Synthetic Metals 162 (2012) 4448

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Improvement of dispersion state and charge separation efciency of hybrid lms of ZnO nanoparticle/conjugated polymers by utilizing methanol as a volatile dispersant
Tanita Hirunprateep a,b , Nisanart Traiphol a,b, , Ruttayapon Potai c , Rakchart Traiphol c,d,
Research Unit of Advanced Ceramics, Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand Research Unit of Advanced Ceramic and Polymeric Materials, National Center of Excellence for Petroleum, Petrochemical, and Advanced Material, Chulalongkorn University, Bangkok 10330, Thailand c Laboratory of Advanced Polymers and Nanomaterials, Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand d NANOTEC Center of Excellence at Mahidol University, Rama 6 Road, Ratchathewi, Bangkok 10400, Thailand
b a

a r t i c l e

i n f o

a b s t r a c t
This contribution introduces an efcient method for fabricating hybrid lms of ZnO nanoparticle/conjugated polymers with improved charge separation efciency. Methanol is utilized as a volatile dispersant for promoting the dispersion of ZnO nanoparticles in chlorobenzene. The increase of methanol concentration from 0 to 20% (v/v) results in systematic improvement of the particle dispersion. The suspensions of ZnO nanoparticles in these solvents are used to prepare hybrid lms of poly[2-methoxy-5-(2 -ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and regioregular poly(3hexylthiophene) (P3HT). The morphologies and optical properties of the hybrid lms, prepared by spin casting, are investigated by atomic force microscopy, UV/vis absorption and photoluminescence (PL) spectroscopy. The hybrid lms obtained from all systems are continuous and exhibit relatively smooth surface. The extent of polymeric chain aggregation in the hybrid lms is hardly affected by the variation of solvent. However, the drop of about 60% of PL intensity is detected when the methanol is added into ZnO/MEH-PPV solution prior to the lm preparation. The drastic decrease of PL intensity indicates signicant improvement of charge separation efciency in the hybrid lms. The investigation of ZnO/P3HT hybrid lms shows consistent results. Our approach is very efcient because the methanol completely evaporates during the fabrication of hybrid lm. 2011 Elsevier B.V. All rights reserved.

Article history: Received 29 August 2011 Received in revised form 14 October 2011 Accepted 10 November 2011 Available online 3 December 2011 Keywords: Photovoltaic cells Bulk heterojunction Solvent effect Interfacial interaction Conjugated polymer Composite materials

1. Introduction In past century, the development of solar cell has emphasized on silicon based materials. However, several disadvantages of the devices include high production cost, high temperature processing and non-exibility. The discovery of conducting polymers allows the utilization of these materials in a new type of photovoltaic device known as plastic solar cell [110]. However, conjugated polymers used as an active component in this device

Corresponding author at: Research Unit of Advanced Ceramics, Department of Materials Science, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand. Tel.: +66 22185541; fax: +66 22185561. Corresponding author at: Laboratory of Advanced Polymers and Nanomaterials, Department of Chemistry and Center for Innovation in Chemistry, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand. Tel.: +66 55 963451; fax: +66 55 261025. E-mail addresses: Nisanart.T@chula.ac.th (N. Traiphol), Rakchartt@nu.ac.th (R. Traiphol). 0379-6779/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2011.11.006

posses rather limited charge separation and charge transportation efciency. Addition of some organic/inorganic nanoparticles into the system can enhance the efciency of plastic solar cell. This concept is known as bulk heterojunction in which the conjugated polymers transport the photo-excited electrons to electrode via the nanoparticles [14,7,8]. Therefore, the ideal structure of bulk heterojunction is a bicontinuous phase of conjugated polymers interpenetrating with interconnected nanoparticles. The high interfacial areas between the conducting polymers and nanoparticles increase charge transporting of electrons and holes for collection at cathode and anode [1,3,4,7]. The nanoparticles that have been utilized as electron acceptors in bulk heterojunction photovoltaics include CdSe, PCBM, C60 , TiO2 and ZnO. The nanoparticles of metal oxides are of interest in this work because of their chemical stability, low cost, high charge carrier mobility, and proper band gap [7]. Although the hybrid lm combines the advantages of conjugated polymers and inorganic nanoparticles, the development of this system into an efcient plastic solar cell needs to overcome

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Fig. 1. (Left) TEM image of ZnO nanoparticles and (right) schematic representation of interfacial interaction between ZnO nanoparticles and methanol in solution of conjugated polymers, MEH-PPV and P3HT, in chlorobenzene.

some obstacles. In general, the inorganic nanoparticles have a polar surface while most of the conjugated polymers are nonpolar molecule. Therefore, the mixing of these materials in liquid or solid phase is rather difcult or results in microphase separation [3,4,7]. Many approaches have been suggested for solving this problem such as the modication of polymeric structure and/or surface treatment of inorganic nanoparticles to promote interfacial interactions [7,1113]. The use of nanorod or hyperbranched inorganic layers is also an efcient method for fabrication of stable interpenetrating structure with conjugated polymer [1416]. However, these approaches are rather complicate for large-scale production. The utilization of conventional surfactants to promote the dispersion of inorganic nanoparticles has also been studied [17,18]. The apparent drawback of conventional surfactants is that they tend to remain coated on surface of the inorganic nanoparticles after the fabrication process due to their high boiling point. Since surfactants are organic material with no conducting properties, the coated molecules inevitably obstruct the transporting of electrons from the conjugated polymer to the inorganic nanoparticles. Therefore, it is desirable to use the surfactant-free process for fabrication of plastic solar cell [7,19]. Many studies have observed that the use of mixed solvents such as chlorobenzene/pyridine, chlorobenzene/tetrahydrofuran, chlorobenzene/chloroform, chloroform/pyridine and others to codisperse inorganic nanoparticles and conjugated polymers leads to plastic solar cell with good power conversion efciency [7,2027]. However, systematic study on the roles of each solvent on the morphology and charge separation efciency of hybrid lms was not presented. This work aims to utilize a mixed solvent approach to prepare hybrid lms of conjugated polymers and ZnO nanoparticles. Mixtures of chlorobenzene and methanol at various ratios are used to co-disperse the ZnO nanoparticles and conjugated polymers prior to the fabrication of hybrid lms. While chlorobenzene is a good solvent for poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and regioregular poly(3-hexylthiophene) (P3HT), the hydroxyl group of methanol is expected to interact with ZnO surface (see Fig. 1). The increase of interfacial interactions between the inorganic nanoparticles and the non-polar conjugated polymers are expected to enhance the dispersion. In contrast to conventional surfactants, the boiling point of methanol is very low, allowing simple removal after the fabrication process. 2. Experimental The MEH-PPV (Mn = 75,000 g/mol, Mw /Mn = 3.5) and regioregular P3HT (Mn = 42,300 g/mol, Mw /Mn = 1.9) were purchased from SigmaAldrich. The ZnO nanoparticles were obtained from Nano

Materials Technology (Thailand). The primary size of ZnO nanoparticles ranges from about 20 to 50 nm (see Fig. 1). The solvents, chlorobenzene and methanol, used in this study are analytical reagent grade. The ZnO nanoparticles at 2.5 wt.% concentration (28 mg/mL) were dispersed in chlorobenzene (CBZ) by stirring with magnetic bar for 30 min. The suspension was subjected to an ultrasonication in ultrasonic bath (S30H Elmasonic, Elma) for 10 min and followed by an ultrasonication using ultrasonic probe (High Intensity Ultrasonic Processor VC/VCX, Sonics & Materials, Inc.) for 15 min. The ultrasonicating processes were repeated 4 times. The resultant suspension was ltered through nylon membrane with 0.45 m pore size to remove large agglomerates. The suspension was divided into three portions. Methanol at concentration of 10% (v/v) and 20% (v/v) was introduced into the samples while chlorobenzene was used to dilute the suspensions to provide the same concentration of ZnO nanoparticles in all samples. The suspensions were stirred for about 1 h to allow equilibrium state. The MEH-PPV and P3HT powders were added into the suspensions of ZnO nanoparticles. The concentration of polymers was 5 mg/mL. The samples were continuously stirred at room temperature for about 16 h to allow complete solubilization of the polymers. All samples were kept under dark during the sample preparation. Prior to the addition of conjugated polymers, the ZnO suspensions in pure chlorobenzene and mixed solvents were dropped cast on a polished silicon wafer. The dispersion state of ZnO nanoparticles in each system was revealed by utilizing atomic force microscopy (AFM) (SPI3800N Nanoscope II, Seiko Instument Inc., Japan) operating in ambient conditions. The cantilever was fabricated from Si3 N4 with a spring constant of about 15 N/m. The diameters of ZnO domains were measured from full width at half height maximum. The averaged values were obtained from at least 50 measurements. The hybrid lms of ZnO nanoparticles/conjugated polymers were prepared by spin casting from the mixed solutions onto cleaned silicon wafer or quartz slide. The spinning speed was kept at 1000 rpm for 10 s. The substrates were cleaned by soaking in a mixture of conc. H2 SO4 and 30% H2 O2 (7:3, v/v) at 80 C for 1 h. The substrates were rinsed by distilled water several times and dried with N2 gas. Morphologies of the lms were investigated by utilizing AFM in intermittent contact mode. The AFM was also used to measure the lm thickness. A needle soaked with chloroform was used to scratch the lms. The AFM scanning of this area allowed the determination of lm thickness, which was about 70 nm. The presence of ZnO nanoparticles in the hybrid lms was conrmed by using thermogravimetric analysis (TGA) and Fouriertransformed infrared spectroscopy (FT-IR). The TGA measurements also detected about 5 wt.% of ZnO nanoparticles within the hybrid lms. The ZnO concentration in all lms is comparable as further revealed by FT-IR measurements. The UV/vis absorption and photoluminescence (PL) spectra of the hybrid lms were measured from Analytica Specord 100 and Perkin-Elmer LS55 spectrometers, respectively. Three samples were measured for each condition. For the PL measurements, the samples in each series were measured at the same time. The measurements were repeated several times to minimize experimental errors. The PL spectra were normalized to the absorbance of each lm at the excitation wavelength prior to the comparison.

3. Results and discussion The effects of methanol additives on dispersion state of ZnO nanoparticles in suspensions were investigated by utilizing AFM. The ZnO suspensions in pure chlorobenzene and mixed solvents were dropped cast on a polished silicon wafer. Fig. 2 illustrates AFM

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Fig. 2. AFM topography images of ZnO nanoparticles on silicon wafer. The samples were prepared by drop casting from the ZnO suspensions in (a) pure chlorobenzene, (b) mixture of chlorobenzene and 10% (v/v) methanol and (c) mixture of chlorobenzene and 20% (v/v) methanol.

Fig. 3. AFM topography images of (ac) ZnO/MEH-PPV and (df) ZnO/P3HT hybrid lms. The hybrid lms were prepared by spin casting from the ZnO/conjugated polymer solutions in (a and d) pure chlorobenzene, (b and e) mixture of chlorobenzene and 10% (v/v) methanol and (c and f) mixture of chlorobenzene and 20% (v/v) methanol.

Fig. 4. Absorption spectra of (a) ZnO/MEH-PPV and (b) ZnO/P3HT hybrid lms. The hybrid lms were prepared by spin casting from the ZnO/conjugated polymer solution in (1) pure chlorobenzene, (2) mixture of chlorobenzene and 10% (v/v) methanol and (3) mixture of chlorobenzene and 20% (v/v) methanol. The spectra were normalized and shifted vertically for presentation.

topography images of ZnO nanoparticles prepared from different conditions. It is obvious that the dimension of ZnO agglomerates systematically decreases upon increasing the ratio of methanol in the mixed solvents. For the sample obtained from pure chlorobenzene, large ZnO agglomerates are detected. The averaged diameter

is about 93 38 nm. When the ratios of methanol in the mixed solvents are increased to 10 and 20% (v/v), the diameter of ZnO agglomerates decreases to 63 10 nm and 39 10 nm, respectively. This result indicates that methanol behaves as a dispersant for ZnO nanoparticles in the chlorobenzene. It has been known

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Fig. 5. PL spectra of (a) ZnO/MEH-PPV and (b) ZnO/P3HT hybrid lms. The hybrid lms were prepared by spin casting from the ZnO/conjugated polymer solution in (1) pure chlorobenzene, (2) mixture of chlorobenzene and 10% (v/v) methanol and (3) mixture of chlorobenzene and 20% (v/v) methanol. The PL spectra were normalized to the absorbance at the excitation wavelength of each lm, 500 nm for the MEH-PPV and 475 nm for the P3HT. The hybrid lms were annealed at 90 C for 1 h.

that ZnOH, Zn-O and ZnOH2 + groups are present at the surface of ZnO nanoparticles [28,29]. These groups can preferably interact with the hydroxyl group of methanol while the methyl group provides favorable interaction with the organic medium (see Fig. 1). The increase of interfacial interactions leads to the improvement of dispersion state of ZnO nanoparticles. Our result is consistent with previous study by Rhodes and coworkers where turbidity measurement is utilized to probe the dispersion state of ZnO nanoparticles in suspension [24]. They observed that the addition of methanol into suspensions of ZnO nanorods and nanocrystals in chlorobenzene led to drastic decrease of turbidity, corresponding to the improved dispersibility. Methanol is a poor solvent for MEH-PPV and P3HT. The addition of methanol into solutions of the polymers in chlorobenzene inevitably reduces the polymersolvent interactions [3133]. This could affect the lm morphology as well as the chain organization within the lms. Fig. 3 illustrates AFM topography images of ZnO/MEH-PPV and ZnO/P3HT hybrid lms prepared by using different solvents. The hybrid ZnO/MEH-PPV lm obtained from pure chlorobenzene system is smooth and continuous. The increase of methanol ratio in the mixed solvents causes the appearance of large domains. The results obtained from the ZnO/P3HT lms are consistent. The formation of large domains within the lms is attributed to the agglomeration of polymers during the fabrication process due to the decrease of solubility. However, the lms are still continuous, which is an important requirement for their utilization in plastic solar cell. The chain organization within the lms is further explored by utilizing UV/vis absorption spectroscopy. It has been known that inter- and intrachain segmental aggregation of MEH-PPV and P3HT alters the HOMOLUMO energy gap of chromophores [3034]. The absorption bands of MEH-PPV and P3HT aggregates shift to lower energy region compared to those of the isolated chains. Therefore, the comparison of absorption bands of the hybrid lms can reveal the magnitude of chain aggregation [34]. Fig. 4 illustrates the absorption spectra of ZnO/MEH-PPV and ZnO/P3HT lms prepared by using different solvents. The absorption spectra of all ZnO/MEHPPV lms exhibit a broad and featureless pattern. The detection of relatively high absorbance at 550 nm indicates the existence of aggregates within the lms [31,34]. The increase of methanol ratio in the mixed solvents hardly affects the absorption pattern. This result indicates that the formation of large polymeric domains illustrated in Fig. 3 does not lead to the increase of segmental aggregation. For the system of ZnO/P3HT lms, the absorption bands at about 525, 550 and 600 nm correspond to segmental aggregates [32,33]. Similar to the system of ZnO/MEH-PPV lms, the increase of methanol ratio in the mixed solvents causes the formation of large polymeric domains but hardly affects the pattern of

absorption spectra. Therefore, the magnitude of aggregates in each series of the hybrid lms is comparable. The charge separation efciency within the hybrid lms is explored by utilizing photoluminescent spectroscopy. In general, the charge separation of photo-excited electrons is competed by the charge recombination process, which emits photons as a product [14,7,8]. The PL intensity, therefore, indicates the extent of charge recombination process. The lesser PL intensity corresponds to higher charge separation efciency. Fig. 5 illustrates PL spectra of ZnO/MEH-PPV and ZnO/P3HT lms prepared by using different solvents. The PL intensity of all spectra is divided by the absorbance at the excitation wavelength of each lm. This process is necessary for normalization of the excited chromophores. The PL spectra of ZnO/MEH-PPV lms consist of a peak at 590 nm accompanied with broad shoulder at 645 nm, which correspond to the photoemission of aggregates [31,34]. The PL spectra of all lms exhibit similar pattern, indicating same type of the emitter. However, the PL intensity of the hybrid lms fabricated by using the mixed solvents is much lower. Fig. 6 compares the integrated PL intensity of the hybrid lms fabricated by using different solvents. The presence of 10% (v/v) methanol in the mixed solvent causes about 60% drop of PL intensity. The increase of methanol ratio to 20% (v/v) results in slight drop of PL intensity. Since the fraction of aggregates as well as the ZnO nanoparticles is comparable in all lms, the drastic drop of PL intensity corresponds to signicant increase of charge separation efciency. The improvement of dispersion state of ZnO nanoparticles within the hybrid lms provides higher interfacial area with conjugated polymers, facilitating the charge separation process. The annealing of hybrid lms at 90 C for 1 h slightly affects the PL intensity but the trend remains the same. Previous studies have

Fig. 6. Relative PL intensity of ZnO/MEH-PPV and ZnO/P3HT hybrid lms (open symbols) before and (lled symbols) after the annealing at 90 C for 1 h.

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shown that the improvement of charge separation efciency within the hybrid lms leads to the increase of short circuit current density, ll factor and power conversion efciency of the photovoltaic device [22,25,36]. The investigation of ZnO/P3HT lms shows similar results. Fig. 5b illustrates PL spectra of the hybrid lms fabricated by using different solvents. All spectra exhibit the same pattern but the PL intensity is weaker in the hybrid lms prepared by using the mixed solvents. However, the decrease of PL intensity is less obvious compared to the ZnO/MEH-PPV system. For the nonanneal lms, the drop of PL intensity is less than 10%. The drop of PL intensity to 20% is observed when the hybrid lms are annealed at 90 C for 1 h (see Fig. 6). The annealing process in this system probably promotes the interfacial contact between ZnO nanoparticles and P3HT within the lms [35,3739]. The free volume or pores at nanoparticle/polymer interface, which occur during the evaporation of solvent, is reduced due to the reorganization of polymeric chains. The annealing also promotes the crystallinity of P3HT, leading to the increase of hole conductivity [40]. It is important to note that the investigation by using infrared spectroscopy does not detect the presence of methanol in the hybrid lms. Therefore, the methanol can be utilized as a volatile dispersant for ZnO nanoparticles in organic medium. Previous studies have shown that the amount of ZnO nanoparticles in the hybrid lms must be increased to relatively high concentration to provide high efciency photovoltaic device [25,26,41]. In our study, the concentration of ZnO nanoparticles is limited to 5 wt.%. This is attributed the synthetic method of the ZnO nanoparticles, a spray pyrolysis, which produces high fraction of hard agglomerates. Only a small fraction of ZnO nanoparticles can be re-dispersed into the chlorobenzene medium by using an ultrasoncation process. However, the low concentration of ZnO nanoparticles is a good experimental condition for demonstrating the role of methanol as a dispersant. Since the improvement of ZnO nanoparticle dispersibility in the mixture of cholorbenzene and methanol arises from local phenomenon, we believe that the methanol should be able to stabilize ZnO nanoparticles at higher concentration. In fact, Beek and coworkers showed that the ZnO nanoparticles synthesized in methanol medium can be redispersed in chlorobenzene up to 75 mg/mL [25,26]. In this system, the methanol is never fully dried to prevent the formation of hard agglomerates. We suggest that the presence of small amount of methanol serves as a dispersant for ZnO nanoparticles. 4. Conclusions Our study demonstrates that methanol can be utilized as a volatile dispersant for promoting the dispersion of ZnO nanoparticles in organic medium. The addition of 20% (v/v) methanol leads to great improvement of dispersion state of ZnO nanoparticles in chlorobenzene. The hybrid lms of ZnO/MEH-PPV and ZnO/P3HT fabricated by using mixtures of chlorobenzene and methanol as solvents are continuous and exhibit relatively smooth surface. The chain organization of conjugated polymers within the hybrid lms is hardly affected by the presence of methanol. However, the charge separation efciency is signicantly improved due to the increase of interfacial area between conjugated polymers and ZnO nanoparticles. The low boiling point of methanol allows complete evaporation during the fabrication process of the hybrid lms. Therefore, it has a potential for utilization in the fabrication process

of plastic solar cell. We are currently investigating this concept on other types of conjugated polymers and nanoparticles. Acknowledgements This research is nancially supported by National Metal and Materials Technology Center (MTEC), National Science and Technology Development Agency (project code MT-B-53-POL-26481-G). This research is also partially supported by National Center of Excellence for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, NANOTEC Center of Excellence at Mahidol University and Center for Innovation in Chemistry. References
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