JOURNAL OF CHEMICAL PHYSICS

VOLUME 120, NUMBER 24

22 JUNE 2004

Stokesanti-Stokes anomalies under surface enhanced Raman scattering conditions

R. C. Maher and L. F. Cohena)
The Blackett Laboratory, Imperial College London, SW7 2BW London, United Kingdom

P. Etchegoinb)
The McDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical and Physical Sciences, Victoria University of Wellington, Wellington, New Zealand

H. J. N. Hartigan, R. J. C. Brown, and M. J. T. Milton

National Physical Laboratory, TW11 OLW Teddington, Middlesex, United Kingdom

Received 25 November 2003; accepted 22 March 2004 The possibility of achieving anti-Stokes stimulation and/or pumping under surface enhanced Raman scattering conditions has been the source of intense controversies in the literature. With the aim of clarifying some of the aspects of this problem, we study theoretically and experimentally the situation in a model system which highlights some of the difculties in the interpretation of the data. We show that many of the assumptions often presumed in the literature need to be assessed with care in each case. Through careful experiments we show, in particular, that the anti-Stokes/Stokes ratio for a specic mode in the same sample can depend on the chosen laser wavelength. This latter effect is a manifestation of the inuence of the internal plasmon resonances hot spots in the result. Different possibilities and further research directions are highlighted and discussed. 2004 American Institute of Physics. DOI: 10.1063/1.1739398

I. INTRODUCTION AND OVERVIEW

Surface enhanced Raman scattering SERS 1,2 is a powerful tool for spectroscopy with a myriad of applications in problems of physical chemistry3,4 and the life sciences.5,6 However, many basic aspects of SERS are still under intense discussion. The purpose of this paper is to shed some light into one of these controversial topics in SERS, namely, Stokes/anti-Stokes stimulation and its possible applications. Specically we shall show that the anti-Stokes/Stokes ratio for a given SERS active medium can depend on laser wavelength and a variety of experimental conditions that need to be controlled before any interpretation can be achieved. We give here a detailed account of previous works for the sake of completeness and highlight different opposing views. Kneipp and co-workers7 were the rst to point out that the extremely large enhancements seen in SERS can result in vibrational population pumping and, accordingly, in I as /I s ) above the an increased anti-Stokes/Stokes ratio ( exp( /kBT); where v is the expected thermal value v frequency of the Raman vibration and I as , I s , the antiStokes aS and Stokes S intensities, respectively. Further evidence of aS pumping in carbon nanotubes, was provided by the same group subsequently.8,9 The interest in SERS pumping is not only the fundamental aspects of nonlinear optics, but also its potential use in metrology. Vibrational pumping by a Raman process is a form of stimulated scattering; we shall use hereafter stimulation and pumping as synonyms in this context. Under normal conditions, I s is
a b

Electronic mail: l.cohen@imperial.ac.uk Electronic mail: pablo.etchegoin@vuw.ac.nz

proportional to i the laser intensity (I L ), ii the Raman cross section s , and iii the number of scattering centers n. The same holds for I as , with as instead of s , except for the added Boltzmann factor. Hence, by assuming that s and as are the same an assumption which is not valid for SERS I as /I s brings back no informain many cases , the ratio tion on . Conversely, if SaS pumping is achieved, nonlinear terms are generated on the aS intensity. The lowest order close to the threshold of stimulation introduces a quadratic term in 7 which does not factor out now in . Thus, by measuring close to the threshold it is possible, in principle, to obtain a value for and, from here, the SERS enhancement factor can be estimated which is desirable for quantication. Signals in SERS active media have a strong contribution from hot spots;10 there is now considerable evidence of their importance in SERS and we have recently surveyed some of their salient properties.11 Nevertheless, the problem of transforming the effect of hot spots into quantitatively meaningful data is very highly intractable. The difculty in characterizing the complex topologies that produce them and the fact that they are relatively rare events is the main reason. In a colloidal uid, for example, there will be occasionally a geometrical arrangement that produces a hot spot, but the vast majority of congurations will produce a moderate or even negligible enhancement in comparison. However, these rare events contribute with the highest by several orders of magnitude intensities and carry the heaviest weight in the outcome of the result. The quantitative link between the result and the microscopic origin depends, accordingly, on subtle details of the statistics of very rare events; a very difcult undertaking, in general.
2004 American Institute of Physics

0021-9606/2004/120(24)/11746/8/$22.00

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J. Chem. Phys., Vol. 120, No. 24, 22 June 2004

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The stimulation process described originally by Kneipp et al.7 has several anomalies which have not been fully appreciated yet. The most salient of them is the fact that a normal stimulated Raman process in molecules displays a very sharp exponential threshold above which a signicant depletion of the Stokes eld is observed. One would naively infer that this should also happen under SERS conditions, due to the additional boost provided by hot spots. This is not the case, however. The Stokes intensity behaves linearly with power with no signicant depletion over a wide range below and above the threshold, while the anti-Stokes eld has a quadratic dependence in the same range much weaker than a normal threshold. Despite the much more imperfect conditions of phase matching affecting the SaS pumping due to the intrinsic random nature of SERS active media this result can also be interpreted in terms of the existence of hot spots. The aS signal increases because it has a substantial contribution from hot spots, but these are a minority with respect to all the molecules where the Stokes process is being generated and no substantial depletion on the Stokes side is seen accordingly. The counterviews on the existence of SERS pumping are varied; Moskovits et al.12,13 have argued against this interpretation and have also cast serious doubts on the claimed order of magnitude of the enhancements. They argue13 that there is no known physical mechanism capable of achieving the 1014 1015 enhancement claimed in many reports; it would imply electric eld intensities that would completely destroy the chemical identity of the SERS probes. Frequency changes and activation of new modes are sometimes seen under SERS conditions, but never to an extent easily attributed to a radical change in chemical structure. Moreover, they conducted several experiments where no evidence of stimulation could be observed, casting some doubt on the real origin of the stimulation. Finally, they argued that anomalies in aS/S ratios could be attributed to differences between S and aS and/or the presence of hidden resonances in the system.12,13 Some of these conclusions have been partly supported in one of our previous papers.11 The main conclusion we would like to carry onto the next sections is that while some authors nd experimental hints for the existence of stimulation, others seem to nd no evidence whatsoever and the issue of stimulation under SERS conditions is to date far from being resolved.
II. BASIC ASPECTS OF SERS STIMULATION

FIG. 1. Schematic view of the effect of stimulation on the anti-Stokes/ Stokes ratio. At small incident laser power, should correspond to the thermal value at room temperature RT , indicated by a dashed line. In the prestimulation region, may start rising above the value at RT if anti-Stokes pumping becomes a considerable fraction of the thermal population. If other nonlinear optical effects are not present, a threshold for stimulation followed by a rapid exponential increase and subsequent saturation could be reached. In this picture, the average contribution of SERS and hot spots results in a change of the initial working point along this curve. Two schematic examples are shown: L 1 is a laser that does prot as well as L 2 does from the presence of hot spots and amplication. This results in different scaling factors along the stimulation curve, for the presence of hot spots is equivalent to an increase in the effective power density. See the text for further details.

We start the discussion with a Gedanken experiment: We obtain the aS/S ratio of a mode in a normal not SERS medium and this corresponds to the Boltzmann factor at temperature T. It will be independent of the laser intensity (I laser) at low powers, provided that laser heating or other indirect effects are not generated. Assume also that we have an arbitrarily large supply of I laser . If increased continuously, we might reach a situation in which some prestimulation occurs. The increase in the phonon population on the S side starts to be seen on the aS intensity above the thermal population. Hence, may rise above the thermal value typically linearly14 in this prethreshold region. At some point, the stimulation threshold can be reached, followed typically by a

rapid increase and saturation. The exact extent of the prestimulation region and the threshold depend on the characteristics of the sample, Raman cross sections, the gain, the presence of losses and/or feedback, phase matching conditions, etc. Stimulation is never actually achieved in this way under CW illumination, for thresholds would be so prohibitively high that other nonlinear effects from bleaching to dielectric breakdown will take place well before. The situation is schematically depicted in Fig. 1. Let us now add the contribution of SERS. Consider two different lasers L 1 and L 2 which prot from resonances with hot spots by very different extents. If L 1 does not prot very effectively from hot spots, the average enhancement factor will be small. On the contrary, if L 2 interacts very strongly with them and resonates with the colloidcolloid surface plasmon interactions,11 the average enhancement factor can be very high. This is effectively like having a scaling factor between the two lasers; for the same input power they will both operate in two completely different regions of the curve in Fig. 1. This implies that may display very different values in the region of the measurement, and may or may not show a more evident power dependence. The real picture derived from this Gedanken experiment is, in fact, much more complex. To start with, the Stokes/ anti-Stokes ratio has a weak laser-wavelength dependence if we add the 4 dependence of the scattering cross section.

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It becomes more signicant for modes with the largest Raman shifts. Even assuming S and aS to be the same, the correct expression for should be
laser laser
v v

4 4

exp

/k B T .

prefactor is normally neglected by assuming v . Under stimulation conditions with different lasers laser separated by several eV, however, the prefactor should be formally included for it produces a different limiting value for when I laser0. For the 633 nm line of a HeNe laser, for example, is larger than that for the green 514 nm Ar ion laser line by an amount which depends on the phonon energy under consideration. Last, but not least, issues of scattering and absorption should be formally included in the analysis of the experimental results. Jackson et al.15 were the rst to stress the importance of reabsorption in the interpretation of the SERS intensities in colloidal Au-nanoshell uids. One might argue that , being a ratio, is less affected by this problem, but the absorption and scattering coefcients can be substantially different at the aS and S frequencies. For a typical active mode in organic compounds with a Raman shift of 1500 cm 1, there is a difference of 0.37 eV between the aS and S frequencies. The difference between absorption and scattering at both frequencies can be substantial and dependent on the proximity of intrinsic or collective plasmon resonances. In this section, accordingly, we listed several of the potential factors affecting the measurements of . We believe that measurements of without addressing the issue of internal resonances can lead to completely different results depending on experimental conditions. It is the purpose of the next section to show this explicitly with carefully prepared experiments. The

FIG. 2. Calibration of the response of the system on a log scale for a 633 nm HeNe laser, using -carotene and b 514 nm laser, using the dye TPPS4 . The results are compared with the theoretical s from 1 . The full aS/S spectra of both compounds are shown in the insets. This method eliminates any possible systematic error in the numbers obtained for coming from the intrinsic response of the system.

III. EXPERIMENTS A. Experimental method and samples

SERS experiments have been performed on Ag-colloids prepared by citrate reduction as described by Lee and Meisel.16 The colloids produced from this preparation technique have a size distribution with a mean diameter of 50 nm and an estimated particle concentration of 35 pM. Immediately before use, colloids were concentrated by centrifugation to remove excess liquid and enabling a tenfold increase in concentration. Samples were prepared by mixing 16 mM KCl activating agent and 10 5 M Rhodamine 6G RH6G with the colloids in the ratio 1:1:2, respectively. The colloid is concentrated to boost the presence of hot spots and reduce the integration times on the aS side. Spectra were gained by a Renishaw confocal Raman microscope with a X60 immersion objective index matched to water . Experiments in a colloidal uid have the specic purpose of avoiding photobleaching and local heating problems in successive measurements during the time span of the experiment; the sample is being constantly renewed by diffusion. Due to the large dye concentration, scattering volume, and integration

times involved, each measurement represents individually a spatial average over colloidal distributions geometries ; i.e., a statistical property of the sample. Data were recorded without polarization analysis with integration times in the range 0.1 60 s, and with 10 to 1000 accumulations, depending on incident power. Both aS and S scattering were measured in the same run under identical experimental conditions until a reasonable signal to noise ratio is achieved on the aS side. We used both the 633 nm line of a HeNe laser and the 514 nm line of a Ar laser as excitations in all experiments. The estimated power densities at full power for the 633 nm 514 nm laser under perfect focusing conditions without the colloid were 2 10 12 W/m2 3 10 12 W/m2 . We prefer to plot our data in terms of the incident power because the focusing area is poorly dened in a highly dispersive medium like a colloidal fuild. The intensity was varied by either a calibrated lter wheel, or the regulation of the laser power supply together with a calibrated photodiode. To obtain physically meaningful values for the response of the system at different wavelengths should always be a matter of concern. We calibrated our system using aS/S ratios of normal nonenhanced signals from known organic compounds with many Raman active lines. We used the dye TPPS4 and -carotene to calibrate the response around the 514 and 633 nm ranges, respectively; was then calculated for all visible peaks and compared to the theoretical values at room temperature. In this manner, calibration curves which compensate any possible response of i the collecting optics, ii the notch lter, iii the grating, and iv the CCD were obtained and are shown in Fig. 2. General overviews of the S and aS spectra for both substances are shown in the insets. Calibration procedures are most crucial for modes with large Raman shifts, for the difference between S and aS frequencies can be large enough to produce a measurable change in

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J. Chem. Phys., Vol. 120, No. 24, 22 June 2004

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FIG. 3. Experimental anti-Stokes/Stokes ratios for the 610 cm 1 peak of RH6G as a function of incident power for both 633 and 514 nm lasers. The theoretical constant values expected at room temperature for both lasers are shown as thick horizontal lines. The ratio obtained for the 514 nm laser is consistently lower and shows a very weak laser power dependence, unlike the ratios for the 633 nm laser which are always higher by a factor of 10 and they consistently show a dependence on incident power. These results highlight how different the outcome of can be by changing the laser frequency for the same sample and under identical experimental conditions. The interpretation of the difference between the two results can only be achieved if the coupling of the lasers to internal resonances is taken into account. See the text for further details.

FIG. 4. Raw data on the Stokes left and anti-Stokes right sides for both 633 light gray and 514 nm dark gray lasers at the same incident power 0.5 mW . Note the change in scales for both cases. We only show the region around the 610 cm 1 Raman active mode of RH6G on both sides. A much larger anti-Stokes/Stokes ratio for the 633 nm line is evident from the data. In addition, the 633 nm ratios have the power dependence displayed in Fig. 3, while the 515 nm data for remains approximately constant throughout.

detectivity between the two. The data in Fig. 2 show that only minor corrections are required from the spectral response of our system. None of the anomalies we are going to report can be ascribed to a systematic error in the detection and/or normalization. SERS measurements were done at several different incident powers for both lasers. S and aS Raman peaks were tted with standard Voigt functions PeakFit with subtracted backgrounds to obtain .
B. Results

We concentrate rst on the 610 cm 1 Raman active mode of RH6G. The reason is twofold: i it is the most intense mode closer to the laser and, therefore, the correction for the response of the system is small and ii the aS side is substantially populated at room T producing data of extremely good signal to noise ratio in very short times. The experiments for the two lasers are done one after the other in the very same sample within a period of 3 4 h and, therefore, without risk of degradation or change in the experimental conditions. The data for this mode provides the best possible assessment on whether other effects are inuencing the results. Figure 3 shows the results for for both lasers. The thick horizontal lines represent the power independent theoretical values of at room T including the 4 correction in 1 . Several anomalies are immediately obvious. The values of for the 514 nm laser are mostly independent of the incident power, while the 633 nm line shows some variation. In addition, values for 514 nm are roughly an order of magnitude smaller that those for the 633 nm line and suppressed with respect to the expected theoretical value. The opposite holds

for the 633 nm line. As far as we are aware, all possible systematic errors have been eliminated from the experimental procedure; the difference in s has a physical meaning. These results are reproducible over many different batches of samples and even a different micro-Raman spectrometer. The importance of these results, and one of the main points of our paper, is the fact that even in a carefully prepared experiment like this the values of for a given mode and its laser power dependence can be very different depending on the experimental conditions, the laser wavelength, and the nature of the internal plasmon resonances. A more visual representation of the data in Fig. 3 can be obtained by looking directly at the raw data in both the Stokes and anti-Stokes sides for both lasers. We show an example in Fig. 4 for the 610 cm 1 mode at low incident powers 0.5 mW . Figure 4 shows precisely how different the ratios can be depending on the laser wavelength. The explanation of the data in Figs. 3 and 4 involves several aspects: i imbalance between the aS and S cross sections due to the presence of plasmon resonances in the colloids one of the issues raised by Moskovits et al.12,13 , ii hot-spot protability of the different lasers needed to explain why the 633 nm laser data has a power dependence unlike the 514 nm , and iii residual absorption produced by the colloids. We explain in what follows why the three ingredients are required. The surface plasmon absorption of our colloids increases very slowly from the near infrared NIR region and peaks at 400 nm in the near uv.4 Even though collective resonances can contribute with absorption features below the main single-colloid plasmon resonance, the overall absorption spectrum is still dominated by the latter, as can be seen by a simple absorption spectrum in the colloidal uid.4 The asymmetry in the absorption between the aS and S sides is more pronounced for the 514 nm than for the 633 nm laser lines. This can explain why the experimental values for appear

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FIG. 5. Power dependence of for the 1510 cm 1 Raman mode of RH6G under 633 nm illumination. A feature resembling a threshold of stimulation can always be seen for this mode, unlike the 610 cm 1 in Fig. 3. As in Fig. 3 the power independent theoretical value of the ratio is shown as a horizontal line. See the text for further details.

suppressed for the 514 nm line, as compared to the 633 nm. But absorption works only in one direction; it cannot explain why for the 633 nm laser is higher than the theoretical values. The answer to this can only come from different intrinsic asymmetries in the cross sections for the two lasers, produced by the fact that the molecule is immersed in a SERS active medium. We are going to substantiate this aspect qualitatively in the next section. Finally, it is the issue of the 633 nm laser showing some power dependence while the 514 nm remains relatively at throughout. This can only be explained if the average enhancement factors for the two lasers are different. Direct laser resonances with hot spots must happen more often and be more intense for the 633 nm laser to boost into a region where some power dependence starts to be seen; this is precisely the difference between L 1 and L 2 in Fig. 1, in which one is pushed further up into the prestimulation region by proting more effectively from the average enhancement factors. It is quite clear from the general knowledge of interacting plasmons in complex metallic environments that the 633 nm laser will interact with different types of resonances than the 514 nm laser. The exact nature of the resonances in a colloidal uid, however, cannot be directly ascertained through the SERS signals. This will be the subject of the next section. Furthermore, an additional question arises at this stage: if the 610 cm 1 shows some evidence of a power dependence associated with prestimulation , is it actually possible to see stimulation in other modes? Raman stimulation is a survival of the ttest effect in the sense that many modes may show prestimulation but once a threshold is achieved for one of them it will be that mode that survives. This happens for the Raman modes with the largest intrinsic s. It is actually the combination of a larger cross section and the specic Raman shift of a mode that denes what its intrinsic amplication will be. Figure 5 shows the power dependence of the 1510 cm 1 Raman mode of RH6G, which is one of the

most intense in the normal spectrum. Measuring the values of for this mode is more challenging for two main reasons: i the aS signals are very weak and for small incident powers integration times can be very large up to 8 hours , and ii over periods of many hours special care must be taken with the long term stability of the colloid which is, in turn, a function of the KCl content. By taking care of all these details, however, we found that the 1510 cm 1 does show a power dependence with a characteristic threshold compare with the qualitative picture in Fig. 1 . We found also that this kink can be shifted depending on the KCl content, but systematic studies have not been performed yet. This could be in agreement though with the idea that KCl controls the average intercolloid distances and, therefore, the density of hot spots. The data in Fig. 5 resembles a standard picture of Raman stimulation threshold in a lossy medium, a situation expected from the intrinsic residual absorption of the colloids. This result is again reproducible over many different batches of colloids, even though the position of threshold itself can change slightly from batch to batch. To nish this section, we draw back to the original question of whether SERS stimulation can exist or not. The results from our experiments suggest that a stimulation or prestimulation prole typical of a lossy medium can be seen under reproducible experimental conditions, but the same sample can produce a negative result for a different laser in the same incident intensity range. This is, in fact, a manifestation of how important the role of internal resonances are in the denition of the outcome of a specic experiment, and we believe it to be partly the reason for the many discrepancies in the literature. In the next section we justify some of the afrmations regarding the statistics of hot spots given above.

IV. NUMERICAL SIMULATIONS

We show in this section that many of the ingredients needed to explain the SERS aS/S ratios can be understood qualitatively with a simple model. Theoretical calculations of electromagnetic SERS enhancements can be rather involved and require simplications in ways that are problem specic. The discrete dipole approximation DDA 17 has been used within the framework of SERS to study the absorption, scattering, and near/far eld distributions. SERS enhancements for simple colloid congurations like dimers18 or interactions with extended surfaces1921 taking also into account multipolar contributions have been calculated before. Many of these studies reveal that the dipole approximation may be used safely in a variety of problems,18 unless the colloid density is extremely high. We have reviewed recently the basic aspects of the DDA and, accordingly, we only present here a very schematic outline, leaving the details to the original papers.17,2224 A given structure is divided into small cells with characteristic dimension d (d ; wavelength of the light . The polarization at the ith cell P i is Pi
i i E tot ,

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J. Chem. Phys., Vol. 120, No. 24, 22 June 2004

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where i is the local polarizability and E tot the total electric eld at site i. The total electric eld is
i i i E tot E inc E dip , i where E dip is the eld produced by all other dipoles j i the ith cell, and E inc is the incident eld, i E inc E 0 e i k r i t

3 i at

with k ( 2 / ), , and E 0 the wave vector, frequency, and amplitude of the incident light, respectively. r i is the coordinate of the ith cell. The electric eld at cell i is24
i E dip

Ai j P j ,

with e ikr i j 2 k rij Ai j P j r 3j i rij Pj 1 ikr i j r 2j i , 6

r 2j P j 3r i j r i j P j i

where r i j r i j (i j) is the distance between cells i and j, respectively, and k k . The solution of the 3N 3N linear inhomogeneous equations i 1 P i A i j P j E 0e i
k r i

gives the answer to the problem. All the elds have a e i t time dependence. Several important physical quantities can be obtained i from E tot . The normal enhancement factor G for an aS or S process is typically dened as25 G aS,S M where the M E tot
laser

M /E inc

laser

sign holds for the aS S process, and

2

I tot

/I inc

If there is no polarizable medium then G 1, but G can be either or 1 depending on whether the eld is locally enhanced or suppressed. A measure of the asymmetry between the aS and S signals produced by the different electromagnetic couplings of a specic site at laser v is the ratio R G aS /G S , which affects directly ( R aS / S ) and factors out automatically the contribution from the laser itself. Even ignoring the difference between aS and S , R will be a statistical measure of the imbalance produced between the emission at the aS or S frequency in the Raman process by immersing the molecule in a SERS active medium. The comparison between two different Rs at two different laser frequencies is what we wish to gain from the calculation. Besides the asymmetry, which plays the role of an overall offset for , we are interested in the statistics of the M factors in 8 at the laser frequency itself, for two different lasers. The statistics of the factor M ( ) I tot( )/Iinc( ) contains the information on how frequent and intense hot

spots are for a given laser at a specic point. The comparison between two lasers provides, accordingly, information on which one prots and boosts more effectively the intensity further up into the prestimulation or stimulation region in Fig. 1 and, in this manner, which laser is more likely to exhibit a power dependence in . The asymmetry R at one specic point must be weighted by M ( laser) at that place. The aS and S elds may display a large asymmetry at some point but this will be irrelevant to the nal result if the laser cannot reach that place very effectively. The local enhancement of the laser M provides, accordingly, the appropriate weighting factor for the different asymmetries. We study then two quantities i the local enhancement at the laser frequency M ( laser) I tot( laser)/I inc( laser), and the average weighted asymmetry 1/N N M i ( laser)G aS /G S , where i runs over N different rani domly generated colloid geometries. The calculation proceeds as follows: We take a xed volume of 200 200 200 nm3 and distribute inside a given number of colloids with diameter 20 nm at random. The number of colloids xes the concentration; we work with relatively low concentrations (N 40) to ensure the validity of the dipole approximation.18 Each colloid becomes one cell of the DDA method and it is assigned a scalar polarizability taken from the optical properties of Ag tabulated in the literature.26 We calculate then the electromagnetic properties of the cluster and evaluate the M factors at laser and laser v in the center of the box observation point , where the probe molecule is assumed to be. We take v 1000 cm 1 as a representative value for organic compounds. By repeating this calculation over very many different clusters (2 104 to 1 105 ) we obtain a statistical view into the coupling of an arbitrary place to the main frequencies of the problem. The laser is assumed to impinge the clusters always from the same direction and with a xed polarization. All relevant physical quantities can be obtained directly from the M factors at different frequencies. Direct overlap inside a colloid of the observation point is explicitly avoided. In Fig. 6 we show M ( laser) I tot( laser)/I inc( laser) at the observation point for 2 104 different clusters at both laser 633 and 514 nm. A series of spikes can be observed for certain clusters. These are hot-spot occurrences at the observation point. An example of the internal intensity distribution for one of the spikes at 633 nm with a hot spot close to the center of the cluster is shown in Fig. 6 c . Note that the scale of intensities is logarithmic and that this particular cluster has more than one hot spot at least three inside. A striking difference in the statistics can be seen with a naked eye: hot spots occur more often and are more intense in general for laser 633 nm. 27 A simple quantication of this effect by calculating the average of M ( laser) over 105 clusters shows that M (633 nm) 4M (514 nm), which is equivalent to say that the intensity at 633 nm is boosted by 300% with respect to an equivalent intensity at 514 nm by proting from plasmonplasmon interactions inside the cluster. Interestingly, our simulations show that if the density of the colloids keeps increasing, this latter property is reverted. The reason for this is that in very dense geometries of colloids, plasmonplasmon interactions become more delocalized,

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shows trends in the right direction to explain the data, another reminder of how important it is to address the issue of internal resonances in SERS active media to link the experimental values with microscopic physical magnitudes. Further work on theoretical aspects to gain some insight into the essential details needed for a microscopic understanding of the phenomenology behind the SERS aS/S-ratio problem is in progress and will be published elsewhere.28
V. DISCUSSION AND CONCLUSIONS

FIG. 6. Enhancement factors M ( laser) for 2 104 different random geometries at a specic point in the middle of the clusters for 633 a and 514 nm b . The spikes in M are hot spots at the laser frequency; they occur more often and are more intense for the 633 than for the 514 nm laser at this colloid concentration. This can be interpreted as the 633 nm laser proting from local plasmon resonances which are redshifted, very localized, and in resonance with the laser frequency Ref. 11 . The different statistics and intensities for both lasers can explain why the red 633 nm line is boosted to a prestimulation region unlike the 514 nm line in the same incident power range. In c we give a visual representation of a cluster producing one of the spikes in a . The intensity distribution along three different mutually orthogonal planes cutting the cluster through the middle can also be seen. The intensity scale is logarithmic, with a difference of seven orders of magnitude between white and black. Note the presence of an intense hot spot seen in the intensity map close to the middle of the cluster. This specic cluster has at least three hot spots inside. See the text for further details.

and the advantage of a highly localized redshifted resonance, as described elsewhere,11 is lost. There is, accordingly, a crossover in density of this effect which is currently under investigation. The different average enhancements between the two lasers is one of the key ingredients to explain why one may show signatures of prestimulation while the other remains constant in the same intensity range, and this simple model shows very clearly how that difference can arise from the statistics of hot spots. On the issue of the asymmetry, the average of 1/N N M i ( laser)G aS /G S over the same 105 clusi ters produces an asymmetry in from the different coupling of the aS and S elds which is 31% larger for the 633 nm laser. In fact, the experimental value is the ratio of the averages of G aS and G S , rather than the average of the ratio. This second quantity gives an asymmetry of 22.3% instead; this is because the average of the ratio tends to weight the cases with larger asymmetries in a slightly more favorable manner. These numbers for M and the asymmetry are smaller compared to what is observed experimentally. Admittedly, part of the problem relies on the simplicity of the model and the approximations involved, but in the case of the asymmetry the comparison becomes more favorable when the combined effect of absorption is also included. All in all, irrespective of the exact quantitative agreement, this model

In a way, our observations here bring closer several apparently conicting claims by many groups. Here we showed a clean and reproducible SERS experiment in which either the values of can be different, or hints of stimulation can be seen, depending on how the experiment is carried out. Our paper does not solve the outstanding issue of the inuence of rare events the hot spots on the quantitative aspects of SERS, but it does show that anomalous Stokes/anti-Stokes ratios of different types, and even evidence of stimulation or prestimulation, can exist depending on laser wavelength. We have, in addition, explored the underlying concepts needed to explain the observed phenomenology. The laser frequency, in particular, plays a decisive role in its coupling with individual or collective plasmon resonances to determine the experimental conditions, the type of hot spots that will be activated, and, ultimately, the inuence on the quantitative and qualitative aspects of the nal result. Estimates are bound to be qualitative at this level of modelling due to the neglect of absorption effects and their intrinsic approximations in the discrete dipole approximation. The main lesson we would like to highlight from our results here is that even in a clean and reproducible SERS experiment only the combination of effects like (i) absorption, (ii) the boosting effect of internal resonances at different wavelengths through hot spots, (iii) the intrinsic dependences of a normal Raman effect, and (iv) internal asymmetries between the coupling of the aS and S elds, begins to explain very basic experimental facts of the aS/S ratios. We believe that avoiding the issue of what the internal resonances are for a specic SERS active medium can lead to unrealistic quantitative results for cross sections and other microscopic parameters, as well as wrong conclusions on the existence or absence of stimulation. We found also that modes with higher Raman cross sections do show a power dependence with a prole typical of a stimulation threshold in a lossy medium, as in Fig. 5. The effect of laser wavelength on this threshold is being extensively studied at the moment.28 The issue of SERS quantication for metrology and the very nature of the hot spots are far from being resolved at this stage, but we hope our contribution here provides some progress in understanding of the causes and the limitations of the method in an area of intense scientic debate and promises for potential applications.
ACKNOWLEDGMENTS

Two of the authors P.E. and L.F.C. acknowledge partial support for this work by the Engineering and Physical Sci-

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J. Chem. Phys., Vol. 120, No. 24, 22 June 2004

Anomalies in surface enhanced Raman scattering

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ences Research Council EPSRC of the UK under Grant No. GR/R28775. The rst author R.C.M. acknowledges partial support from the National Physical Laboratory NPL . Thanks are due to A. McRoberts UCL for providing the TPPS4 dye for calibration.
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