1:1.25; (c) scheme of the discussed main stages of the aniline poly

ppearance of polaron absorption bands (not shown) was observed26a]. This qualitative change in the system is not displayed in theCP profile (Fig. 1a) but obviously means that under investigatedonditions some units of growing pernigraniline chains are reducedy the monomer to emeraldine state before the OCP maximum hasppeared i.e. earlier than it is known [32,34,36,37]. Consequently,he OCP growth decelerates and OCP amounts to maximum value,hich corresponds to both an ultimate content of pernigraniline

nd depletion of the oxidant in the solution. In the absence of thexidant, the pernigraniline is completely reduced at stage t4 by theonomer remnant and OCP falls to the value which is determined

y a quantity of PANI formed in emeraldine state.As it follows from the above description, four stages of the

niline polymerization process are observed under investigatedonditions (Fig. 1). At the same time, to our knowledge, typicallynly three stages are considered—IP (t1), formation of pernigrani-ine (t2) and emeraldine (t3) (e.g. [32,36a]). The stage of formationf aniline oligomers in pernigraniline state as a separate phase inCP profiles is not considered despite their frequently displayedomplex shape (e.g. [32,40,41]).

It is well known that aniline polymerization in a presence of aisperse phase is strongly accelerated [42]. However, we found thecceleration differed for all the above stages of this process in theresence of SiC nanoparticles, polycarbonate, PVDF and polyamidearticles. Specifically, in presence of SiC nanoparticles, stages t2nd t3 were accelerated after appearance of insoluble pernigrani-ine phase much stronger than before this appearance (∼35 minnd 125 min vs. ∼20 min respectively) (Fig. 1b). This fact suggests

hat nanosized pernigraniline shells appearing at surface of SiCanocrystals or other particles, give their own catalytic input (addi-ional to one of the disperse phase) into the polymerization rate.

Scheme of the above discussed main stages of the aniline poly-erization is shown in Fig. 1c.

ence of SiC nanoparticles (∼0.06 wt.%). Caniline = 0.009 M, molar ratios An:CSA = 1:1.5,ation.

Naturally, the aniline polymerization rate depends not only onpresence or absence of the disperse phase but also on other par-ticipants of the process. Specifically, their effect can be seen fromchanges of the OCP profile depending on the substituent in ani-line molecule, the acid used and its concentration (Fig. 2). Thus, asone can see from the time of appearance of the OCP maximumin the OCP profile, introduction of the electron donating OCH3substituent in benzene ring of the monomer (o-metoxyaniline)resulted in acceleration of the polymerization process as com-pared with the aniline case (Fig. 2). Naturally, a change of thesubstituent should affect the polymerization specificity. Thus,as it has been shown recently [43], OCP profiles and rates ofpolymerization of such substituted anilines as o-anisidine (o-metoxyaniline) and ethylaniline strongly differ in absence andpresence of initiating additives of p-phenylenediamine and anilinedimer.

Judging by the position of the OCP maximum, the 20-foldincrease of TSA concentration leads to ∼1.5-fold acceleration ofthe polymerization process (Fig. 2). Approximately the same coef-ficient we calculated from the known data obtained during OCPmonitoring of higher concentrated aniline (0.1 M) polymerizationsolutions with about 6-fold increase of HCl concentrations in therange of 0.4–2.51 M [44]. This accelerating effect of the acid con-centration is not unexpected because it is well known that pH ofaniline polymerization solution strongly influences aniline oxida-tion and the rate of this process [39,42]. Nature of the acid alsoaffects aniline polymerization rate and OCP profile shape. Thus,OCP maximum of the aniline polymerization appears earlier in

a presence of TSA than in the case of CSA under other equalconditions (Fig. 2). Besides the shape of the OCP profile in thecase of TSA is more pronounced than in case of CSA. The reasonsof these differences are not completely clear yet and are underinvestigation now. But for the moment, from general consider-

2256 A.A. Pud et al. / Synthetic Metals 159 (2009) 2253–2258

F t of OCo he pop

aah

e(fOFtptiamttTtfK(crttci

Fg

ig. 2. Effect of (a) the substituent, acid and its concentration on the developmenxidant nature on the OCP profile and PANI yield of the aniline polymerization in tresence of TSA.

tions we can say that difference in chemical structure, surfacectivity, size of anion and pKa of the acid should be importantere.

Peculiarities of aniline polymerization both in absence and pres-nce of dispersion phase strongly depend on the oxidant nature[45], Figs. 1 and 2). Thus, there is the difference in the persul-ate and the weaker oxidants effectiveness and development of theCP profiles (shown on the example of polycarbonate dispersions,ig. 2b). This can be seen both from the OCP maximum height andhe PANI yield (Fig. 2b). It is indicative that if in the case of strongersulfate oxidants ((NH4)S2O8, K2S2O8) we can judge about ofhe polymerization rate by appearance of the OCP maximum [36],n the case of the weaker oxidants (K2Cr2O7, KIO3 and H2O2) itppears impossible. Specifically, in the latter case, the OCP maxi-um appears much earlier but its height is substantially less than in

he former one. Furthermore, the polymerization runs much slowerhat can be seen from the development of the OCP profiles (Fig. 2b).his resulted in the fact that the polymerization completed (whenhe OCP gets minimal constant values) in the case of the persul-ates after ∼5.5 h (Fig. 2b), while in the case of the weaker oxidants2Cr2O7, KIO3 and H2O2 it finished after ∼26 h, ∼48 h and 48 h

not shown) respectively. Moreover, in the latter case there is noorrelation between the PANI yields (Fig. 2b) and known standard

eduction potentials of these oxidants (1.33 V, 1.2 V, 1.78 V respec-ively [45a,c]) although the correlation exists if compare groups ofhe strong and weak oxidants. Basing on the above data, it is diffi-ult to explain the causes of the observed differences between andnside the both groups. Studies of these effects are ongoing. For

ig. 3. HRTEM SiC/PANI–CSA (ratio 83.9/16.1 w/w) (a), TEM images of PVDF/PANI–DBSAuest–host nanocomposite (c).

P profile of the polymerization at reagent ratios are the same as in Fig. 1; (b) thelycarbonate dispersion (the initial ratio of An:polycarbonate = 2.5:97.5 w/w) in the

the moment we can mention only the known dependence of PANImolecular mass and quality on the oxidant nature [45b].

The diluted aniline polymerization approach allowed us toobtain host–guest composite particles with PANI shell and a coreof other component (SiC, PVDF particles) that was confirmed bymicroscopy images (Fig. 3). However, using Raman and IR spec-troscopy we did not find noticeable interaction between bothcomponents of these core–shell composites unlike known systemswhere surface of a polymer or inorganic core contained functionalgroups or surfactants, which were involved in hydrogen, donor-acceptor, ionic or covalent bonding with PANI [1,2,6,21,34,46]. Inour case macromolecules of PANI are probably physically adsorbedat the core surface. Nevertheless, photoluminescence of the inor-ganic semiconductor SiC was quenched by the organic polymersemiconductor PANI obviously due to dissipation of excitationenergy or charge separation at their interface as it was observedin different hybrid semiconductor nanocomposites [8–11,47].

The formation of core–shell structures by aniline polymeriza-tion in the presence of dispersion phase is not always possible.Obviously, this depends on the particles ability to adsorb themonomer and PANI and/or to interact with acid and oxidant, whichare in the reaction mixture. Thus, in case of chemically unstable CdSnanoparticles PANI did not form shells, but it formed nanofibers,

which embedded these nanoparticles (Fig. 3c). This morphologyis very similar to one of the nanocomposite prepared by anilinepolymerization in the presence of In2O3 nanoparticles [48]. Themorphology similarity of our PANI/CdS and known PANI/In2O3 [48]nanocomposites suggests chemical instability of In2O3 nanopar-

(ratio 95.2/4.8 w/w) core–shell particles (b) and CdS/PANI–DBSA (44.4/55.6 w/w)

Metal

tiaaskpsco

mtmbhmpp(

wina

ascotpd

agoofi

avctpIvPtaib

4

ttactc

dt

[

[

[

[

[

[

[[[[[[

[

[[

[

[

[

[

[

[[[[

[

[

[

[

[

A.A. Pud et al. / Synthetic

icles in the polymerization environment resulting probably inmpossibility of formation of PANI overlayer at the unstable surfacend in a nanofibrillar growth of PANI in the reaction solution bulks it was observed in absence of a dispersion phase [30–32,40]. Theuggestion of the In2O3 nanoparticles instability agrees with thenown etching of indium-tin-oxide, based mainly on In2O3, witholy(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) havingtrong acidic nature [49]. Unlike the above SiC case, photolumines-ence of CdS nanoparticles was not suppressed probably becausef poor contact between components.

Analyzing percolation curves of conductivity of compressionolded films made of core–shell powders of doped PANI with

he common polymers, we found that in case of the inert poly-er (PVDF, polycarbonate) the quite high conductivity could

e obtained (∼0.1–0.4 S/cm) at 3–4 wt.% of PANI–DBSA even atigh temperature. But when using the polyamide (PA-11, PA-12)atrix, the conductivity level was less by 3 orders of magnitude

robably owing to basic nature of amide nitrogens [50], which com-eted with PANI for acid-dopant at high temperature of molding195–240 ◦C).

Naturally, tensile strength of these composite films decreasedith increase of PANI loading due to functioning PANI as a defect

n the polymer matrix [6]. But this decrease (∼5–10%) was not sig-ificant at the PANI loading less than 4–6 wt.%, which still providedsuitable composite conductivity for antistatic applications.

Importantly that the PANI composites with PVDF, polycarbonatend PA-11,12 are characterized not only with high thermostabilityhown by TG measurements, but also with high themostability ofonductivity, that is of critical importance for industrial treatmentf these materials. For example, increase of compression moldingemperature from 200 ◦C to 240 ◦C of the PVDF/PANI–DBSA com-osite powder (4.8 wt.% of PANI–DBSA) resulted in the inessentialecrease of conductivity of the films from 0.4 S/cm to 0.02 S/cm.

The conductivity data testify that nanosized PANI shells, whichre synthesized at common polymer particles surface (Fig. 3), are aood prerequisite for formation of conductive percolation networkf high quality at enough low polyaniline loadings for conditionsf compression molding. The existence of such a network was con-rmed by OM images of the compression molded films.

Enough high conductivity of these films suggested their possiblepplication as a hole-transporting layer as was shown for indi-idual PANI [51]. To check this suggestion the PVDF/PANI–DBSAomposite as a p-type organic semiconductor was pressed at highemperature on the surface of n-type inorganic semiconductorolycrystalline CdS. Current–voltage characteristics of this planar

n/CdS/(PVDF/PANI–DBSA)/In heterostructure showed a photo-oltaic response with an open circuit voltage Voc ∼ 0.3 V. Thus, theANI–DBSA composite can be used for development of hybrid pho-ovoltaic devices. To our best knowledge this is the first attempt topply PVDF/PANI–DBSA composite as a hole-transporting materialn photovoltaic heterostructure. Studies of this application possi-ility are ongoing.

. Conclusions

Measurements of OCP of the aniline polymerization allow easyracking both different stages of formation of PANI shell at a par-icle surface and an effect of acid-dopant, oxidant, disperse phasend their concentration on this process. This opens possibilities toontrol both a thickness of PANI layer at the particles, which are in

he polymerization mixture, and to affect properties of the ultimateomposite.

The prepared polyaniline host–guest composites have con-uctivity, mechanical properties and thermostability suitable forreatment in melting conditions. The possible application of the

[[

[

[

s 159 (2009) 2253–2258 2257

composite film in photovoltaic heterostructure has been demon-strated.

References

[1] R. Gangopadhyay, A. De, Chem. Mater. 12 (2000) 608.[2] S.K. Ghosh, in: S.K. Ghosh (Ed.), Functional Coatings by Polymer Microencap-

sulation, Wiley-VCH, 2006.[3] B.J. Goldsworthy, M.J. Burchell, M.J. Cole, S.P. Armes, M.A. Khan, S.F. Lascelles,

S.F. Green, J.A.M. McDonnell, R. Srama, S.W. Bigger, Astron. Astrophys. 409(2003) 1151–1167.

[4] O. Yavuz, M. Ram, M. Aldissi, in: V. Erokhin, M. Ram, O. Yavuz (Eds.), The NewFrontiers of Organic and Composite Nanotechnology, Elsevier, 2008.

[5] W.J.E. Beek, R.A.J. Janssen, in: L. Merhari (Ed.), Hybrid Nanocomposites forNanotechnology: Electronic, Optical, Magnetic and Biomedical Applications,Springer US, 2009.

[6] A. Pud, N. Ogurtsov, A. Korzhenko, G. Shapoval, Prog. Polym. Sci. 28 (2003)1701–1753.

[7] H. Johnston, F.M. Kelly, K.A. Burridge, T. Borrmann, Int. J. Nanotechnol. 6 (2009)312–328.

[8] N.C. Greenham, X.G. Peng, A.P. Alivisatos, Phys. Rev. B 54 (1996) 17628–17637.[9] S. Günes, N.S. Sariciftci, Inorg. Chim. Acta 361 (2008) 581–588.10] D.J. Milliron, A.P. Alivisatos, C. Pitois, C. Edder, J.M.J. Frechet, Adv. Mater. 15

(2003) 58–61.11] R. Pokrop, K. Pamuta, S. Deja-Drogomirecka, M. Zagorska, J. Borysiuk, P. Reiss,

A. Pron, J. Phys. Chem. C 113 (2009) 3487–3493.12] J. Ormond-Prout, D. Dupin, S.P. Armes, N.J. Foster, M.J. Burchell, J. Mater. Chem.

19 (2009) 1433–1442.13] A.L. Rogach, J.M. Lupton, in: K. Müllen, U. Scherf (Eds.), Organic Light Emitting

Devices. Synthesis, Properties and Applications, WILEY-VCH, 2006.14] P.T. Sotomayor, I.M. Raimundo Jr., A.J.G. Zarbin, J.J.R. Rohwedder, G.O. Netoc,

O.L. Alves, Sens. Actuators B 74 (2001) 157–162.15] B. Rajesha, K.R. Thampi, J.-M. Bonard, H.J. Mathieu, N. Xanthopoulos, B.

Viswanathand, J. Power Sources 141 (2005) 35–38.16] R.C. Patil, S. Radhakrishnan, Prog. Org. Coat. 57 (2006) 332–336.17] E.T. Kang, K.G. Neoh, K.L. Tan, Prog. Polym. Sci. 23 (1998) 277–324.18] S. Bhadra, D. Khastgir, N.K. Singh, J.H. Lee, Prog. Polym. Sci. 34 (2009) 783–810.19] Y. Cao, P. Smith, A.J. Heeger, Synth. Met. 48 (1992) 91.20] A. Pron, P. Rannou, Prog. Polym. Sci. 27 (2002) 135–190.21] (a) C. Barthet, S.P. Armes, S.F. Lascelles, S.Y. Luk, H.M.E. Stanly, Langmuir 14

(1998) 2032–2041;(b) C. Barthet, S.P. Armes, M.M. Chehimi, C. Bilem, M. Omastova, Langmuir 14(1998) 5032–5038.

22] L.G.B. Bremer, M.W.C.G. Verbong, M.A.M. Webers, M.A.M.M. van Doorn, Synth.Met. 84 (1997) 355–356.

23] M.A. Khan, S.P. Armes, Adv. Mater. 12 (2000) 671–674.24] J. Stejskal, O. Quadrat, I. Sapurina, J. Zemek, A. Drelinkiewicz, M. Hasik, I. Krivka,

J. Prokes, Eur. Polym. J. 38 (2002) 631–637.25] A. Korzhenko, A. Pud, G. Shapoval. Patent US 7211202/European Patent

EP1428857 (2007).26] (a) A.A. Pud, Yu.V. Noskov, A. Kassiba, K.Yu. Fatyeyeva, N.A. Ogurtsov, M.

Makowska-Janusik, W. Bednarski, M. Tabellout, J. Phys. Chem. B 111 (2007)2174–2180;(b) A. Kassiba, W. Bednarski, A. Pud, N. Errien, M. Makowska-Janusik, L.Laskowski, M. Tabellout, S. Kodjikian, K. Fatyeyeva, N. Ogurtsov, Y. Noskov,J. Phys. Chem. C 111 (2007) 11544–11551;(c) A.A. Pud, Yu.V. Noskov, G.V. Dudarenko, G.S. Shapoval, Theor. Exp. Chem. 44(2008) 54–59.

27] A.E. Wiersma, L.M.A. Van Der Steeg, T.J.M. Jongeling, Synth. Met. 71 (1995)2269–2270.

28] J. Stejskal, P. Kratochvil, S.P. Armes, S.F. Lascelles, A. Riede, M. Helmstedt, J.Prokes, I. Krivka, Macromolecules 29 (1996) 6814–6819.

29] K.Yu. Fatyeyeva, A.A. Pud, G.S. Shapoval, M. Tabellout. Patent Ukraine 77566(2006).

30] N.R. Chiou, A.J. Epstein, Adv. Mater. 17 (2005) 1679–1683.31] N.R. Chiou, A.J. Epstein, Synth. Met. 153 (2005) 69–72.32] D. Li, R.B. Kaner, J. Am. Chem. Soc. 128 (2006) 968–975.33] Z. Wang, J. Yuan, D. Han, L. Niu, A. Ivaska, Nanotechnology 18 (2007)

115610.1–115610.5.34] L.H.C. Mattoso, E.S. Medeiros, D.A. Baker, J. Avloni, D.F. Wood, W.J. Orts, J.

Nanosci. Nanotechnol. 9 (2009) 2917–2922.35] Y. Haba, E. Segal, M. Narkis, G.I. Titelman, A. Siegmann, Synth. Met. 106 (1999)

59–66.36] (a) S.K. Manohar, A.G. MacDiarmid, A.J. Epstein, Synth. Met. 41 (1991) 711–714;

(b) Y. Wei, K.F. Hsueh, G.W. Jang, Polymer 35 (1994) 3572–3575.37] H.S. Kolla, S.P. Surwade, X. Zhang, A.G. MacDiarmid, S.K. Manohar, J. Am. Chem.

Soc. 127 (2005) 16770–16771.38] S. Shreepathi, R. Holze, Langmuir 22 (2006) 5196–5204.

39] I. Sapurina, J. Stejskal, Polym. Int. 57 (2008) 1295–1325.40] X. Zhang, H.S. Kolla, X. Wang, K. Raja, S.K. Manohar, Adv. Funct. Mater. 16 (2006)

1145–1152.41] P.J. Kinlen, J. Liu, Y. Ding, C.R. Graham, E.E. Remsen, Macromolecules 31 (1998)

1735–1744.42] K. Tzou, R.V. Gregory, Synth. Met. 47 (1992) 267–277.

2 Metal

[

[

[

[[

258 A.A. Pud et al. / Synthetic

43] H.D. Tran, I. Norris, J.M. D’Arcy, H. Tsang, Y. Wang, B.R. Mattes, R.B. Kaner,Macromolecules 41 (2008) 7405–7410.

44] P. Sbaite, D. Huerta-Vilca, C. Barbero, M.C. Miras, A.J. Motheo, Eur. Polym. J. 40

(2004) 1445–1450.

45] (a) A. Pron, F. Genoud, C. Menardo, M. Nechtschein, Synth. Met. 24 (1988)193–201;(b) Y. Cao, A. Andreatta, A.J. Heeger, P. Smith, Polymer 30 (1989) 2305–2311;(c) S.A. Ahmed, S.R. Takui, in: F. Mohammad (Ed.), Specialty Polymers Materialsand Applications, IK International Pub. House, New Delhi, 2007, pp. 23–75.

[

[

[[

s 159 (2009) 2253–2258

46] Y.-G. Han, T. Kusunose, T. Sekino, Chem. Lett. 37 (2008) 858–859.47] O.P. Dimitriev, N.A. Ogurtsov, A.A. Pud, P.S. Smertenko, Yu.P. Piryatinski, Yu.V.

Noskov, A.S. Kutsenko, G.S. Shapoval, J. Phys. Chem. C 112 (2008) 14745–14753.

48] A.Z. Sadek, W. Wlodarski, K. Shin, R.B. Kaner, K. Kalantar-zadeh, Nanotechnol-

ogy 17 (2006) 4488–4492.49] M.P. de Jong, L.J. van Ijzendoorn, M.J.A. de Voigt, Appl. Phys. Lett. 77 (2000)

2255–2257.50] V.G. Kulkarni, B. Wessling, European Patent EP0536915 (1999).51] R.W.T. Higgins, N.A. Zaidi, A.P. Monkman, Adv. Funct. Mater. 11 (2001) 407.