A Facile Route of Polythiophene Nanoparticles via Fe3+Catalyzed Oxidative Polymerization in Aqueous Medium

SUN JONG LEE,1 JUNG MIN LEE,1 IN WOO CHEONG,2 HOOSUNG LEE,3 JUNG HYUN KIM1 Nanosphere Process and Technology Laboratory, Department of Chemical Engineering, Yonsei University, 134 Shinchon-Dong, Seodaemoon-Gu, Seoul 120-749, Republic of Korea Department of Applied Chemistry, Kyungpook National University, 1370 Sankyuk-dong, Buk-gu, Daegu 702-701, Republic of Korea
3 2 1

Department of Chemistry, Sogang University, 1-1 Shinsoo-Dong, Mapo-Gu, Seoul 121-742, Republic of Korea

Received 8 May 2007; accepted 13 November 2007 DOI: 10.1002/pola.22544 Published online in Wiley InterScience (www.interscience.wiley.com).

We have demonstrated that unsubstituted thiophene can be polymerized by Fe3-catalyzed oxidative polymerization inside nanosized thiophene monomer droplets, that is, nanoreactors, dispersed in aqueous medium, which can be performed under acidic solution conditions with anionic surfactant. Besides, we proposed a synthetic mechanism for the formation of the unsubstituted polythiophene nanoparticles in aqueous medium. This facile method includes a FeCl3/H2O2 (catalyst/oxidant) combination system, which guarantees a high conversion (ca. 99%) of thiophene monomers with only a trace of FeCl3. The average particle size was about 30 nm, within a narrow particle-size distribution (PDI 1.15), which resulted in a good dispersion state of the unsubstituted polythiophene nanoparticles. Hansen solubility parameters were introduced to interpret the dispersion state of the polythiophene nanoparticles with various organic solvents. The UVVisible absorption and photoluminescence (PL) spectrum were measured to investigate the light emitting properties of the prepared unsubstituted polythiophene nanoparticle emulsions. According to nonnormalized PL analysis, the reduced total PL intensity of the polythiophene nanoparticle emulsions can be rationalized by self-absorption in a wavelength range less than C 500 nm. V 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 20972107, 2008 Keywords: conjugated polymers; dispersion; Fe3-catalyzed oxidative polymerization; nanoparticles; nanoreactor; polythiophene
ABSTRACT:

INTRODUCTION
Polythiophene is an important component of conjugated polymers, usable in a wide range of applications. Polythiophene has been the subject of intensive research during the last two decades. Because of a p-conjugated carbon backbone,
Correspondence to: J. H. Kim (E-mail: jayhkim@yonsei. ac.kr)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 46, 20972107 (2008)
C V 2008 Wiley Periodicals, Inc.

polythiophene exhibits a number of interesting electrochemical, electrochromic, luminescent, and shielding properties, which provides a basis for various new technologies.13 Thiophene derivatives can be oxidized chemically,2,4,5 photochemically,3,69 or electrochemically1 and polymerized to corresponding oligo or polythiophenes. The processability of those materials is, however, so poor as to impede their practical applications. Recently, solid layers of conjugated polymers have been successfully prepared for various electrical and electro-optical devices, for example,
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light-emitting diodes,10 solar cells,11 and eldeffect transistors.12 Generally, these layers have been deposited from an organic solution of polymers. However, the solubility of polythiophene in most organic solvents and water is extremely low. Therefore, intensive efforts have focused on the development of highly soluble and easy-toprocess polythiophenes by incorporating alkyl,13 aryl,14 or alkysulfonyl groups5 for organic solvents and carboxylic2 or sulfonic acids4 for water. Despite the progress achieved in these studies, the yield of polythiophene was often low, and the process itself is expensive or requires the use of toxic solvents.15,16 Until now, the oxidative polymerization of unsubstituted thiophene in an aqueous medium has never been reported due to several critical problems, such as the poor water solubility of polythiophene, the low oxidizing activity of the catalysts, and an extremely low conversion. Here, we proposed the formation of polythiophene nanoparticles via Fe3-catalyzed oxidative polymerization of unsubstituted thiophene inside nanosized droplets of the thiophene monomer, that is, nanoreactors, dispersed in the aqueous phase. This facile method includes a FeCl3/H2O2 (catalyst/oxidant) combination system and is different from the conventional oxidative polymerization of thiophene in chloroform.17 In addition, an enhanced processability is expected, since thinlm deposition with nanoparticles can be easily achieved by ink-jet printing1821 or screen printing22,23 techniques, which have been recently reported.

without further purication. Distilled and deionized (DDI) water was used throughout the experiments. Preparation of Polythiophene Nanoparticles Polythiophene nanoparticles were synthesized in a 250-mL double-jacketed glass reactor, which was tted with a reux condenser, a nitrogen gas inlet, an ingredient inlet, and a Teon-blade mechanical stirrer. The reaction temperature was 50 8C and maintained with a thermostat. The stirring rate was 300 rpm. The reaction procedure is as follows: SDS (0.021 mol, 6.0 g), which was dissolved in 135 mL of DDI water, was added to the reactor. Thiophene monomer (0.143 mol, 12.0 g) was dropped into the aqueous SDS solution. Hydrogen peroxide (0.793 mol, 27 g, 50% aq. solution) was added to the reactant mixture solution. FeCl3 (1.1 3 104 mol, 18.0 mg) in 15 mL of DDI water was added to the reactant mixture solution, and then this mixture was stirred for 12 h at 50 8C. Nitration of Polythiophene Nanoparticles The nitration of the unsubstituted polythiophenes was carried out using the mixed acid (95% H2SO4:61% HNO3:H2O 1.00:0.17:0.13 v/ v). An excess amount of the mixed acid was added to the polythiophene nanoparticles (80 mg for all the polythiophenes), and the mixture was stirred for 4 h at 40 8C. After cooling to room temperature, the mixture was poured into cold water. The nitrated polymer was collected by ltration, washed with water, and then dried under vacuum.24 Dispersion of Polythiophene Nanoparticles in Various Organic Solvents The prepared polythiophene nanoparticles were cleaned, using a dialysis tube for 5 weeks. One milliliter of polythiophene nanoparticles were dried in 10-mL vial glasses at room temperature under vacuum, and then various organic solvents were added to the vial glasses with a mild stirring. Characterization Solid Content, Particle Size, and Particle-Size Distribution of the Polythiophene Nanoparticles The solid content of the nal latex, as determined by a gravimetrical analysis method, was
Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

EXPERIMENTAL
Materials Thiophene monomer (Acros Organics) was refrigerated at 5 8C until use. Sodium dodecyl sulfate (SDS, Samchun Pure Chemical), lithium dodecyl sulfate (LiDS, Acros Organics), dodecyl trimethyl ammonium bromide (DTAB, Acros Organics), didodecyl dimethyl ammonium bromide (DDAB, Acros Organics), Span 80 (Ducksan Chemistry Co., LTD), and Tween 80 (Ducksan Chemistry Co.) were purchased and used as received, without further purication. Ferric Chloride (anhydrous FeCl3, Kanto Chemical) and hydrogen peroxide (H2O2, DC Chemical) were used as catalysts and oxidants. They were dried at 20 8C in the vacuum oven before use. They were all analytical grade and used

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9.23 wt %. The particle size and particle-size distributions were measured by a transmission electron microscope (TEM; H-7600, Hitachi) and capillary hydrodynamic fractionation instrument (CHDF; CHDF-2000, Matec Applied Sciences). Molecular Weight and Molecular-Weight Distribution of the Nitrated Polythiophenes Molecular weight and molecular-weight distribution of the nitrated polythiophenes were obtained using gel-permeation chromatography (GPC, Waters Co.) equipped with a series of Waters1 columns (HR4, HR3, HR2, HR1), HPLC pump, RI detector, and data module at 40 8C. Molecular weights were determined from the refractive index data, which were analyzed with Waters Breeze1 System. Polystyrene standards and universal calibration was adapted to reduce measuring error. Eluent was tetrahydrofuran (THF) with a ow rate of 1.0 mL/min. Photoluminescence Properties of the Polythiophene Nanoparticles The UVVisible absorption spectra were obtained with a UVVis spectrophotometer (UV1601PC, Shimadzu). Photoluminescence spectra were recorded with a spectrouorophotometer (RF-5301PC, Shimadzu). The excitation was incident at an angle of 08 onto the front face of the sample, and the emission was recorded in reection at an angle of 908 with respect to the surface normal.

RESULTS AND DISCUSSION

Figure 1(a) shows a schematic for the formation of the polythiophene nanoparticles in aqueous medium. In this work, polythiophene nanoparticles were produced from stable thiophene monomer-swollen micelles, with a size of 5 20 nm. The polymerization mechanism includes the following ve steps: (a) the formation of stable monomer-swollen micelles (stabilization step), (b) the diffusion of Fe3 ions from the aqueous phase to the anionically charged interface of the micelles (diffusion step), (c) a reaction between thiophene monomers and the Fe3 ions (initiation step), (d) a reaction between the cationic thiophene monomeric radicals (propagation step), and (e) the oxidation of the Fe2 ion and regeneration of Fe3 (its original state) by H2O2
Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

(regeneration step). The repetitive process of the steps from (c) to (e) is a recyclable reduction oxidation process, which leads to a high conversion of the thiophene monomers in aqueous medium. Figure 1(b) shows the mechanism proposed for the Fe3-catalyzed oxidative polymerization of thiophene. The rst and second steps are prereaction steps, which create stable and reactionfavorable conditions. The third step consists of the oxidation of the monomer and transformation into its cationic radical. This step involves the coupling of two radicals to produce the dihydro dimeric dication that leads to a dimer after the loss of two protons and rearomatization. In the fourth step, the dimer, which is more easily oxidized than the monomer, turns into its cationic radical by Fe3 ions and undergoes a further coupling with a monomeric or oligomeric cationic radical. A high concentration of cationic radicals around the vicinity of the micelle is expected due to the electrostatic attraction between sulfate (OSO3 ) groups from the 3 ions, which are drawn into micelles and Fe the interface of the monomer-swollen micelle from the water phase. In the fth step, Fe2 ions are transformed into Fe3 ions by a reaction with H2O2, which guarantees a high conversion of thiophene monomers with only a trace of FeCl3. Oxidative polymerizations of thiophene, using several different oxidants, were carried out, and samples were taken at various intervals and analyzed. The timeconversion curves for these samples are shown in Figure 2. Figure 2(a,b) shows the conversion curves for the polymerization of thiophene monomers (0.143 mol, 12.0 g), using (a) FeCl3 (1.1 3 104 mol, 18.0 mg) and (b) H2O2 (0.793 mol, 27 g) as an oxidant, respectively. The nal conversions were only about 4.8% and 10.2%, respectively. However, 99% of the nal conversion was achieved in the FeCl3/H2O2 (catalyst/oxidant 1.1 3 104 mol/0.793 mol) combination system, as seen in Figure 2(c). A very large molar concentration of FeCl3 (e.g., FeCl3: thiophene 2.5:1) is often used for the bulk and solution polymerizations of thiophene; however, it should be removed from the nal product to obtain a sufcient photoluminescence property due to the quenching effect of the FeCl3.25 On the other hand, there is no need to remove FeCl3 in the current work because only a trace of FeCl3 was used. In addition, it would be much easier to remove the trace of FeCl3 through washing after

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Figure 1. (a) A schematic illustration of the mechanism for the preparation of polythiophene nanoparticles via Fe3-catalyzed oxidative polymerization. (b) Detailed reaction mechanism of thiophene via Fe3-catalyzed oxidative polymerization.

centrifugation,26 dialysis,27 or extraction method with ethylenediaminetetraacetic acid (EDTA) solution28 since the produced polythiophene was in particle form. FeCl3 is believed to exist on the surface of the produced polythiophene nanoparticles because a reaction between thiophene monomers and the Fe3 ions happened at the surface of growing particles due to the electro static attraction between sulfate (OSO3 ) groups 3 and Fe ions, which are drawn into the surface of the monomer-swollen micelle. Figure 3 shows the nal conversions for polythiophene nanoparticles prepared at various pH conditions, using pH 2, pH 4, pH 7, and pH 10 buffer solutions. The nal conversions were about 99.4%, 99.1%, 35.3%, and $0%, respectively. From this result, we concluded that acid-

Figure 2. Conversiontime curves for polythiophene nanoparticles prepared by Fe3-catalyzed oxidative polymerization in aqueous medium. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

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Figure 3. Final conversions for polythiophene nanoparticles prepared at various pH conditions (at 12 h reaction time).

ity of the mixture solution affected the chemical activities of oxidants, that is, the FeCl3 and H2O2. In the current catalytic system, the oxidizing power of H2O2 is most important in ensuring the high conversion of thiophene monomers, since Fe2 ions are transformed into Fe3 ions by a reaction with H2O2. Generally, oxidizing power of oxidizing agents can be estimated by the standard reduction potential (Eo). The less positive the value of the standard reduction potential, the more stable the species is and the less easily it is reduced. The standard reduction potentials of FeCl3 and H2O2 in acidic solution were 0.771 and 1.776 V, respectively, at pH 0. Therefore, H2O2 can easily oxidize Fe2 ions to Fe3 ions due to the higher standard reduction potential of the H2O2 in acidic solution. On the contrary, the standard reduction potentials of the FeCl3 and H2O2 in basic solution (pH 14) were 0.56 V and 0.88 V, respectively. H2O2 can also easily oxidize the Fe2 ions to Fe3 ions because the situation of the higher standard reduction potential of H2O2 remained unchanged in basic solution; however, FeCl3 was more stable and easily not reduced but oxidized in basic solution because the standard reduction potential of the FeCl3 was the negative value (i.e., 0.56 V). Therefore, FeCl3 cannot oxidize thiophene monomers to cationic radicals, which react with other cationic radicals to make the polythiophene nanoparticles. In addition, Fe2 ions and Fe3 ions transform into iron salts form in basic solution. These salts do not allow the monomer-swollen micelles to maintain colloidal stability in the aqueous medium
Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

during the polymerization, even though the excessive surfactant was used. These results caused a relatively low conversion of thiophene monomers in basic solution. Typically, all elements including FeCl3 and H2O2 in positive oxidation states begin to exist in water as hydrated cations and then undergo reactions between the cations and the water to neutralize their positive charges. These reactions ultimately alter the pH of the solution; thus, we should maintain the suitable low pH value. Figure 4 shows the conversiontime curves for Fe3-catalyzed oxidative polymerization of thiophene using three types of surfactants. The polymerizations of thiophene were performed by using each SDS, LiDS, as anionic surfactants, Span 80, Tween 80, as nonionic surfactants, and DTAB, DDAB, as cationic surfactants. Ionic surfactants were used to investigate the effects of the electrostatic interactions between ionic groups of the surfactants and Fe3 ions on the monomer conversion. As seen in Figure 4, the nal conversions were about 99.9%, 99.5%, 49.0%, 46.2%, 25.5%, and 21.0%, respectively. From these results, one can see that anionic surfactants were more effective in preparing polythiophene nanoparticles with high monomer conversions. This is because the electrostatic attractive interaction between sulfate (OSO3 ) 3 groups from the micelles and Fe ions guarantees a high concentration of cationic radicals around the vicinity of the micelles. In the case of the cationic surfactants, the situation was quite the opposite of the anionic surfactants. A

Figure 4. Conversiontime curves for Fe3-catalyzed oxidative polymerization of thiophene using several different surfactants.

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Figure 5. TEM images of 30-nm unsubstituted polythiophene nanoparticles with a raspberry-like morphology: (a) Polythiophene aggregates at low magnication (310,000). The inset on the right depicts an individual polythiophene nanoparticle at high magnication (350,000). (b) The particle size and size distribution of the polythiophene nanoparticles, measured using a CHDF.

very low concentration of cationic radicals around the vicinity of the micelle is expected due to the electrostatic repulsive interaction between cationic head groups ((CH3)3N) of the cationic surfactants and Fe3 ions. The repulsive force was sufcient to hinder from proceeding polymerization reactions among the monomeric or oligomeric cationic radicals. Consequently, the usage of the cationic surfactants led to low monomer conversions due to the electrostatic repulsion with Fe3 ions. Contrary to ionic surfactants, nonionic surfactants are relatively free from the electrostatic interactions. With nonionic surfactants, it is clear that very stable aqueous dispersion can be produced and that the adsorbed layers of the nonionic surfactants are producing repulsion between two emulsions greater than that expected on the basis of electrostatic effects. These steric stabilization effects allow the monomer-swollen active micelles to maintain colloidal stability in the aqueous medium during the Fe3-catalyzed oxidative polymerization. Meanwhile, Fe3 ion is attracted to lone pair electrons of oxygen atoms in polyethylene oxide chain of nonionic surfactants.29 Consequently, Fe3 ions dissolved in the water medium are drawn into thiophene monomer droplet interface, where the Fe3 ions come to react with thiophene monomers. However, the molecular diffusion of the

Fe3 ions toward thiophene droplet interface by the attractive interaction with lone pair electrons of oxygen atoms is less effective than that by the electrostatic attractive interaction. Therefore, the difference of attractive driving force for the Fe3 ions caused a lower conversion of thiophene monomers than that of anionic surfactants, but higher conversion than that of cationic surfactants. Figure 5 shows the TEM micrograph and particle-size distribution of the polythiophene nanoparticles. Figure 5(a) shows some aggregates of the polythiophene nanoparticles and the individual particles with a raspberry-like morphology. The average particle size of the individual particle is about 30 nm, which is in good agreement with capillary hydrodynamic fractionation (CHDF) data in Figure 5(b). The CHDF data shows a unimodal peak of polythiophene nanoparticles. From the particle size and particlesize distribution data, a good dispersion state of the polythiophene nanoparticles was expected. In Figure 6, the photographic image of polythiophene nanoparticles in various organic solvents was shown. The dispersion state showed that the polythiophene nanoparticles were welldispersed in many polar solvents except acetone. Hansen solubility parameters (d2 d2 d2 t p d d2 ) were introduced to interpret the dispersion h state of the polythiophene nanoparticles with
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Figure 6. Dispersion state of the unsubstituted polythiophene nanoparticles in various organic solvents (10 g polythiophene/1L solvent at room temperature). [Color gure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

various organic solvents. The solubility parameter includes cohesive energy from the dispersive component (dd), a permanent dipoledipole interaction component (dp), and the hydrogen bonding component (dh). Hansen solubility parameters of various solvents are listed in Table 1. The dispersion state seems to depend on the total solubility parameter (dt) of the solvent, which can be well demonstrated with the photographic image of the polythiophene nanoparticles in various solvents as shown in Figure 6. Among the solvents, THF and acetone show relatively poor dispersion states while their dt values are close to those of good solvents, such as NMP or DMF. To explain this result, the 3D plot of the three components of Hansen parameters for various solvents is shown in Figure 7. From Figure 7, it can be concluded that both dh and dp are the important factors governing the dispersion state. Thiophene is a heterocyclic compound with one sulfur atom; therefore, hydrogen atoms from organic solvents are attracted to the lone pair of electrons on the negatively polarized sulfur atom of thiophene to form a hydrogen bond. The sulfur atom of thiophene is more electronegative than hydrogen and has a lone pair of electrons. The lone pair orbital of the sulfur atoms in polythiophene projects into the space away

from the positively charged nuclei, promoting a considerable charge separation and large contribution to the dp. As a result, the dispersion state of the polythiophene nanoparticles in polar solvents, such as alcohol, DMSO, DMF, and NMP, is better than in nonpolar solvents. Figure 8 shows the emissions of polythiophene nanoparticle emulsions with respect to varying reaction time, under a 365-nm UV irradiation. Polythiophene is known as a typical, red-color-emitting material. However, the emission color of the polythiophene nanoparticle emulsions was not red at less than 80% conversion, after 4 h. This result implied that high-molecular-weight polythiophene was not formed until that conversion. The Fe3-catalyzed oxidative polymerization seems to follow reaction routes similar to a step-growth polymerization mechanism, as seen in Figure 1(b).30 At an early stage of Fe3-catalyzed oxidative polymerization, the growth of the polymer chain is somewhat slow because one proceeds slowly from the monomer to dimmer, trimer, tetramer, pentamer, and so on. These reactions proceed until eventually large polymer molecules consisting of large numbers of monomer molecules have been formed in the monomer-swollen micelles. Any two cationic species can react with each other

Table 1. Hansen Solubility Parameters of Various Organic Solvents at 25 8C Organic Solvents Solubility Parameters (MPa1/2) dd dp dh dt Methylene Chloride 18.2 6.3 6.1 20.3

MeOH 15.1 12.3 22.3 29.7

DMSO 18.4 16.4 10.2 26.6

EtOH 15.8 8.8 19.4 26.6

DMF 17.4 13.7 11.3 24.8

NMP 18.0 12.3 7.2 22.9

THF 16.8 5.7 8.0 19.4

Acetone 15.5 10.4 7.0 20.1

Chloroform 17.8 3.1 5.7 19.0

Hexane 14.9 0 0 14.9

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Figure 7. 3D plot of dispersion states versus the three components of Hansen solubility parameters of various solvents.

throughout the course of the Fe3-catalyzed oxidative polymerization. However, the situation is quite different from the conventional step polymerization with regard to the molecular weights of the prepared polymers.

Figure 9 shows a variation of weight-average molecular weight (Mw) of nitrated polythiophene nanoparticles with percent conversion for the Fe3-catalyzed oxidative polymerization. Samples were taken at various intervals and analyzed after nitration. The obtained original polythiophene nanoparticles were insoluble in organic solvents. After the nitration, however, the nitrated polythiophene nanoparticles became soluble in THF, DMF, and DMSO, and the estimation of the molecular weights of the original polythiophene nanoparticles by GPC became possible. The amount of the obtained nitrated polythiophene nanoparticles was about 90 mg. The degree of nitration was calculated from the N/C molar ratio obtained in elemental analysis. Analytical data of nitrated polythiophene nanoparticles gave an N/C molar ratio of (10.84/ 14.01)/(37.18/12.01) 1.00N/4C, corresponding to a degree of the nitration of 1.00: Analysis calculated for (C4HNO2S 0.26H2O)n: C, 37.25; H, 1.19; N, 10.86. Found: C, 37.18; H, 1.18; N, 10.84. As shown in Figure 9, the nitrated polythiophene nanoparticles showed Mw values of 12216240, corresponding to the degree of the polymerization (DP) values of 9.649.1, which were calculated from the Mw value determined by GPC analysis of the nitrated polythiophenes

Figure 8. Time-evolution emission of polythiophene nanoparticle emulsions with varying reaction time under 365-nm UV irradiation. Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

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formed, electrons would be more easily transferred to the near neighbor conjugated molecules through the conjugated long chain back-

Figure 9. Variation of weight-average molecular weight (Mw) of nitrated polythiophene nanoparticles with percent conversion for the Fe3-catalyzed oxidative polymerization.

and the degree of nitration.24 Consequently, we could estimate molecular weights of original polythiophene nanoparticles with 7884029 g/mol from DP of nitrated polymers. We have obtained a fairly good approximation of Mw values of the original unsubstituted polythiophene nanoparticles. From Figure 9, it was conrmed that the progress of molecular weights during the Fe3catalyzed oxidative polymerization is quite different from that of the conventional step polymerization. Figure 9 shows a linear increase of molecular weight with conversion, which indicates that the polymerization mechanism departs from the normal step pathway. This is quite similar to the situation observed in certain ionic chain polymerizations, which involve a fast initiation process coupled with the absence of reactions that terminate the propagating reactive centers. More specically, a high-molecularweight polymer is obtained in step polymerization only near the very end of the reaction (>98% conversion).31 On the other hand, in the Fe3-catalyzed oxidative polymerization, a relatively high-molecular-weight polymer can be obtained in the middle of the polymerizing reaction (>80% conversion) as seen in Figure 9. This is because the oligomers (dimmer, trimer, tetramer, and so on) are more easily oxidized than the monomer and turn into their cationic radical forms and undergo a further coupling with a monomeric or oligomeric cationic radical.32 The emission color of the polythiophene is directly dependent on the effective conjugation chain length. If once relatively large molecules were
Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola

Figure 10. (a) UVVis absorption spectra of polythiophene nanoparticle emulsions prepared by Fe3-catalyzed oxidative polymerization with varying reaction time, (b) normalized, and (c) non-normalized PL spectra of polythiophene nanoparticle emulsions with varying reaction time (excitation wave length 400 nm).

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bone of the polymers with the high molecular weight. As a result, a reaction for about 6 h was required for the complete manifestation of the original red emission. Figure 10(a) shows the UVVis absorption spectra of polythiophene nanoparticle emulsions with varying reaction time at the polythiophene concentration of 1.0 3 103 M. A broad absorption with kUV 400 nm was observed at all the Max reaction intervals, as shown in Figure 10(a). As seen in Figure 10(b), each PL intensity was normalized to compare a shift of kPL for each samMax ple. The kPL of the polythiophene nanoparticle Max emulsions showed a red-shift from 484 to 511 nm. In addition, an increase of the PL intensity was observed at a wavelength range of 600 650 nm after 6 h, which resulted from the selfabsorption, that is, some emitted photons are absorbed by other solute molecules in solution due to overlapping with photoabsorption and photoemission wavelengths of molecules33,34 of the polythiophene nanoparticles in a wavelength range less than 500 nm. The self-absorption in a wavelength range less than 500 nm resulted in a transformation of the PL spectrum shape. This result was corroborated by the non-normalized PL spectra from Figure 10(c). The total PL intensity of the polythiophene nanoparticle emulsions decreased due to self-absorption as the polymerization progressed.

solvents, such as THF, chloroform, methylene chloride, and hexane. From the Hansen solubility parameters, it was concluded that the dispersion state of polythiophene nanoparticle was predominantly affected by the dipole and hydrogen bonding interactions. A broad absorption with kUV about 400 nm was observed during Max the polymerization. The red-shift from 484 to 511 nm in the maximum wavelength (kPL ) of Max PL intensity and the increase of the PL intensity at a wavelength range of 600650 nm resulted in red-emitting PL property of the unsubstituted polythiophene nanoparticle emulsions. Self-absorption of the polythiophene nanoparticles caused a reduced PL intensity, and which was also conrmed by a non-normalized PL analysis. Most important, this facile method will allow the improved processability of the unsubstituted polythiophene nanoparticles in various electrical and electro-optical applications without introducing any additional chemical conversion steps.
This work was nancially supported by the Ministry of Education and Human Resources Development (MOE), the Ministry of Commerce, Industry and Energy (MOCIE), and the Ministry of Labor (MOLAB) through the fostering project of the Lab of Excellency and the Ministry of Commerce, Industry, and Energy (MOCIE) through the project of NGNT (No. 100231352005-11 and 10024160-2006-12).

CONCLUSIONS
In summary, unsubstituted polythiophene nanoparticles with 30 nm diameter were successfully prepared using Fe3-catalyzed oxidative polymerization in aqueous medium. Ninety-nine percent monomer conversion was achieved in acidic solution with a trace of FeCl3, which usually deteriorates the photoluminescence (PL) property of polythiophene nanoparticles. Among ionic and nonionic surfactants, anionic surfactants were more effective in preparing the unsubstituted polythiophene nanoparticles with the high conversion of thiophene monomers. Owing to its ne particle size of the polythiophene, it could be well dispersed in both aqueous media and various organic solvents, and which suggested a good processability in the fabrication of electroluminescent devices. Among several organic solvents, the polythiophene nanoparticles were well-dispersed in many polar solvents except acetone, compared to nonpolar

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Journal of Polymer Science: Part A: Polymer Chemistry DOI 10.1002/pola