‘Downloaded via NATL IYST OF TECHNOLOGY RINUIBKELA on November &,2019 at 15:56:33 (UTC). ‘See ktpspb acs orgeurngpbelies for opine onow to legthnately re publahed are. Tite JOURNAL OF PHYSICAL CHEMISTRY Letters) New Nano Architecture for SERS Gayatri Kumari and Chandrabhas Narayana* pubsacsorgPCL Applications (Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O, Bangalore 560064, India © Supporting Information ABSTRACT: iver silica gold sandwich nanoparticles were synthesized by a multistep sceded growth process and were characterized by UV-vis spectroscopy, transmission lectzon microscopy and Xray difraction. Gold islands allow pssage of ight through the ‘revices into the silica Iyer, and the ser core—slca shell behaves ike a mizoy, this reacting the light incident on st These structures facilitate ight amplification dae to mixing of light waves from the multiple rellectons. Sandwich nanoparticles show SERS ‘enhancement of ~10, This enhancement factor is old larger in magnitude than that of simular nanoparticles without the silver core under identical experimental conditions SECTION: Physical Processes in Nanomaterials and Nanostratures Nira sto facing propa ovng to tn castence of surface plasmons (collective osclation of Surface fee electrons) in them. These properties change as the nanoparticle composition, shape,” size,“® charge, and dielectric properties of the surrounding medium change?” ‘These effects are manifested as a change in surface plasmon resonance (SPR) for metal nanoparticles, among which silver and gold feature the most. When two or more metas are present in a single nanoparticle, the optical properties are determined by the dielectric properties ofall of the constituent metals forming the nanoparticle. Many groups have reported bimetallic nanoparticles formed by successive reduction ofthe constituent metals!" The case of silver and gold nano- particles is particularly intresting due to their similar latice constants (Au: 4.078 A; Ag: 4086 A). As early as 1964, Moriss and Collins reported the synthesis ofa goldsilver multilayer colloid.” However, the major work and reports started appearing only about a couple of decades back. Alloying silver and gold causes intermetallic interactions. Schierhom and Liz- Marain used slca layer between a gold core and ster shell to prevent the intermetallic interaction!" Halas and colleagues have shown liferent types of tunable plasmonic nanoparticles of silver and gold, which can find application in SERS.“ Kim eta. showed a method to prepare silver nanostructures on silica spheres for SERS? Surfaceenhanced Raman scattering (SERS) is the enhance- ment of the Raman signal due tothe presence of the molecule in the vicinity of the nanopartcles."! There are two mechanisms that are currently accepted for SERS enhancement, clectromagnetc and chemical enhancement.” Electromagnetic enhancement is the enhancement of the electric field around the molecule due to the interaction of light with the surfice plasmon ofthe nanoparticles.” Chemical enhancement occurs ‘when a charge-transfer complex is formed between the ACS Publications ©2072 Arwan ni sce molecule and the nanoparticle. The SERS enhancement factor is inversely proportional to the distance from the nanoparticle and dies off atthe rate of 1/r fora molecule at a distance r from the nanoparticle." Thus, to observe SERS, the molecule must lie in the vicinity of the nanoparticles (within 1 nm). Lian C. T. Shoute et a. showed an increase in the Raman signal intensity ofthe analyte adsorbed on a planar sandwich substrate of slicon—sliasver, owing to the constructive interference of incident light and refracted light” In most of the applications of SERS, especially in the case of a bio- molecule, nanoparticles ae preferred instead of solid substrates as they canbe dispersed in solutions. Due tothe inert nature of | {ld toward biomolecules, in vivo application of SERS would require a nanoparticle architecture where god is exposed tothe biochemical environment. In ths Lette, we report the synthesis of silver-silica~gold sandwich nanoparticles, as shown in Figure 1, and their application as SERS substrates, Sandwich nanoparticles show two surface plasmons corresponding to the silver core and the gold island shell. The sandwich nanoparticle architecture provides a consistent 10° enhancement in SERS signal due to the additional contribution from the reflected component from the silver surface embedded in the silica matrix In addition, we have synthesized a nanoparticle where by tuning the silica layer, one can produce an excellent SERS substrate for in vivo applications and diagnostic. Sandwich nanoparticles were prepared by a stepwise seeded ‘powth process (Scheme 1). Figure 23 (purple curve) shows the extinction spectra of the slver nanoparticles capped with Received: February 2, 2012 ‘Accepted: Api 10, 2012 Pablished: Apel 10, 2012 0 eanng. p90 441 Py Ch Lt 91 3, N90195‘The Journal of Physical Chemistry Letters Figure 1. Schematic of the slver~sllcsgold sandwich nanoparticle ana path of light through i resulting in muliple reflections. PVP, which has a SPR at 422 nm. Silver nanoparticles were coated with silica by fllowing « modified Stober® process Wherein TEOS in an ethanolic solution of ammonia was used."™ Ammonia catalyzes the formation of a silica shell on silver nanoparticles in ethanol. It hydrolyzes TEOS to form Si(OH) which condenses overtime to form a silica shell Coating silver nanoparticles with a silica shell of ~40 nm causes a red shift in the SPR from 422 to 429 nm due to the increase in the refractive index of the surrounding medium (Figure 2, green curve). For the incident lght to go and passthrough the intermittent sila layer and get reflected from the slver core itis necessary to make the gold layer perforated or in the form of islands, Grevices or gaps in the gold layer would facilitate light penetration through the silica layer. The best way to create this would be to have gold nanoparticles deposited on the alica layer. Oldenburg etal. had originally shown the formation of ‘gold shells by growth of gold clusters on a sca sphere using sodium borohydride as the reducing agent.?-™ However, it ‘was later observed by Graf etal. chat using a strong reducing agent not only causes growth of small gold particles attached to the siicaephere but also results in new nucleation of gold particles in the solution, which must be prevented”® Further, it ‘was shown by Theissen et al. that the use of hydroxylamine hydrochloride would result in the growth of gold nuclei already present inthe solution while suppresing the formation of new nuclei” Duff et al. modified ths method and ued it to grow clusters bya seeding process." Later, these methods were used in combination by Graf et al. to grow a gold shell on silica heres Grafs method of gold coating on slica was modently modilied to. synthesize silver—siica—gold sandwich nano- Particles. Gold has very litle afinity for silica. Therefore, the silica surface was functionalized with silane coupling agent 3-aminopropyltriethorysiane (APTES) to assist the binding process. The generation of god nucleation sites on the APTES- ‘modified silica surfice, prior to the growth of the gold shell, led to the development of a hump at around 523 1m in the eatincton spectra (Figure 2b, blue cuve).It is also observed thatthe SPR for silver shifts from 429 to 40S nm forthe seeded nanoparticles. This decreat is attributable to the reduced size of the silver core. Gold has a higher postive eduction potential (+15 V) than silver (+08 V), Therefore, upon addition ofthe core-shell solution to the gold nanoparticle solution, some of the free Au! ion permeates the silica shell and oxides the silver core thus reducing its size, Complete oxidation of slver bby Aw" is prevented by the nearly nonporous nature of the sila shell, a was found by the BET measurements (igure St, Scheme 1. Scheme of Formation of Sandwich Nanoparticles ae ‘eos 120m e@— ss anc 0H to) — ha@si0,gAu seed — Ao@s10,@hu — 510,@04 Extinction Wavelength (om) igure 2. Normalized extinction spectra of (3) silver (purple) and siver coremsiea shell (green) nanoparticles and (b) slver-aliea- god seed (Glue), the sandwich nanoparticles (eed), and sca eore™gold inland nanoparticles (Sark gry) mn ere‘The Journal of Physical Chemistry Letters Figure 5. TEM images for dierent steps of synthess of slver~sliagold Shall, () gold seeds on slvercore~slica shell nanoparticles and () sver—» sandwich nanstructres. (4) Silver nanoparties,(b) ser eore—stica slca~go sandwich nanoparticle. The row i (c} point tothe core Where complete oulation of slvr has occured. Seale bar = 100 (ad) and 30 nm () Supporting Information). However, during the growth of the {old island, Au" ions were added to the sed solution, which right oridize slver. To prevent this, (a) an optimal con- centration of arochloric acid wa selected, and (b) the reducing agent (hydroxylamine hydrochloride) and gold salt (aurochlorie acid) solution were added simultaneously dropwise. Also, the concentration of aurochloric acd was adjusted to achieve gold islands of definite size. It was also observed that potassium carbonate is not required for the growth of gold islands as used in earlier cases. Use of KyCO,/HAUCl rather aids oxidation of tive bythe Axion; hence is ute must be avoided, Extinction spectza ofthe sandwich partle show two prominent peas, at around 407 nm corresponding tothe slver core and at $24 nm corresponding to 8~10 nm of a gold idand (Figure 2b, red curve), As the gold coverage on the surface increases, the light penetrating the silica shell is partly blocked, and hence, there is 4 decrease in the intensity of the silver peak The rise in the intensity ofthe gold peak i attributable to the increase in the numberof the gold islands ‘Figure 3 shows the TEM images capturing the four steps of synthesis of sandwich nanostructures. As expected, here, We tome ofthe silver core oxidized completely or reduced in size partly due to oxidition by gold ions. Therefore, not all particles had a core inside ofthem, as can be seen ina couple of particles inthe TEM picture, which was intentionally selected (Gee arrows in Figure 3c). However, it is worth mentioning that moat ofthe particles had the core intact in them. ‘To se the effect the of dielectric layer thickness, lver—aiica core—shell nanoparticles of varying. shell thickness were prepared, Figure S2 (Supporting Information) shows the exine- tion spectra of silverslica core~shell nanopartiles with diferent shell thicknesses. It can be seen that the SPR of the core-shell particles changes by only 8 am (Eom 422 to 430 nm) upon increasing the silica shell thickness from 25 to 60 nm. Figure 3 (Supporting Information) shows the TEM image of core~shell parties. Figure S4 (Supporting Informa: tion) shows the TEM image of sandwich nanoparticles with diferent shell thicknesses. Farther, the densities and the sizeof gol islands onthe silica shell were varied. Figure $5 (Supporting Information) shows the extinction spectra of sandwich nanoparticles with diferent densities of gold islands. It is observed that the gold island SPR changes from $24 to $30 to S41 nm as their densities con the sca shell are inceased. The TEM image ofthe particles ‘with dliferent gold iland densities is shown in Figure S6 (Supporting Information). ma Figure 4. FESEM picture of sler~siica-gold sandwich nano- patie. Figure 4 shows the FESEM picture of the sandwich nanoparticles, which clearly shows that the particles are monodisperse in nature. The particle size dstibution of the ‘andwich nanoparticles is shown in the Supporting Information (Figure $7). THe XRD pattem of the slversice-gold fandwich nanoparticles (Supporting Information Figure S8) ‘shows four signature peaks marked by the indices (111), (200), (220), and (311), confirming the fc structure of the metals in the nanoparticle, and abroad hump in the 29 region of 22~25° is attributed to the slica shell” The peak for gold and silver are broad and too close to be distinguished. ‘We here demonstrate the use of the sllveraicr~gold sandwich nanostructures at a SERS substrate. Its common to tse thiophenol a an analyte. Figure Sa shows the SERS spectra of thiophenol at diferent concentrations. The peaks at 996, 1021, 1074 and 1571 em” are characteristic ofthiophenol and correspond to the out-of plane ring deformation, in-plane ring deformation and C=C symmetric stretch, CC asymmetric stretch and C-S stretch, and C-C symmetric bending modes, respectively." The enhancement factor G is given by? g= xh Gk ‘were yan Ig ae the normal Raman and SERS intensities of the peak at 995 em“ repectively. Cy and Cy are the respective ean W061 Cem 131‘The Journal of Physical Chemistry Letters —ra . on A —10°m ey —si0,@Au a 2 2 : i i i ‘wavenumber fm) averumber fm’) a —neas0,@n0 —siojant z z Wavenumber(em") Figure 5. (a) SERS spectra of thiphenol at diferent concentrations on Ag@SiO,@Au sandwich nanoparticles. (b) SERS spectra of 10-* M thlophenal on Ag@SiO,@Au and Si,@Au nanostructures. (c) SERS spectra of 10°” M thiophenol on AG@SIO,@Au and SiO,@AL nanostructures. The laser wavelength used was 632.8 nm, and the power wa 8 mW atthe sample concentrations of thiophenol in the normal Raman and the SERS measurements. The conservative estimate of the SERS enhancement factor was found to be 10 in the ease of slver— siica~gold sandwich nanoparticles. SERS of R6G was alo recorded with sandwich nanoparticles (Supporting Information Figure $9) "The enhancement factor was found to decrease when the silica hell thickness was increased to 60 nm or decreased to 25 nm (Figure S10 Supporting Information). The enhancement factor alo decreased by a factor of about 2 when the gold island densities were increased (Figure S11 Supporting Information). High loading of gold on sia may not allow light to penetrate cr come out fom the sandwich nanoparticles and hence can be reponsble for the lower SERS enhancement actor. “To illustrate thatthe core is indeed helping in enhancing the Raman signal, sllca core—gold shell nanoparticles without silver core were synthesized and characterized by UV-visible (Figure 2b dark gray) and TEM (Figure S12. Supporting Information), Figure Sb and ¢ shows the SERS spectra of 10" snd 10°” M solutions of thlopheno, respectively, on Ag@ Si0,@Au and SiQ,@Au nanostructures. It was abserved that the enhancement factor for Ag@SiO,@Au was sx times higher than that forthe Si0,@Au nanoparticles (Figure $b), while the detection limit (concentration detectable by SERS) of Ag@ SiO,@Au was 100 times higher than that of SiQ,@Au nano- patiles (Figure Sc). To explain the greater enhancement of sandwich nanoparticles, as shown in Figure 1, we propore that the incident ight (11) fling inthe crevices between the gold islands gete transmitted (¢1) through the nica layer where It is reflected (72) by the slver core. The transmitted light can undergo multiple reflections before emerging from the gap beneeen the islands. The regions where the incident (2) and refracted light (r3) constructively interfere (satisfying Bragg’s condition) wil be the postions of high fed intensity. Analyte present in such regions will experience an increated slectic field, and hence, high Raman intensity is observed. In addon to ths, the plasmon coupling between the gold islands on the surface wil also have a strong contribution to the enhancement of the Raman signal. It in some way similar to that from Baesa et al's report of enhancement of the Raman signal of an adsorbed monolayer of Cj onan aluminum metal surace wth‘The Journal of Physical Chemistry Letters. a alica overlayer asa result ofthe interference of incident and reflected coherent beams.” In conclusion, we have demonstrated a facile method to yatheszesliverilicagold sandwich nanoparticles exhibiting two SPRs at 407 and $22 nm fora siver core and gold iland, respectively. The density of gold islands on a silica surface and the thickness ofthe sllca layer (~ 40 nm) were optimized to {get the least etched slver core and maximum SERS intensity. A SERS enhancement factor of 10* was achieved forthe sandwich nanoparticles. Its proposed that multiple reflections leading to constructive intreference of light waves give rise to high SERS enhancement, which was counter-veriied by the use of silica ore~goldlaland shel nanoparticles, where enbancement was found to decrease by a factor of 6 and the detection limit decreased by 100 times under similar experimental conditions ‘The plasmon coupling among the gold islands on the surface is also responsible for the signal enhancement. Sandwich nano- particle canbe a potential substrate for SERS, and these can be incorporated for biodetection (due to the presence of nontoxic {gold and an inet sia surface) in the fatre. EXPERIMENTAL METHODS Synthesis of Silver Core~Siica Shell. Te stver cores shell nanoparticle (Ag@SiO,) was prepared by the method given by Chaorong Li et al:® Briefly, 100 mL. of absolute ethanol (Commercial Alcohols, AR) and 50 mL, of mill-C water was ‘vigorously stirred at 80 °C; 10 ml, of a 0.05 M aqueous solution of silver nitrate (Sigma Aldrich) was added to the water alcohol misture and stired for $ min, while heating continuonly, Then, 20 mi of2$ mM poly-N-vinyl pyrrolidone (Loba Chemie) was added in aliquots of 1 mi in $ min, After the mixture was stired for 20 min at 80 °C, § ml of OL M NaOH (Merck) was added to the solution. ‘The solution was cooled, and the stirring was continued for 2h, after which silver nanoparticles were obtained For the siica coating, $0 mL. of absolute ethanol, § mL of ammonia solution (28-33%, Merck), and 1 mL of teraethyl orthoslicate (Merck) in aliquots of 200 uL were added to the PVP-capped silver nanoparticles. This soktion was stired overnight (12 h) at room temperature. The Ag@SiO, ranopartiles formed were washed with a 1:1 soltion of ethanol and water. In order to remove the bare sica nanoparticles formed in the process, core—shell nanoparticles were centrifuged 2 8000 rpm, and the supernatant was Urown. The nanoparties were dried at 100 °C before gold coating To obtain diferent sca sell thicknesses, the volume of TEOS ‘was varied; 600 pil and 1, 2, and 4 mL of TEOS was added to obtain silica shells of 25, 4, 50, and 60 nm, respectively Formation of Gold’ Island on Silica Shells and SERS Experiments, Gold coating over Ag@SiO; nanoparticles was done by using a modled approach for gold coating on silica given by Christina Graf et al; $0 mg ofthe above synthesized Ag@SiO, nanoparticles was suspended in 10 mL of a 2% solution ‘of APTES (Sigma Aldrich) in ethanol. This was then washed with ethanol and redispersed in $0 mL of ethanol. Gold nanoclusters (2. nm) were prepared by adopting the method given by Dulf et al* For the gold coating first, gold nanoclusters were deposited on the Ag@SiO, nanoparticles. Briefly, 45.5 mL of water was putin a 100 mL round bottom (RB) flask. To this, 1.5 mL of 0.2 M NaOH was added while sting, and 120 4L of an 80% aqueous solution of tetrakis (hydroxymethy)phosphonium chloride, THPC (Sigma- Aldeich), was diluted with water to make a total volume of 10 mb Then, 1 mi of the diluted THPC solution was added to the RB. Nex 2 mL of a 25 mM dark aged solution of aurochlorie acd, HANCl, (Spectrochem), was added to the above mixture, resulting in the formation of orange—brown hhydeosols of gold An interval of 2 min was maintained between the addition of HAuCl, and THPC. It is advinble t0 use freshly prepared solution of gold chuster as they are unstable and have the tendency to agglomerate ‘The APS-modiied Ag@SiO, nanoparticles (50 ml.) were added dropwise to the gold nanoparticle solution in 10 min ‘The solution was sited for 12. Free gold nanoparticles were removed by centrifuging at 8000 rpm and decanting the supernatant. The washed nanopartides were redisperied in 100 mab of water, sized for 1 h to form a uniform colloidal solution, and kept for aging in a refrigerator at 4°C for a week. ‘A022 mM HAuCl, solution (100 ml) and $0 ml. of a 1.8 mM hydroxylamine hydrochloride (Fluka) solution in water were added simultaneously dropwise to the precurior Ag@ SiOyseeded nanoparticles while stirring. Sting was continued for 1 after the final addition. The color of the nanopatiles changed from black to reddish brown as the god island grew For diferent densities of gold islands on the silica shel, the APTES concentration in ethanol was changed, and the com centration of HAuCl, was varied from 0.11 #0 0.44 mM in the gold island grow solution, For SERS, 1 mL of Ag@SiO\@Au was cxnteifuged and secispersed in 200 iL of water. Then the analyte was mixed with the nanoparticles, and 1 jl. of the minture was dropped and died on a glass side, SERS of the dried sample was recorded, ‘Characterization. UV-visible extinction spectra of the colloids were recorded from the dilute solutions in a 1 cm quartz cell using a Perkin-Elmer Lambda 900 spectrometer. TEM ts were performed using a JEOL 3010 with an operating voltage of 300 KeV. Samples for TEM were prepared by drop coating on a Formvar-film-covered carbon- coated copper gid. The powder XRD pattern was recorded ‘with Cu-Ker radiation (Bruker D8 discover; 40 KV, 30 mA). Raman and SERS measurements were performed by a custom- built Raman. microscope with a He-Ne laser of 6328 nm ‘wavelength, described elsewhere." ASSOCIATED CONTENT © Supporting information BET measurements, extinction spectra, TEM of sliver core silica shell and sandwich nanoparticles, partie sae ditebuton, XRD pattem, TEM picture of slicagold core-shell nano- parties, nd SERS with core-shell and sandwich nanoparticles. ‘This material is avalable free of charge via the Internet at hxp://pubsacs.org AUTHOR INFORMATION Corresponding Author "Erma: cbhas@jncas.acin, Notes ‘The authors declare no competing financial interes. ACKNOWLEDGMENTS ‘The authors acknowledge Swedish Research Links and JNCASR for providing the financial support. We are thankful to Dr. Usha Tumkurkar for doing the TEM measurements and Dr. Karthik Bala for the FESEM measurements, me ean ps0 641 Py Chm Lt 8131‘The Journal of Physical Chemistry Letters REFERENCES (1) Nl, PN; Wu, W; Zhao, Hs Hater, Ls Schl EA; Maye, ML M, Layer by Layer Processing and Optical Poperies of Core/Alloy Nanostrutices. Ane Chem See. 2011, 133, 52245227 (@) Rea, Ly Sanches Cones, §; Garcla Ramos, J. Vi Morel, G. ‘Mixed Silver/Gold Colloids. A Study of ‘Theis Formation, Morphology, and Surface Enhanced Raman Activity. Leng 2000, 1s, 9722-9728, (3) Krebig, Us Genze, 1. Optial Absorption of Siall Metalbe Paris. Surf. So. 1985, 156, 678-700. (4) Malwa, M. Jy Ling). ¥3 Hensie, Jz Yang, P. Anisteopie Etching of Ser nanoparticles for Plsmonie Strctares Capable of Single Particle SERS. J.Am. Chem Soe 2010, 132, 258274 (S) Son, Yj Xia, Y. Shape Controlled Symhese of Go and Siver Nanoparticles, Scone 2002, 295, 2176~2179. (6) Jan PK; Lee, K Sy El-Sayed, LHL; EISayed, M.A. Calealted Abwoiption and Scatenng Properties of Gold Nanoparticles of Diferent Sie, Shape, and Compostion: Applications in Biological Imaging and Biomedicine J. Phyz Chem. B 2006, 110, 72387248, (7) Ya ¥. ¥s Chang 8S; Lee, C. Ly Wang C. RC. Gold Nanorode: Electrochemial Sythess and Optical Properties. J. Phy. Chem B 1997, 101, 6561-6554, (8) ia, R; Cao, ¥. Cy Hao, Es Méteang, G8, Sehat G. Cz Mirkin, CA. Controlling Anisotropic Nanoparticle Growth Through Plasmon Exatatlon, Nature 2003, 425, 487—490 (©) Stoller, P Jacobsen, Vz Sandoghdar, V. Measurement of the Complex Dilectie Constant ofa Single Gold Nanoparticle, Opt Lat, 2006, 31, 2474-247, (10) Underwood, 8; Mulvaney, P, lsc of the Solution Reactive Index on the Calor of Gold Colds. Langmuir 1994, 10, 3427— 3430. (11) Malin, M. Py Marphy, C.J Soltion Phae Symes of Sub-10| ram AuwAg Alloy Nanoparticles Novo Let, 2002, 2, 1235-1237 (12) Toshing, N; Harada, My Yamazaki Y; Asakura K. Catalytic Activity and Structural Analysis of Polymer Protected Au-Pd Bimetalie Clusters Prepared by the Simultaneous Reduction of HAUCL, and PAC, Phys Chom. 1992, 96, 9927-9933, (13) Moris, R'H Collin, I. F. Optical Properties of Malayer Colloids J. Chem Phys. 1964, 47, 3357-3363. (14) Schiehom, M; LirMand, LM. Synthesis of Binetalie Colloids with Tailored Intermetallic Separation. Nano Lett 2002, 2, BH (15) Wang, Hy Halas, NJ. Mesoscopic Au Meatball Particles, Ad ‘Mar 2008, 20, #20825. (16) Talley, C.E; Jackin, J.B Oubee, Cs Grady NK; Hallas. Wy Lane, 8. My Her, TLR; Nordlande, Py Halse, N. J. Surtice [Enhanced Raman Seatering fom Individual Aw Nanoparticles and Nanoparticle Dimer Substrates. Nano Let 2005, 5, 15691874, (17) Jackson, J. By estat, 81 Hitch, L. Ry Weal J. Le; Hala, IN. J. Controling the Srfice Enhanced Raman Eifect via the Nanoshell Geometry. Appl Phys Let, 2003, 82, 287258, (18) Jackson, J. Bj Halas, NJ. Surface Enhanced Raman Scatesing on Tunable Plasmonic Nanoparticle Substrates, Pr. Natl. Acad. Se USA 2008, 101, 17930-17935, (19) Bardhan, R; Mobheree, S3 Mita, No As Levit, 8. Da Nordander, Py Halas, N, Jy Nanomphereina-Nanoehel, A Simple Nanomatryusha |. Pigs. Chene C 2010, 114, 7378-7383. (G0) Kim, K; Kim, 1. $3 Park, H. K. Facle Method to Prepare Surfce Enhanced Raman Scattering Active Ag Nanostructures on Sila Spheces.Lengrir 2006, 22, 8083-8088, (21) Moskovits, M. Surce Eahanced Spectoscopy. Rev. Mod. Phy 1985, 57, 783-826 (22) Campion, A; Kambhampati, P, Surface-Enhanced Raman Sealtering. Chem Soc. Re. 1998, 27, 241—250 (23) Teng. Ly Zhe, Ty Lis, Z. Approaching the Hlstomagnes Mechanism of Surisce Enhanced Raman Scattering: From Self [Actembled! Arrays to individual Gold Nanoparicles, Chem Soe. Res 2011, 40, 1286-1304, ms (24) Campion, Ay Iranecky, Jy I Chis CM; Fasten MO the Mechanism of Chemiesi Enhancement in Surace Enhanced Raman Seating J. Am. Chem, So 1995, 117, 1180711808, (G5) Aroca RSurpie Enhanced Vibrational Spcreopy, Joho Wiley 1 Sons: Chichestes, UX, 2006; » 3 (25) shoute 1. CT; Beeps, A.J, Mahmoud, AM; Hue, K Ds MeCrery, R. L. Optic Interience Elks to the Design of Substrates for Satu Eabanced Raman Spectroscopy. Appl Spectre 209,63, 133-140. (G7) Shouts, LCT. Muliayer Substrate Medisted Tuning Resonance of Plusmo and SERS EP of Nanoroctred Siver ‘ChemPhysCher 2010, 11, 2539-254, (28) Stober, W; Fink A; Bobs, £. Contolled Growh of Monosepeee’ Silica Spheres in the Micron Sie Range, J. Collid Intce Sa 1968, 26, 2-89 (29) Oldenburg 5. Jp Ave, RD Wesco, S. Ly Haas, N.. Nanoeogieering of Opti! Resonance, Chem. Phy Lat. 1994, 28, prety (0) Oldenburg S.J Hale, 6D, Jaon,J.Bs Halas, NJ Light Seatering ftom Dipole and Quadrupole Nanovhell Antennas. Appl Pine Lett 1999, 75, 1055-1085. (G1) Oldenburg & Js Jahn, J. By Wester, 8, Ly Haas, N. Ingued Exincon Froperses of Gold Nanohels Appl Phy. Let 1999, 75, 2897-2899. {G2} Oldenburg S.J Wester, 5. Ly Avert, R Dy Haas, N.. Suse Enhanced Raian Satesing in the Nea lniaced Using Metal NanosbelSobstates [Chom Phys 1999 111, 4729-8735 (53) Thenen, PKalled Beh 1928, 29, 122-146 (64) Daft DG; Baker, A; Eabardy, P,P A New Hydrosl of Gold Cloter 1, Formation and Pare Ste Vartion Langu 1983, 9, 2301-2308 (85) Graf, Ci vn Blnderen, A Metioieeste Calla Core Shel Paricles for Photon Applstion:Lavgmir 2002, 18, 24 535 (35) Pol, VG Gedanken, Ay Calderon-Moreno, J. Deposition of Gold Nanopuies on Sia Spheres A Sonochemie Approach. Chon. Mater 2003, 15, LLLL=1118 (99) Bryant, M.A Jo, SLs Pemberton, JE. Raman Satering fiom Monolier Pisa of Thiophene! and 4-Meeaplopyridine at Patina Suraes Lanprair 1998, 8, 753-756 G8) U.S) We, Dy Xo, X; Gu, R. There and Experimental Stadier ‘on the Advortion Behavior of Thiophenol on Gold Ninoparices J Ramon Spero. 2007, 38, 1436~1483 69) aes W. 5; Lani Sayer Itverence Eahanced Raman Sspecuosopy. Appl Phy Lett 1982, 6, 19-21 {4o) Ls Cy Mey} Li 8; Lu Ny Wang Ls Che, Bs Dong, W.Oae- Pot Synthesis of AgA@SIO(2) Ag Sandwich Nanostructures. Nan tehnaogy 2010, 31, 245602245607 (Gl) amar, G.'V. P; Narpana, C. Adapting » Fhorescence Microscope to Prior Surce Enhanced Raman Spectroscopy. Cur Se 2007, 95, 778-781.