Fluorescent polymeric Nanoparticles Fabricated by plasma polymerization Under Atmospheric Pressure and Room temperature

Ping Yang1, Jing Zhang2, Ying Guo2 1 College of Material Science and Engineer, Donghua University, Shanghai, 200051 2 College of Scinece, Donghua University, Shanghai, 200051

Abstract: Fluorescent pyrrole nanoparticles were first synthesized through plasma polymerization under atmospheric pressure and room temperature. The fine spherical polypyrrole nanoparticles with a diameter of 100-200 nm are uniformly distributed. FTIR was used to investigate the structure of atmospheric pressure plasma polymerized polypyrrole nanoparticles (AP-PPy nanoparticles). The structure analysis indicates that the nanoparticles keep a better retention of the pyrrole structure. The effect of power on the optical properties of AP-PPy nanoparticles were analysised with UV-Visble absorption and PL spectra. Polarization induced coplanarization of pyrrole and high level of chain stock during the nucleation and growth of nanoparticles. This leads to a better conjugation of chains, and avoids the aggregation quench. Thus polypyrrole nanoparticles exhibit a strong fluorescence emission at the range of 415nm to 450nm with different power. This technology will help the realization of practical optoelectronic nanodevice applications of fluorescent polymeric nanoparticles.
Keywords: atmospheric pressure plasma polymerization, polypyrrole nanoparticles, fluorescence 1. Introduction Fluorescent organic polymer-based nanoparticles have become the research hotspot in recent years, as a result of their large diversity in molecular structure and optical properties that are of potential use in optoelectronics and biologics [1-8]. This research has, to date, principally focused on colloidal-state fluorescent organic nanoparticles, which can readily be prepared with simple reprecipitation methods [1-9]. To explore the collective properties of fluorescent organic nanoparticles as well as to realize practical device applications, however, reliable methods of transferring and aligning them with large surface areas on solid substrates are required. Electrophoretic deposition [10], lithographic patterning [11], and ink-jet printing of organic/inorganic nanoparticles [12] have been proposed as methods appropriate to this purpose. As all these methods are based on the strategy of transferring preformed fluorescent organic nanoparticles onto the substrate, which demands separate nanoparticle synthesis and complicated handling, we decided to explore the possibility of in-situ generation of fluorescent organic nanoparticles on large-area substrate. Herein, fluorescent AP-PPy nanoparticles have been first fabricated from nonfluorescent pyrrole monomer by atmospheric pressure plasma polymerization. Atmospheric pressure plasma polymerization has many advantages. The utmost advantage is that atmospheric plasma technology allows the circumvention of one of the major drawbacks of current low-pressure plasma technologies, namely the need for expensive and limited-volume vacuum equipment. Besides these advantages, plasma polymerization under atmospheric pressure has some other advantages over deposition under low pressure. Since the chance that a gas molecule collides with another is higher under atmospheric pressure than under vacuum, energy transfer is more efficient. Under vacuum, the monomer molecules are often fragmented because the plasma species are highly energetic. The lower energy of plasma

species under atmospheric pressure results in a better retention of the chemical structure [13]. This technology will integrated in traditional microelectronic fabrication process and help the realization of practical optoelectronic nanodevice applications of fluorescent polymeric nanoparticles. The fluorescent AP-PPy nanoparticles in this paper were synthesized by a homemade nonequilibrium atmospheric plasma reactor using pyrrole as the precursor and Ar as the carrier gas. The morphology and chemical structure of the polypyrrole nanoparticles have been characterized using SEM, FTIR (NEXUS670 spectrophotometer). The UV-visible absorption (PerkinElmer Lambada 35) and PL spectra (Hitachi F-4500) were used to investigate the optical properties of the polypyrrole nanoparticles. 2. Results and Discussion In the plasma area, the monomer molecules are converted into active radicals as a consequence of electron collision. Effect by the electric field of plasma, the radicals were be polarized. Then these charged radicals become precursors of chain reactions leading to nucleation process. When the pyrrole molecules get closer to nucleation and growth, coplanarization of pyrrole and high level of chain stock can be induced by polarization. After synthesis, uniform nanoparticles were grown on the glass substrate. Figure 1 (a) shows the morphology of the typical nanoparticles obtained at the power of 480W, the fine spherical polypyrrole nanoparticles with a diameter of 100-200 nm are uniformly distributed over the surface of the glass substrate. As shown in Figure 1(b), the diameter of the polypyrrole nanoparticles obtained by laser particle analyzer was in the range of 100-200 nm, mainly in 150 nm, this is in accordance with the results get from SEM. During formation of nanoparticles, the coplanarization of pyrrole and high level of chain stock leads to a better conjugation of chains. This avoids the aggregation quench. Thus AP-PPy nanoparticles show different optical properties from bulk polypyrle. The AP-PPy nanoparticles show a broad peak at 340 nm (with width of 23nm). Compared with the electrical polymerized polypyrrle, we believe that this peak correspond to the transition of undecomposed PPy backbone [14]. With the increase
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Fig. 1. Scanning electron micrograph of polypyrrole nanoparticles (a) and particle size distributing obtained by laser particle size analyzer (b).

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Fig. 2. (a) UV-visible absorption and (b) fluorescence spectra of polypyrrole nanoparticles.

of discharge power from 390W to 480W the absorption intensity decrease, however, when the discharge power increase from 480W to 510W, the intensity increase. The plasma polymerization leading to the formation of spherical nanoparticles is accompanied by dramatic fluorescence changes. Obvious fluorescence was detected in nanoparticles of nonfluorescent polypyrrole. When excited by laser with wavelength of 350nm, the polypyrrole nanoparticles exhibit a fluorescence emission at the range of 415nm to 450nm, with the increased power from 390W to 510W. Contrary to the UV-visible spectra, the fluorescence intensity of the AP-PPy nanoparticles was increased versus the increase of discharge power, company with the red-shift of the fluorescence peak. The increase of fluorescence intensity may induced by the increased conjugated length of the AP-PPy, as the increase of discharge power.

FTIR spectrum of the polypyrrole nanoparticles was displayed in Figure 3. There are mainly three broad absorption peaks, at 3200-3580cm-1 1570-1700 cm-1 and 950-1200 cm-1, respectively. The broad peaks at approximately 3427 cm-1 is assigned to typical N-H/C-H stretching vibration [15]. The broad peak at 1570-1700 cm-1 are a combination of a number of absorptions corresponding to C=C and
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Fig. 3. Fourier transform infrared spectra of polypyrrole nanoparticles

C=N in plane vibrations in the pyrrole structures, and C=O stretching vibration cause by oxidation.Amine salts may also contribute to this absorption [16]. The peaks at 950-1200cm -1 are related to =C-H in plane vibration in the pyrrole structures and NH 2 wag, respectively [17]. The C-H asymmetry stretching shows a slender peak at 2928 cm -1. When the pyrrole rings are broken, branching and crosslingking reactions tend to occur predominatly. Thus, primary and secondary amines appear in polypyrrole nanoparticles. This induces the appearance of weak peak at the 1384 cm -1 which attribute to the secondary amines C-N stretching [18]. The appearance of peak at 784 cm -1 is also likely to be due to different substitution effects. 3. Conclusion Fluorescent pyrrole nanoparticles were first synthesized through plasma polymerization under atmospheric pressure and room temperature. The fine spherical polypyrrole nanoparticles with a diameter of 100-200 nm are uniformly distributed over the surface of the glass substrate. FTIR analysis indicated that the polypyrrole keep a better retention of pyrrole structure. The AP-PPy nanoparticles show a broad peak at 340nm, which correspond to transition of undecomposed PPy backbone. With the increase of discharge power from 390W to 480W the absorption intensity decrease, however, when the discharge power increase from 480W to 510W, the intensity increase. When the pyrrole molecules, radicals and ions get closer to nucleation, growth and formation of nanoparticles, coplanarization of pyrrole and high level of chain stock can be induced by polarization. This leads to a better conjugation of chains, and avoids the aggregation quench. The AP-PPy nanoparticles exhibit a fluorescence emission at the range of 415nm to 450nm, with the increased power from 390W to 510W. Contrary to the UV-visible spectra, the fluorescence intensity of the AP-PPy nanoparticles was increased versus the increase of discharge power, company with the red-shift of the fluorescence peak. The increase of fluorescence intensity may induced by the increased conjugated length of the AP-PPy, as the increase of discharge power. Atmospheric pressure plasma polymerization can accomplish in-situ generation of fluorescent organic nanoparticles on large-area substrate. The better retention of monomer chemical structure helps it achieve the results that achieved by chemical methods and avoids environmental concerns arising from solvent usage. Thus this technology will help the realization of practical optoelectronic nanodevice applications of fluorescent polymeric nanoparticles. Reference [1] B. K. An, S. K. Kwon, S. D. Jung, S. Y. Park, J. Am. Chem. Soc., 124, 14410 (2002). [2] S. J. Lim, B. K. An, S. D. Jung, M. A. Chung, S. Y. Park, Angew. Chem., 116, 6506 (2004). [3] L. Xi, H. B. Fu, W. S. Yang, J. N. Yao, Chem. Commun., 4, 492 (2005). [4] A. D. Peng, D. B. Xiao, Y. Ma,W. S. Yang, J. N. Yao, Adv. Mater., 17, 2070 (2005). [5] M. Han, M. Hara, J. Am. Chem. Soc., 127, 10951 (2005). [6] F. Wang, M. Y. Han, K. Y. Mya, Y. B. Wang, Y. H. Lai, J. Am. Chem. Soc., 127, 10350 (2005). [7] N. Makarava, A. Parfenov, I. V. Baskakov, Biophys. J., 89, 572 (2005). [8] Y. Y. Sun, J. H. Liao, J. M. Fan, P. T. Chou, C. H. Shen, C. W. Hsu, L. C. Chen, Org. Lett. 8, 3713 (2006). [9] D. Horn, J. Rieger, Angew. Chem., 113, 4460 (2001). [10] R. C. Hayward, D. A. Saville, I. A. Aksay, Nature,404, 56 (2000). [11] F. Hua, J. Shi, Y. Lvov, T. Cui, Nano Lett., 2, 1219 (2002).

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