P M.P andP M,Poster Session, Thursday, June 17Theme F686 - N11233D Silver Plasmonic Structure for Surface Enhanced Raman Scatter<strong>in</strong>g11Mehmet KahramanPUMustafa ÇulhaUP P*Genetics and Bioeng<strong>in</strong>eer<strong>in</strong>g Department, Faculty of Eng<strong>in</strong>eer<strong>in</strong>g and Architecture,Yeditepe University, Kayisdagi, Istanbul, TurkeyAbstract- The construction of highly reproducible and enhanc<strong>in</strong>g novel SERS substrate is achieved by controll<strong>in</strong>g the <strong>in</strong>ter-particle distance andaggregate size. In order to control aggregation size and number of nanoparticle <strong>in</strong> one aggregate, micro-well are prepared with the softlithography. In this method, first, the diluted latex microsphere (1.6 μm) are spread as a th<strong>in</strong> film us<strong>in</strong>g “convective assembly” method on aglass slide, then, polydimethylsiloxane (PDMS) is prepared on the latex th<strong>in</strong> film. F<strong>in</strong>ally, the PDMS film is removed and latex particles arewashed with an organic solvent. The PDMS stamp with micro-wells is filled with concentrated AgNPs coated with CTAB for further analysisus<strong>in</strong>g SERS. SEM and AFM were used for the characterization of the prepared surfaces. Rhodam<strong>in</strong>e 6G is used as a probe molecule to7-9characterize the substrate. The enhancement factor and limit of the detection of the prepared substrates are found to be 3.7x10P Pand 1.0x10Prespectively.Nanosize metal particles and semiconductors have uniqueoptical, magnetic and electronic properties that do not have <strong>in</strong>their bulk form. These properties have been used for manyapplications of science and technology such as; nanoscalechemical sensors, data storage, quantum dots lasers,electronics and SERS substrates [1-4]. The size, shape andtype of the noble metal and aggregate properties ofnanoparticles and <strong>in</strong>ter-particle distance are the criticalparameters <strong>in</strong>fluenc<strong>in</strong>g SERS activity [5-8] due to their<strong>in</strong>fluence on surface plasmons (SPs) that are responsible forthe major enhancement (electromagnetic enhancement)[9] <strong>in</strong>SERS mechanism. The <strong>in</strong>ter-particle distance strongly<strong>in</strong>fluences the enhancement factor and it was reported that the<strong>in</strong>ter-particle distance must be 2-4 nm for the optimal SERSenhancement [10]. Although there is an effort to uselithographic methods to control <strong>in</strong>ter-particle distance, thesemethods generally time consum<strong>in</strong>g, expensive and needskilled personnel.In this study, 3D silver plasmonic structures were preparedwith the concentrated silver nanoparticles. First, th<strong>in</strong> film(Figure 1 A) of the latex was prepared us<strong>in</strong>g “convectiveassembly” method [11]. The experimental parameters such asconcentration of latex spheres, mov<strong>in</strong>g stage velocity anddropped volume were studied. Second, PDMS was preparedon the latex th<strong>in</strong> film by bak<strong>in</strong>g at 70 °C for 1 hour. Figure 1 Bshows SEM image of the micro-wells prepared with the 1.6m latex sphere on PDMS. As is seen, the size of the microwellsis slightly smaller (1.4 m) than the size of the latexnanoparticles. This is possibly due to the high viscosity of thepolymer mixture <strong>in</strong> which latex nanoparticles are completelyburied. Therefore, the size of prepared micro-wells decreasesabout 200 nm. F<strong>in</strong>ally, micro-wells were filled us<strong>in</strong>g“convective assembly” method with the concentrated silvernanoparticles conta<strong>in</strong><strong>in</strong>g CTAB, which was used to <strong>in</strong>crease ofthe hydrophobic property of the silver nanoparticles andcontrol <strong>in</strong>ter-particle distance <strong>in</strong> the aggregates (Figure 1C).The enhancement factor was calculated us<strong>in</strong>g IRSERSR/IRBulkR x7CRBulkR/CRSERS Rformula and found as 3.0x10P P. This enhancementfactor is also consistent with 2-4 nm <strong>in</strong>ter-particle distances[12]. The reproducibility of the prepared substrate was testedus<strong>in</strong>g the peak height, area and <strong>in</strong>tensity of the ten peaks at-11512 cmPP. The percent coefficient variance (CV) was foundto be about 10. Limit of the detection (LOD) of the substrate-9was 1.0x10PACFigure 1. A) SEM image of the prepared th<strong>in</strong> film of the 1600 nmlatex sphere, B) micro-wells of 1600 nm latex sphere, C) micro-wellsfilled with silver nanoparticles.In conclusion we demonstrate that novel SERS substratespossess<strong>in</strong>g high sensitivity, enhancement factor andreproducibility by the controll<strong>in</strong>g of the <strong>in</strong>ter-particle distanceand aggregate size.This work was supported by TÜBTAK and YeditepeUniversity.*Correspond<strong>in</strong>g author: HTmculha@yeditepe.edu.trT[1] A. P. Alivisatos, Science 271, 933 (1996).[2] L. E. Brus, Appl. Phys. A, 53, 465 (1991).[3] Y. Wang and N. Herron, J. Phys. Chem. 95, 525 (1991).[4] P. C. Lee and D. Meisel, J. Phys. Chem. 86, 3391 (1982).[5] S. R. Emory, W. E. Hask<strong>in</strong>s, and S. Nie, J. Am. Chem. Soc. 120,8009. (1998).[6] T. Jensen, L. Kelly, A. Lazarides, and G. C. Schatz, Journal ofCluster Science 10, 295 (1999).[7] E. J. Zeman, and G. C. Schatz, J. Phys. Chem. 91, 634 (1987).[8] J. Jiang, K. Bosnick, M. Maillard, and L. Brus, J. Phys. Chem. B107, 9964 (2003).[9] M. Moskovits, Rev. Mod. Phys. 57, 783 (1985).[10] A. M. Schwartzberg, C. D. Grant, A. Wolcott, C. E. Talley, T. R.Huser, R. Bogomolni, and J. Z. Zhang, J. Phys. Chem. B 108, 19191(2004).[11] P. M. Tessier, O. D. Velev, A. T. Kalambur, J. F. Rabolt, A. M.Lenhoff, and E. W. Kaler, J. Am. Chem. Soc. 122, 9554 (2000).[12] J. Jiang, K. Bosnick, M. Maillard, and L. Brus, J. Phys. Chem. B107, 9964 (2003).B6th Nanoscience and Nanotechnology Conference, zmir, 2010 646
P onP viaPP wereP upPoster Session, Thursday, June 17Theme F686 - N1123Superhydrophobic Micropatterned Polymer Surfaces Synthesized by Us<strong>in</strong>g Styrene-Flurometacrylate Random Copolymers11UUur CengizUP P*, H. Yldrm ErbilP1PGebze Institute of Technology, Chemical Eng<strong>in</strong>eer<strong>in</strong>g Department, 41400, Gebze-KocaeliAbstract- In this work, we present a novel method for fabricat<strong>in</strong>g polymer th<strong>in</strong> films conta<strong>in</strong><strong>in</strong>g micro-patterned spherical particles vary<strong>in</strong>g <strong>in</strong>the range of 400 nm to 8 m by dip-coat<strong>in</strong>g process <strong>in</strong> polymer solution. We can control the distribution of the particle size via adjust<strong>in</strong>g theconcentration of the PS-ran-FMA copolymer, the solvent/non-solvent ratio and withdrawal speed of dip coater. Styrene-fluoromethacrylateorandom copolymer were synthesized <strong>in</strong> supercritical carbondioxide (scCOR2R) at 250 bar and 80 P PC us<strong>in</strong>g AIBN as a free radical <strong>in</strong>itiator. It wasfound that the optimal concentration of polymer solution was 25 mg/mL and withdrawal speed of 41 cm/m<strong>in</strong> to obta<strong>in</strong> the narrowest particledistribution on the surface. Surfaces conta<strong>in</strong><strong>in</strong>g the microparticles were characterized with the water contact angle measurement, opticalomicroscopy and SEM. Superhydrophobic surfaces hav<strong>in</strong>g a water contact angle up to 160P obta<strong>in</strong>ed with this novel method.Polymer surfaces composed of two or three dimensionalrepeat<strong>in</strong>g uniform units are called “patterned polymeric1surfaces”P P. These patterned surfaces are referred to micropatternedand nano-patterned surfaces with respect to theirdimensions. The polymeric micro/nano patterns providesome new properties to the surface which change withrespect to chemical nature and shape of the material. For<strong>in</strong>stance, Erbil et al. (2003) obta<strong>in</strong>ed micro-structured gellikeporous super-hydrophobic surfaces hav<strong>in</strong>g a waterocontact angle of 160P the method of phase separationus<strong>in</strong>g isotatic propylene (iPP) hav<strong>in</strong>g a water contact angleoof 105P nonpatterned surfaces with different2solvent/<strong>in</strong>solvent couplesP P. There are other methods toform micro patterned polymeric surfaces. Recently Wanget al. have obta<strong>in</strong>ed micro and nano patterned polymericstructures via phase separation by dropp<strong>in</strong>g polymer1,4solution onto non-solventPP. This method is easier thansoft lithography method whose application is difficult andexpensive.In this study, uniform micro patterned polymericsurfaces were obta<strong>in</strong>ed with particle diameters chang<strong>in</strong>gbetween 400 nm and 8 μm. In the first step, p(ST-ran-FMA) copolymers were synthesized <strong>in</strong> sc-COR2R medium.Styrene and Perfluoromethacrylate (Zonly-TM, Dupont)monomers between 5-20 % <strong>in</strong> molar concentration wereocopolymerized <strong>in</strong> scCOR2 Renvironment at 250 bar and 80P PC.Polymerization <strong>in</strong> COR2 Rhas advantages such as be<strong>in</strong>g nontoxic,cheap and no requirement of extra purificationprocess for the produced copolymers.In the second step, th<strong>in</strong> copolymer film coat<strong>in</strong>gs wereproduced via dip coat<strong>in</strong>g glass slides <strong>in</strong>to polymersolutions obta<strong>in</strong>ed by dissolv<strong>in</strong>g the copolymers <strong>in</strong> THF-MEK mixture (%50 wt) at room temperature and add<strong>in</strong>gmethanol as a non-solvent with vary<strong>in</strong>g amount. Then theoptical and SEM images of the formed surfaces wererecorded and the contact angles of the surface weremeasured by us<strong>in</strong>g the KSV-CAM 200 goniometry.When the methanol volume fraction was low, scatteredform of particles with no specific geometry were observedwhich do not have any specific roughness. With the <strong>in</strong>crease<strong>in</strong> the methanol amount, these particles were converted torepeat<strong>in</strong>g, and somewhat uniform spherical particles. The<strong>in</strong>crease <strong>in</strong> the dipp<strong>in</strong>g rate, the particles shr<strong>in</strong>k uniformly atthe beg<strong>in</strong>n<strong>in</strong>g, but after a certa<strong>in</strong> value of dipp<strong>in</strong>g rate, thenthe agglomeration of particles occurred. Figure 1 shows aSEM image of the surface obta<strong>in</strong>ed at an optimum dipp<strong>in</strong>gspeed and different methanol fraction. It is clearly seen fromthe results particle sizes decrease with the <strong>in</strong>crease ofmethanol fraction. Spherical particles hav<strong>in</strong>g differentdiameters between 2-4 m and 400-800 nm are shown <strong>in</strong>fig.1a and 1b respectivelyFigure 1. SEM images of 25 mg/mL p(ST-ran-FMA) solution <strong>in</strong>THF-MEK solvent mixture (50 wt %) with a) 21,4 b) 33.3 wt %omethanol at 22 P PC mixture temparatureIn summary, particles shape and dimensions and watercontact angle results were varied as a function of nonsolventand copolymer concentration. The <strong>in</strong>crease <strong>in</strong> thenon-solvent fraction resulted <strong>in</strong> decrease of the particlediameter from 8 μm down to 400 nm, and <strong>in</strong>crease <strong>in</strong> theoowater contact angle from 117P to 160P P.* Correspond<strong>in</strong>g author: HTucengiz@gyte.edu.trT[1]Wang Y., Liu Z., Han B., Sun Z., Zhang J., Sun D. Adv.Funct. Mater. 2005, 15, 655.[2]Erbil H.Y., Demirel A.L., Avci Y., Mert O. Science 2003,299, 1377.[3]Xia Y.N., Whitesides G.M., Angew. Chem. Int. Ed. 1998, 37,550.[4] Wang Y., Liu Z.,Huang Y., Han B.,Yang G. Langmuir, 2006,22, 19286th Nanoscience and Nanotechnology Conference, zmir, 2010 647
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