Vibrational Spectroscopy 53 (2010) 117120

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Surface-enhanced Raman scattering inducible by recyclable Ag-coated magnetic particles

Jeong-Yong Choi a, Kwan Kim a,*, Kuan Soo Shin b,**
a b

Department of Chemistry, Seoul National University, Seoul 151-742, Republic of Korea Department of Chemistry, Soongsil University, Seoul 156-743, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history: Received 29 August 2009 Received in revised form 8 December 2009 Accepted 7 January 2010 Available online 18 January 2010 Keywords: Fe3O4 particles Silver nanostructure Surface-enhanced Raman scattering (SERS) Adenine

A novel fabrication of Ag-deposited silica-coated Fe3O4 particles and their application as surfaceenhanced Raman scattering (SERS) substrates in chemical analyses are demonstrated. Initially, 426-nm sized spherical magnetite particles composed of 13-nm-sized superparamagnetic Fe3O4 nanoparticles were synthesized, and silver coating was conducted using butylamine as the reductant of AgNO3 in ethanol, after direct silica coating on the Fe3O4 particles. The Ag-deposited silica-coated Fe3O4 particles (Fe3O4/SiO2@Ag) are found to be efcient SERS substrates with the enhancement factor at 632.8 nm excitation to be about 3 106. Since the magnetic particles are readily recovered from the solution phase without centrifugation and/or ltering, these SERS-active magnetic particles must be useful in the Raman spectroscopic analysis of dissolved organic species, as well as thin organic lms. For instance, adenine could be detected down to 10 nM concentrations. In addition, an 1.5-nm thick dye lm on a glass slide could also be detected by Raman spectroscopy after dropping 1.0 mL of Fe3O4@Ag colloids onto the lm. The used Fe3O4/SiO2@Ag particles can then be recycled by treatment with a mild borohydride solution. 2010 Elsevier B.V. All rights reserved.

1. Introduction Noble metallic nanostructures exhibit a phenomenon known as a surface-enhanced Raman scattering (SERS) in which the Raman scattering cross-sections are dramatically enhanced for the molecules adsorbed thereon [1,2]. The rst observation of anomalously intense Raman scattering at a silver electrode was made by Fleischmann et al. [3]. Two groups, Van Duyne and Jeanmaire [4] and Albrecht and Creighton [5], independently repeated this experiment, and proposed that an enormous increase (i.e., a factor of 105 to 106) in the Raman cross-section must have occurred upon adsorption. Enhancement was subsequently found for a variety of molecules adsorbed on several different kinds of surfaces. When the adsorbed molecules are subjected to resonance Raman scattering, it is called a surface-enhanced resonance Raman scattering (SERRS), by which even single-molecule detection is known to be possible, suggesting that the enhancement factor can reach as much as 1014 to 1015 [6,7]. The effective Raman crosssections are then comparable to the usual uorescence crosssections.

* Corresponding author. Tel.: +82 2 8806651; fax: +82 2 8891568. ** Corresponding author. Tel.: +82 2 8200436; fax: +82 2 8244383. E-mail addresses: kwankim@snu.ac.kr (K. Kim), kshin@ssu.ac.kr, shin-1979@hanmail.net (K.S. Shin). 0924-2031/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.vibspec.2010.01.001

To use SERS in routine, on-line studies for analytical purposes [8,9], the substrates should be stable, reproducibly prepared, inexpensive, and easy to make. The fabrication of SERS-active substrates has accordingly been a challenge over the decades. In reality, the enhancement properties of a SERS-active surface are highly susceptible to its method of preparation and therefore its detailed nanostructure. Lots of SERS-active surfaces currently available are thus lacking in stability and/or reproducibility. Electrochemically roughened electrodes [10,11] usually exhibit poor reproducibility. SERS substrates obtained by chemical methods are frequently not clean due to organic contaminants. Vacuum-evaporated metal island lms should be prepared with the evaporation rate and mass thickness of the corresponding metals controlled to obtain the best SERS enhancement; this system is also expensive. Recently, Guo et al. [12] reported a general route to construct multifunctional Fe3O4/metal hybrid nanostructures using 3aminopropyltrimethoxysilane (APTMS) as a linker. We also recently demonstrated that SERS-active Ag-coated Fe2O3 particles can be fabricated, but without using a linker like APTMS, by soaking Fe2O3 in ethanolic solutions of AgNO3 and butylamine [13]. These particles are useful especially in the Raman spectroscopic analysis of organic species in aqueous solutions [14]. This is particularly because magnetic particles are readily recovered from the solution phase without centrifugation and/or ltering. Even naphthalene, a prototype aromatic molecule whose adsorption

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strength to Ag is too weak to observe its intrinsic SERS spectrum, was able to be detected down to 200 nM by using pentachlorobenzenethiol-adsorbed Ag-deposited Fe2O3 particles as the adsorbent. The Fe2O3 particles used earlier were commercial products with very irregular shape and size distribution. Accordingly, it was difcult to enjoy fully the properties of superparamagnetism of nanometer sized Fe2O3 particles. In this work, we have rstly synthesized spherical Fe3O4 particles with a mean diameter of 426 40 nm [15], but are actually composed of $13 nm superparamagnetic particles, and then the as-prepared Fe3O4 particles are coated with SiO2 [12,16] onto which Ag nanoaggregates are nally assembled to endow them with both the superparamagnetism and SERS activity. We demonstrate the usefulness of those Ag-deposited SiO2-coated Fe3O4 particles (hereafter, denoted by Fe3O4/SiO2@Ag) especially in the Raman spectroscopic analysis of the chemical species dissolved in aqueous solutions and also the species present on solid substrates. 2. Experimental Ferric chloride hexahydrate (FeCl36H2O), silver nitrate (AgNO3), sodium acetate, butylamine, adenine, rhodamine B isothiocyanate (RhBITC), polyethylene glycol (MW 3400), poly(allylamine hydrochloride) (PAH, MW 70 kDa), tetraethyl orthosilicate (TEOS, 98%), and silver powder (mAg, 99.9+%) with a particle size of 2.03.5 mm were purchased from Aldrich and used as received. Ammonia solution (28.030.0 wt.%) was obtained from Sanchun Pure Chemical Company. Other chemicals, unless specied, were of reagent grade, and highly puried water, of resistivity greater than 18.0 MV cm, was used throughout the experiments. A neodymium magnet in size of 3 mm in diameter and 3.5 mm in length was purchased from Fisher. RhBITC was grafted to PAH following the literature method [17,18]. From the molar extinction coefcient of RhBITC (eo = 10.7 104 L mol1 cm1), the mean molar ratio of labeled monomers of PAH was estimated to be in the ratio 1:6150. Spherically shaped Fe3O4 particles were synthesized following the protocols of Deng et al. [15]. Initially, FeCl36H2O (1.35 g, 5 mmol) was dissolved in ethylene glycol (40 mL) to form a clear solution, followed by the addition of sodium acetate (3.6 g) and polyethylene glycol (1.0 g). The mixture was stirred vigorously for 30 min and then reuxed at 200 8C for 72 h. After cooling to room temperature, the black products were washed several times with ethanol and then dried at 60 8C for 6 h. The formation of Fe3O4 was conrmed from XRD. According to TEM images, the size of Fe3O4 particles was approximated to be 426 nm in diameter. Ag can be deposited directly onto Fe3O4 particles. However, a more homogeneous deposition of Ag and the increased dispersion stability are accomplished once Fe3O4 is coated with SiO2 beforehand. Accordingly, Fe3O4 particles (10 mg) were dispersed in 30 mL ethanol into which water (8 mL), NH3 (30%, 0.5 mL) and TEOS (0.5 mL) were added with sonication. After 1 h, the black precipitate was collected with a permanent magnet, and rinsed with ethanol three times. Subsequently, 2 mg of silica-coated Fe3O4 (Fe3O4/SiO2) particle was placed in a polypropylene container into which 10 mL of a silvering solution was added, and then incubated for 40 min at 50 8C with vigorous shaking. As a silvering mixture, the concentration of AgNO3 in absolute ethanol was maintained at 4 mM, while that of butylamine was subject to change. The polypropylene container was used to avoid nonspecic silvering of the reaction vessel [13]. The Fe3O4/SiO2@Ag particles were separated from the reaction mixture by using a magnet, and rinsed with ethanol. Subsequently, on one hand, these particles were soaked in the analyte solution and then dried in vacuum prior to the analysis by SERS and, on the other hand, a drop of the colloid solution was placed on a lm to be analyzed.

UV/vis absorption spectra were obtained using a SCINCO S-4100 spectrometer. The magnetic properties were measured using a Quantum Design SQUID Magnetometer. Transmission electron microscopy (TEM) images were obtained on a LIBRA120 transmission electron microscope at 120 kV. X-ray diffraction (XRD) patterns were obtained on a MAC Science Co M18XHF-SRA powder diffractometer for a 2u range of 30808 at an angular resolution of 0.058 using Cu Ka (1.5406 A) radiation. Raman spectra were obtained using a Renishaw Raman System Model 2000 spectrometer. The 632.8 nm radiation from a 17 mW He/Ne laser (Spectra Physics Model 127) was used as the excitation source. Raman scattering was detected over 1808 geometry with a Peltier cooled (70 8C) chargecoupled device (CCD) camera (400 600 pixels). The SERS peak intensity was normalized with respect to that of a silicon wafer at 520 cm1. 3. Results and discussion All the XRD peaks of iron oxides synthesized in this work could be indexed to the magnetite structure of Fe3O4 (JCPDS 75-1609), as in Fig. 1a. The average size of the Fe3O4 nanoparticles deduced from Sherrers formula is about 13 nm. According to the TEM image (see the inset of Fig. 1a), Fe3O4 particles were spherical, but with a mean diameter of 426 40 nm. The discrepancy between the XRD and TEM data could be understood by assuming that the 426-nm sized particles were actually composed of 13-nm sized Fe3O4 nanoparticles. This suggests that Fe3O4 nanoparticles have self-assembled into spherical aggregates. In fact, a close look at the TEM image indicated that large particles consisted of agglomeration of small particles. Disordered pores existed among the primary nanoparticles but within spherical aggregates.

Fig. 1. XRD spectra of (a) Fe3O4 and (b) Fe3O4/SiO2@Ag particles: insets represent the respective TEM images.

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Fig. 3. SERS spectra of RhBITC adsorbed on (a) Fe3O4/SiO2@Ag and (b) commercial mAg particles gathered at 632.8 nm excitation.

Fig. 2. (a) Magnetization curve of the as-prepared Fe3O4 particles measured at room temperature: inset shows a magnied view at low applied elds. (b) A similar magnetization curve measured for Fe3O4/SiO2@Ag particles.

Fig. 2a shows the magnetization curve of the as-prepared Fe3O4 particles measured at room temperature. The curve presents a small hysteresis loop, and the magnetic saturation value is $70 emu/g. From a magnied view of the magnetization curve at low applied elds, the remnant Mr dened as the magnetization at H = 0 is about 1.32 emu/g, while the coercity Hc dened as the eld magnitude necessary to obtain M = 0 is about 9.45 Oe. It has been reported that the magnetic Fe3O4 particles exhibit superparamagnetic behavior when the particle size decreases to below a critical value, generally around 20 nm. The relatively high Ms value with relatively low Hc and Mr values in this work can then be attributed to the small primary particle size of about 13 nm in dimension, as well as to the oriented attachment of primary particles in large spherical aggregates. As mentioned in Section 2, a silica layer was deposited beforehand onto the surface of spherical Fe3O4 aggregates due to irregular deposition of Ag. According to the TEM image, the silica shell thickness was estimated to be about 50 nm. When a very dilute butylamine was used at 4 mM ethanolic AgNO3, Ag nanoparticles with sizes of 530 nm were formed evenly over the silica surface. Upon increasing the concentration of butylamine, much larger Ag nanoparticles were formed at rst, and then the particles gradually coalesced into a network-like structure (see the inset of Fig. 1b). The deposition of silver can be conrmed from the XRD data in Fig. 1b. Four XRD peaks are clearly observed at 2u values of 38.18, 44.38, 64.48, and 77.38 due to the reections of (1 1 1), (2 0 0), (2 2 0), and (3 1 1) crystalline planes of cubic Ag, respectively [19]. The average size of Ag nanoparticles deduced from Sherrers formula is about 30 nm for the sample corresponding to Fig. 1b [20]. Fig. 2b then shows the magnetization curve measured for the Fe3O4/SiO2@Ag particles. The magnetic saturation value has decreased nearly to one third of the initial value after coating with silica and silver, i.e., $25 emu/g. A part of the decrease is due to mass effect of silica and silver, and the remaining part is

due to their diamagnetic shielding. Anyhow, the Fe3O4/SiO2@Ag particles could be magnetically concentrated and readily picked up using a small magnet. We evaluated the performance of Fe3O4/SiO2@Ag particles as SERS substrates initially using rhodamine B isothiocyanate (RhBITC) as a model compound. The most intense Raman spectrum was obtained from the Fe3O4/SiO2@Ag particles manufactured in a 1:1 solution of AgNO3 and butylamine. Although not shown here, the absorbance above 420 nm gradually increased, in UV/vis extinction spectra, toward the near infrared region upon the deposition of silver. It must be due to the Mie plasmon resonance excitation from the silver nanoparticles [21], associated with the electromagnetic enhancement mechanism in SERS. Fig. 3a shows the SERS spectrum of RhBITC adsorbed on Fe3O4/SiO2@Ag particles prepared in an ethanolic solution of 1:1 molar ratio of butylamine and of AgNO3. For reference, Fig. 3b shows the SERS spectrum of RhBITC adsorbed on mAg powders which are known to be effective substrates for the IR and Raman spectroscopic characterization of molecular adsorbates [2224]. The reason for taking the latter spectrum was rst simply to compare its SERS activity with that of Fe3O4/SiO2@Ag particles, but it was intended, if possible, to gure out the enhancement factor (EF) of Fe3O4/SiO2@Ag particles indirectly by comparing their SERS activities under the same experimental conditions. It is seen that the SERS peaks in Fig. 3a are an order of magnitude stronger than the corresponding ones in Fig. 3b. The EF of a typical aromatic thiol such as benzenethiol adsorbed on mAg powders was in fact determined to be 3.8 105 (with 632.8 nm excitation) [25]. Hence the EF factor of Fe3O4/ SiO2@Ag particles may well be more than 3 106. We have subsequently taken a series of SERS spectra for adenine, a compound of biological signicance, by varying its concentration from 104 to 108 M. In agreement with the previous reports, one distinct band is observed at 734 cm1, as shown in Fig. 4, along with a series of weak bands in the region 12001500 cm1; all these bands were assigned previously to the skeletal vibration modes [26]. The graph of the intensity of the adenine peak at 734 cm1 plotted against the concentration of adenine solution allowed us to make analyses of solutions as low as 10 nM based on a signal-to-noise (S/N) ratio of 3. Perhaps it would be worth comparing the present result with that of our previous study. We reported earlier that adenine can be detected as low as 1.0 107 M via SERS using an Ag-coated glass capillary [27]. The detection limit of Fe3O4/SiO2@Ag particles is obviously 10 times lower than that of an Ag-coated capillary. Considering that the concentration of bio-analytes is frequently in the sub-micro molar regime, our Fe3O4/SiO2@Ag particles must be useful for their analysis. Another advantage is that the Fe3O4/SiO2@Ag particles can be recycled by treating with a mild borohydride solution to desorb any organic species from the Ag surface [28].

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Fig. 4. SERS spectra of adenine on Fe3O4/SiO2@Ag gathered by varying its concentration from 104 to 108 M.

with SERS activity, silver coating was conducted using butylamine as a reducing agent of AgNO3 in ethanol, after direct silica coating on the Fe3O4 particles. The most SERS-active particles were manufactured in a 1:1 solution of AgNO3 and butylamine. Comparing the SERS peaks of RhBITC on Fe3O4/SiO2@Ag and commercial mAg powders, the EF factor of Fe3O4/SiO2@Ag particles was estimated to be more than 3 106. Those Fe3O4/SiO2@Ag particles were conrmed to be very efcient SERS substrates usable in the microanalysis of solution and surface species. On one hand, the detection limit of adenine is found to be, for instance, as low as 10 nM based on an S/N ratio of 3. On the other hand, an 1.5nm thick RhBITCPAH lm on a glass slide could be analyzed by Raman spectroscopy by a drop (1.0 mL) of Fe3O4/SiO2@Ag colloids. The present method is cost-effective and suitable for the mass production of SERS-active magnetic particles so that its application prospects are expected to be very high, particularly because the observation of vibrational spectra must be one of the most incisive methods for understanding the chemical and physical phenomena in solutions as well as on a variety of surfaces. Acknowledgements This work was supported by the Korea Science and Engineering Foundation (Grant Nos. R11-2007-012-02002-0 and M10703001067-08M0300-06711-Nano2007-02943) and the Korea Research Foundation (Grants KRF-2008-313-C00390, KRF-2008313-C00411, and 2009-0072467). References

Fig. 5. Raman spectrum taken after dropping 1.0 mL of Fe3O4/SiO2@Ag colloids onto 1.5-nm thick RhBITCPAH lm on a glass slide.

An absorption band could be identied, although weak, at 540 nm in the UVvis spectrum of the RhBITCPAH lm spin cast on a glass slide. Its thickness was determined to be 1.5 nm by ellipsometry. However, the resonance Raman spectrum of the lm was not observable due to a uorescence background. When a drop of ($1.0 mL) of Fe3O4/SiO2@Ag colloids and toluene were placed on the lm, Ag-coated magnetite particles were agglomerated, showing the intrinsic peaks of RhBITC, as shown in Fig. 5. The appearance of the RhBITC peaks must be due to the enhanced electromagnetic eld caused by clustering of the suspended Fe3O4/ SiO2@Ag particles. After taking the Raman spectra, the clustered Fe3O4/SiO2@Ag particles were readily removed from the glass substrate by using a very strong neodymium magnet. Hence the present methodology must be a useful tool in probing the physicochemical characteristics of surface adsorbates on diverse substrates including historic paints. 4. Conclusions Firstly, we have successfully synthesized spherically shaped magnetite particles. According to the XRD and magnetization data, the 426-nm sized spherical particles were composed of 13-nm sized superparamagnetic Fe3O4 nanoparticles. To endow them

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