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DOI: 10.1002/chem.201002027

Surface-Enhanced Raman Scattering of Single- and Few-Layer Graphene by the Deposition of Gold Nanoparticles
Jisook Lee,[a] Sangdeok Shim,[b] Bongsoo Kim,[c] and Hyeon Suk Shin*[a]
Abstract: Surface-enhanced Raman scattering (SERS) of graphene on a SiO2ACHTUNGRE(300 nm)/Si substrate was investigated by depositing Au nanoparticles using thermal evaporation. This provided a maximum enhancement of 120 times for single-layer graphene at 633 nm excitation. SERS spectra and scan images of single-layer and fewlayer graphene were acquired. Singlelayer graphene provides much larger SERS enhancement compared to fewlayer graphene, while in single-layer graphene the enhancement of the G band was larger than that of the 2D band. Furthermore, the D bands were identified in the SERS spectra; these bands were not observed in a normal Raman spectrum without Au deposition. Appearance of the D band is ascribed to the considerable SERS enhancement and not to an Au deposiKeywords: gold · graphene · Raman spectroscopy · surface chemistry tion-induced defect. Lastly, SERS enhancement of graphene on a transparent glass substrate was compared with that on the SiO2ACHTUNGRE(300 nm)/Si substrate to exclude enhancement by multiple reflections between the Si substrate and deposited Au nanoparticles. The contribution of multiple reflections to total enhancement on the SiO2ACHTUNGRE(300 nm)/Si substrate was 1.6 times out of average SERS enhancement factor, 71 times.

Introduction
Raman spectroscopy has been utilized as a powerful tool for the characterization of graphene, as it can identify the number of layers, the electronic structure, the edge structure, the type of doping and any defects in the graphene.[1] A Si substrate with a metal oxide layer of a specific thickness has been employed to enhance the Raman signal, which is called interference-enhanced Raman scattering (IERS).[2] In particular, its enhancement of nearly 30 times of the Raman signal of graphene on a Si wafer with a 300 nm-thick SiO2 layer makes Raman spectroscopy very useful in graphene research.[2b] It has also been reported that inserting a Ag layer between the layers of metal oxide (Al2O3) and Si further enhances the Raman signal. This is ascribed to a combination of IERS and surface-enhanced Raman scattering (SERS).[3] As Ag does not make contact

[a] J. Lee, Prof. H. S. Shin Interdisciplinary School of Green Energy Ulsan National Institute of Science and Technology (UNIST) Banyeonri 100, Ulsan 689-805 (South Korea) Fax: (+ 82) 52-217-2909 E-mail: shin@unist.ac.kr [b] Dr. S. Shim Central R&D Institute, Samsung Electro-Mechanics 314 Maetan-dong, Suwon 443-743 (South Korea) [c] Prof. B. Kim Department of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 305-701 (South Korea) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.201002027.

with the graphene in this case, the enhancement factor of SERS due to the Ag layer only ranged from 5 to 20.[3] The increased enhancement factor to 60 has been recently reported in the system that gold disc was deposited on mechanically exfoliated single-layer graphene.[4a] In addition to that, some SERS studies have been tried in reduced graphene oxide samples with gold nanoparticles[4b,c] and gold rods[4d] and CVD-grown graphene samples with a thermally deposited gold film and a close-packed gold nanosphere layer,[4e] in which enhancement factors were still low. So far, however, any characteristic change depending on the number of graphene layer in SERS has not been reported. The deposition of Au film on graphene was recently reported.[5] The morphology of the Au film, including the grain size and the spacing between the grains when it is deposited on graphene is strongly affected by the layer number of graphene, forming grains of a larger size and spacing in few-layer graphene compared to those in singlelayer graphene. While the difference in the morphology of the Au film could be readily distinguished by scanning electron microscopy (SEM), making possible distinction of graphene samples that have a distribution of different layer numbers, the exact layer number could not be determined. It was also reported from the Raman spectra that the nature of the graphene was not altered after the deposition of Au.[5] The present study reports the SERS of graphene onto which metal nanoparticles are deposited by thermal evaporation. It was found that the enhancement factor of SERS varied strongly depending on the density of the evaporated Au nanoparticles and the excitation wavelength. Moreover, the SERS intensity was higher for single-layer graphene than for few-layer graphene. The D band in a SERS spec-

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trum that did not appear in a normal Raman spectrum before evaporation of Au was also identified. As the appearance of the D band is ascribed to defects in the graphene, SERS can be used to identify defects in mechanically exfoliated graphene. Lastly, the SERS of graphene on a transparent glass substrate was investigated to exclude enhancement by multiple reflections between the Si substrate and deposited Au nanoparticles, which was compared with that on the SiO2ACHTUNGRE(300 nm)/Si substrate.

Results and Discussion
To obtain the SERS spectra, mechanically exfoliated graphene was prepared on SiO2/Si wafer (a thermally deposited SiO2 layer of 300 nm) by following a typical method.[6] A very thin layer of Au was then deposited on graphene by thermal evaporation. Before the evaporation of Au for the SERS measurement, the number of layers of graphene was determined by AFM and also according to the shape and bandwidth of the 2D band at ~ 2680 cmÀ1 in the Raman spectrum. A single layer showed a sharp and single 2D band with a FWHM of less than 30 cmÀ1, whereas the few-layer samples showed broader 2D bands.[7] For determining an optimized experimental condition which shows maximum SERS enhancement factor of graphene, three parameters were investigated: dependence of SERS of graphene on (i) a kind of metal (Ag an Au), (ii) thickness (density) of evaporated metal, and (iii) excitation wavelength. The largest SERS enhancement factor was averagely obtained in the following conditions: Au deposition on graphene with 4 or 5 nm thickness and 633 nm as an excitation wavelength. In the present study, dependence of SERS of graphene on excitation wavelength is first demonstrated and then comparison of the SERS spectra of singlelayer and few-layer graphene is provided. Dependence of SERS of graphene on excitation wavelength: Figure 1 shows the normal Raman and SERS spectra using excitation wavelengths of 532 nm (a), 633 nm (b), and 785 nm (c) (see AFM image of Au nanoparticles deposited on graphene in Figure S1). The SERS enhancement factors determined from the integrated intensity of the G band before and after Au deposition are 12 for 532 nm (a) and 120 for 633 nm (b). The SERS enhancement factor for 785 nm could not be determined because no band in the normal Raman spectrum before the evaporation of Au was observed. Therefore, the present result indicates that the excitation wavelength of 633 nm shows a larger SERS enhancement factor compared to that of 532 nm. This likely arose because 633 nm was close to the surface plasmon resonance wavelength of aggregated Au nanoparticles on graphene (see Figure 2). While the G and 2D bands were distinctly observed in the SERS spectra using the 785 nm laser, no band was observed in the normal Raman spectrum (Figure 1c). Here, the sample in Figure 1c) was a single-layer graphene sample, as

Figure 1. SERS spectra of single-layer graphene samples on which Au of 4 nm (a and b) or 5 nm c) was deposited. The bottom black curves are the normal Raman spectra before the evaporation of Au and the top red curves are the SERS spectra after the evaporation of Au. a) 532 nm laser: incident power of 2 mW and an exposure time of 0.2 second; b) 633 nm laser: incident power of 3.8 mW and an exposure time of 1 second; c) 785 nm laser: incident power of 4 mW and an exposure time of 1 second. The normal Raman spectra were magnified 2 times in a) and 10 times in b).

Figure 2. UV/Vis spectrum of aggregated Au nanoparticles on quartz.

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The G band as a first-order process should be independent of the excitation energy. However, Dong et al. reported recently that interactions between aromatic molecules and single-layer graphene can induce splitting of the G band by lifting the two-fold degeneracy of LO and TO phonons.[8a] That is, their results indicated that aromatic molecules of tetrasodium 1,3,6,8-pyrenetetrasulfonic acid can alter the electron density distribution of the graphene and lead to phonon symmetry breaking at the G point. The results here in Figure 3 exhibit dependence of the G band on the excitation energies, which can be attributed to the interaction between the Au nanostructures and graphene.[8b] In this case, the width of the G band is related to the electron-phonon coupling.[9] The 2D bands are also divided into two components; their frequencies increase with the excitation energy (Figure S3). The frequency–energy dispersion of the 2D bands for the SERS spectra of the Au-coated single-layer graphene was calculated for the deconvoluted 2D bands in Figure S3. The values of Dw/DE are 119 and 127 cmÀ1 eV for bands at a lower wavenumber and a higher wavenumber, respectively, in the deconvoluted 2D bands. Comparison of the SERS spectra of single-layer and fewlayer grapheme: Normal Raman spectra for single-layer and few-layer graphene show different characteristics, especially in terms of the I2D/IG and shape and position of the 2D band. Therefore, it was considered an interesting venture to investigate the difference between the SERS spectra of single-layer and few-layer graphene. The AFM image of the graphene in Figure 4a) exhibits three regions (1–3) which appear to have a different number of layers at each region. Figure 4b) shows the 2D bands of the normal Raman spectra at each region before the evaporation of Au. While the 2D bands at regions 2 and 3 show broad bands with a FWHM of ~ 46 cmÀ1, the 2D band at region 1 shows a single and narrow band with a FWHM of 29 cmÀ1. It was identified from the Raman spectrum (Figure 4b) and thickness at each region in Figure 4a) that region 1 is a single layer and regions 2 and 3 have a tri-layer structure (See Figure S4). As commented previously, an experimental condition was optimized for SERS measurements of single-layer and fewlayer graphene: aggregated Au nanoparticles (thickness of 4 nm) and an excitation wavelength of 633 nm. Figure 4c) and d) show Raman images mapped with the integrated intensities of the G bands before and after the evaporation of Au, respectively. The outstanding difference between Figure 4c) and d) is that the intensity of the G band is higher in the few-layer graphene (regions 2 and 3) than in the singlelayer graphene (region 1) before the evaporation of Au (Figure 4c), whereas it is higher in the single-layer graphene than in the few-layer graphene after the evaporation of Au (Figure 4d). In Figure 4e) and f), showing Raman images mapped with the integrated intensities of the 2D bands, the intensity of the 2D band appears to be similar in the singlelayer and the few-layer graphene before the evaporation of Au in Figure 4e), whereas it is higher in the single-layer graphene than in the few-layer graphene after the evaporation

determined by Raman spectra using a 633 nm laser in which both the G and 2D bands were observed before and after the evaporation of Au (Figure S2). The results may indicate that the resonant effect of graphene with the 785 nm laser is insignificant but that SERS enhances the intensities of the G and 2D bands without selectivity of the electronic transition energy. Considering that the G band is sensitive to external perturbations such as doping and the electric field, deconvolution of the G bands was carried out, as shown in Figure 3. Figure 3 illustrates that the G band with the 532 nm laser in Figure 1a) is a single band at 1583 cmÀ1 and that the G bands in Figure 1b) and c) are divided into two bands at 1575 and 1586 cmÀ1 for 633 nm and 1576 and 1588 cmÀ1 for 785 nm, respectively. In a comparison of the deconvoluted spectra in Figure 3a) and b), an additional band at a lower wavenumber of 1575 cmÀ1 appeared in Figure 3b) using the 633 nm laser with a large SERS enhancement factor. As in Figure 3b), Figure 3c) with the 785 nm laser shows an additional band at a lower wavenumber of 1576 cmÀ1. Therefore, the SERS enhancement factor with the 785 nm laser is expected to be large.

Figure 3. Deconvolution of the G bands in the SERS spectra of Figure 1.

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Figure 4. a) AFM image of graphene in which region 1 is a single layer and regions 2 and 3 have a tri-layer. b) 2D bands of the normal Raman spectra at each region before the evaporation of Au. c) and d) Raman images mapped with the integrated intensities of the G bands in the normal Raman c) and SERS d) spectra. e) and f) Raman images mapped with the integrated intensities of the 2D bands in the normal Raman e) and SERS f) spectra. g) Normal Raman (black curve) and SERS (red curve) spectra extracted at point A (single-layer graphene). h) Normal Raman (black curve) and SERS (red curve) spectra extracted at point B (tri-layer graphene). The Raman images were obtained using a 633 nm laser with an incident power of ~ 3.8 mW and an exposure time of 1 second. In the Raman images, bright color indicates higher intensity.

of Au in Figure 4f). These observations were reproducible in a few different experiments (see Figure S5). These results indicate that the SERS spectra of graphene show different aspects in comparison with the normal Raman spectra. To investigate the differences between SERS and normal Raman spectra closely, the spectra of points A (single-layer) and B (few-layer) before and after the evaporation of Au were extracted (Figure 4g and h). The resulting enhancement factor, I2D/IG, and the FWHM are summarized in Table 1. From the comparison of the intensities of the G and 2D bands in point A of the single-layer graphene before and after the deposition of Au, the enhancement factor was determined to be 120 and 66 for the G band and the 2D band, respectively. Regarding point B for the few-layer graphene, the enhancement factors of the G and 2D bands were found to be 24 and 23, respectively. For both the G and 2D bands, the SERS enhancement factor in the few-layer graphene is much less than half of that in the single-layer graphene. Such a small enhancement in the few-layer graphene can be attributed to the weak interaction between the Au and the sp2 character (or the p electrons) of graphene due to interlayer coupling (van der Waals interaction), which deteriorates the unique electronic property of graphene. However, this does not mean that the sp3 character appears in the fewlayer graphene. The interaction via a charge transfer between Au and single-layer graphene may be stronger than that between Au and few-layer graphene. The charge transfer between Au and graphene can be demonstrated in the splitting of the G and 2D bands shown in Figure 3 and S3; this may be due to the change in the electronic band structure of graphene by Au, leading to the resulting increase of the FWHM. Here, the FWHM of the 2D band in the normal Raman spectra of graphene is less affected by the excitation energy, charge impurity, and other factors, unlike the position and intensity of the 2D band. A similar charge transfer enhancement was introduced in metallic carbon nanotubes. Dresselhaus et al. reported a further enhanced contribution of selective Lorentzian components (at 1540 and 1515 cmÀ1) associated with metallic nanotubes for laser excitation energies within the metallic (Au) resonance window of the surface-enhanced resonance Raman scattering (SERRS) spectra, whereas all SERRS bands in the semiconducting nanotube regime were enhanced by the same amount, as expected from the electromagnetic enhancement mechanism.[10] They explained this effect in terms of a charge-transfer enhancement between the metal and the nanotubes in addition to the strong electromagnetic enhancement mechanism, which specifically describes the occurrence of a resonance condition between the laser energy and the energy separation of the van Hove singularities in the 1D peaks of the electronic density of states of the nanotube when it was modified by interaction with the metal substrate.[10] As graphene does not have van Hove singularities like 1D carbon nanotubes, the SERS intensity of graphene appears to depend on the extent of the interaction between the Au and the graphene. In addition, recent study

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Enhancement factor G band 2D band 120 24 66 23 FWHM of G band Before After 15 –

Table 1. I2D/IG, enhancement factor and FWHM determined from the spectra in Figure 4g) and h). I2D/IG Before point A (single-layer) point B (tri-layer) 2.4 1.2 After 1.3 1.2

of the contact potential difference of graphene indicated that an inter-layer exchange of the carriers within the fewlayer graphene occurs.[11, 12] Thus, the smaller enhancement factor in the few-layer graphene may be due to an charge transfer from the local electromagnetic field enhanced from the Au to graphene layers. The enhancement factor of SERS in the single-layer graphene is higher in the G band than in the 2D band, whereas in the few-layer graphene it is nearly identical in the G band and the 2D band. This indicates that the G band in the single-layer graphene is susceptible to SERS. Such trend in the enhancement factors is reflected in the I2D/IG values. The I2D/IG value of 2.4 in the single-layer graphene before the evaporation of Au decreases to 1.3 after the evaporation of Au. The I2D/IG value in the few-layer graphene before the evaporation of Au is identical to that after the evaporation of Au. Another interesting point in the SERS of graphene is the evolution of the D band, which has not appeared before Au deposition with the exception of it occurring on the edges (Figure 5). The occurrence of the D band results from de-

graphene, which showed a relatively low enhancement factor. The D band was also not observed in the SERS spectra 26 22 45 – – – using the 532 nm laser, showing a smaller enhancement factor at the same positions. Au-induced defects in the few-layer graphene are ruled out, as the D band should appear in the center areas of the fewlayer graphene (Figure 5b) if Au deposition caused defects in the graphene. However, it is not obvious in this study that the Au deposition does not induce defects in the single-layer graphene. Furthermore, Zhou et al. reported Raman spectra of n-layer graphene samples covered with Au film of 5.0 nm in which no D band was observed.[5] Their results indicate that the deposition of Au on graphene by thermal evaporation does not induce any defects, whereas the annealing of the Au film on graphene at 1260 8C for 30 seconds can induce defects.
FWHM of 2D band Before After

Figure 5. Raman images mapped with the integrated intensities of the D bands in normal Raman a) and SERS b) spectra. The Raman images were obtained using a 633 nm laser with an incident power of ~ 3.8 mW and an exposure time of 1 s; scale bars: 1 mm.

fects in the graphene. It is difficult to detect the D band in normal Raman scattering owing to a very small amount of defects, except for the edge of the graphene. Thus, the ability to probe a fine structure, as in the observation of the D band, is an advantage of SERS. This result indicates that defects Table 2. I2D/IG and average SERS enhancement factor of graphene on the glass substrate and average SERS exist, even in mechanically ex- enhancement factor on the SiO ACHTUNGRE(300 nm)/Si substrate. 2 foliated graphene. As shown in I2D/IG Average enhancement factor (glass Average enhancement factor (SiO2/Si Figure 5b), the appearance of substrate) substrate) the D band is clearly due to 2D band[b] Before After G band 2D band G band[a] large enhancement in the SERS single-layer 5.0 3.8 45 34 71 43 of the single-layer graphene, as multi-layer 1.6 1.4 6 5 17 15 it was not observed in the [a] average SERS enhancement factor from 13 points in single-layer samples. [b] Average SERS enhancement center area of the few-layer factor from seven points in tri-layer samples.

SERS of graphene on transparent substrate: When a SiO2ACHTUNGRE(300 nm)/Si wafer was used as a substrate, an additional enhancement by multiple reflections between Si and deposited Au in the SERS enhancement is able to be included. In order to exclude such enhancement by the multiple reflections and investigate only SERS effect, we prepared graphene sample on a glass substrate, followed by Au deposition (4 nm thickness). Figure 6 shows Raman images before and after Au deposition (spectra extracted from the images are provided in Figure S6). The aspect of intensity changes in Figure 6 before and after the evaporation of Au is very similar to results in Figure 4. The intensity of the G band is higher in multi-layer than in single-layer graphene before the evaporation of Au, whereas it is higher in the single-layer than in multi-layer graphene after the evaporation of Au. The intensity of the 2D band is similar in single- and multi-layer before the evaporation of Au, whereas it is higher in singlelayer than in multi-layer graphene after the evaporation of Au. This trend in the intensity changes is reflected in the I2D/IG ratio (Table 2). The I2D/IG ratio of 5.0 in single-layer graphene decreased to 3.8 after the evaporation of Au. The I2D/IG value in multi-layer graphene before the evaporation of Au is very similar to that after the evaporation of Au. These higher intensities for G and 2D bands in single-layer than in multi-layer after the evaporation of Au are due to only SERS. The present system using the glass substrate is

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Conclusion
The SERS spectra of single- and few-layer graphene were measured by depositing Au nanoparticles on graphene via thermal evaporation. An optimum condition for the SERS measurement of graphene was systematically determined by changing the density of the evaporated Au nanoparticles and changing the excitation wavelength. The SERS spectra of single-layer graphene show different aspects from those of few-layer graphene; thus, SERS can be used for the characterization of graphene. The results of this study also provide clues to understanding the interaction between metal and graphene for further study.

Experimental Section
Figure 6. Raman images of single- and multi-layer graphene on glass substrate. Top images (a, b) are for normal Raman spectra before evaporation of Au and bottom images (c, d) for SERS spectra after evaporation of Au. All images were obtained using 633 nm laser of 3.8 mW at exposure time of 0.5 second. The bright color means higher intensity. The number of layer in multi-layer is considered to be 4 or more than 4 from deconvolution of the 2D band. Preparation of grapheme: The graphene samples were prepared by a mechanical exfoliation method known as the “Scotch-tape method” using Kish graphite from Toshiba Ceramics on a 300 nm SiO2/Si substate.[6] The single-layer and multi-layer graphene samples were identified by an optical microscope, AFM (Multimode V, Veeco Inc.), and by Raman spectroscopy. Evaporation of metals: Au and Ag layers were deposited onto the graphene samples at a rate of 0.5 Š minÀ1 using a thermal evaporator (Woosung Hi-Vac). The thickness of metal layer was measured using a quartz crystal microbalance (QCM) with the thermal evaporator. The UV/Vis spectra of the evaporated metals were measured using quartz substrates with a UV/Vis spectrometer (Cary 5000, Varian). Raman measurement: Raman spectra and images were obtained with a micro-Raman system (Alpha 300 s, WITec GmbH) with 532, 633, and 785 nm lasers. The incident laser power was controlled to be less than 4 mW to avoid laser-induced thermal effects or damage. The specific laser power and exposure time for the Raman spectra and images are shown in each figure. The spatial resolution of the Raman images is ~ 360 nm for the 532 nm laser and ~ 430 nm for the 633 nm laser with a 100 ” objective lens (NA = 0.90). The relative orientation of polarization of incident laser beam with respect to the graphene samples was identical before and after Au deposition.

supposed to show no multiple reflection like SiO2ACHTUNGRE(300 nm)/ Si substrate. Average SERS enhancement factor calculated from 4 points in each single- and multi-layer graphene of Figure 6 are summarized in Table 2 and compared with average SERS enhancement factor calculated from SiO2ACHTUNGRE(300 nm)/Si substrate. The average SERS enhancement factor of 45 for the G band on the glass substrate is about 1.6 times less than the average enhancement factor (71 times in Table 2) or 2.7 times less than the maximum enhancement factor (120 times in Table 1) on SiO2ACHTUNGRE(300 nm)/Si substrate. Therefore, the enhancement factor by multiple reflections on SiO2ACHTUNGRE(300 nm)/Si substrate may be 1.6–2.7 times. This result indicates that the enhancement by multiple reflections between Si substrate and deposited Au nanoparticles as well as SERS by Au nanoparticles is working in graphene sample on the SiO2ACHTUNGRE(300 nm)/Si substrate, but its contribution to total enhancement is marginal. Note that 1.6 or 2.7 is not an exact enhancement factor for the multiple reflections between Si and Au on the SiO2ACHTUNGRE(300 nm)/Si substrate because morphology of Au nanoparticles on the glass substrate is not identical to that on the SiO2ACHTUNGRE(300 nm)/Si substrate, indicating that SERS enhancement factors may be different in two substrates. As for the SERS mechanism, it is considered that electromagnetic (EM) and chemical (CM) enhancements co-exist. The EM is supported by dependence of SERS of graphene on excitation wavelength that 633 nm laser corresponding to the surface plasmon band in UV/Vis spectrum (Figure 2) showed larger SERS enhancement factor. The CM mechanism is proposed from difference of SERS enhancement factors between single-layer and tri-layer which may be due to stronger interaction via charge transfer in single-layer than in few-layer. The CM mechanism has been recently reported by the Liu group.[13]

Acknowledgements
This work was supported by the WCU (World Class University) program through the National Research Foundation funded by MEST of Korea (R31-2008-000-20012-0) and by KICOS through MEST in 2009 (No. 2009-00591).

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