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Surface-Enhanced Raman Scattering on a Chemically Etched ZnSe Surface

Syed K. Islam, Maria Tamargo, Richard Moug, and John R. Lombardi*
Department of Chemistry and Center for Exploitation of Nanostructures in Sensor and Energy Systems (CENSES), The City College of New York, 160 Convent Avenue, New York 10031, United States ABSTRACT: We report the observation of surface-enhanced Raman scattering (SERS) from a chemically etched ZnSe surface using 4-mercaptopyridine (4-MPy) as probe molecules. A thin lm of ZnSe is grown by molecular beam epitaxy (MBE) and then etched using a strong acid. Protrusions of hemiellipsoidal nanoparticles are observed on the surface. Using the results of the Mie theory, we controlled the size of the nanoparticles to overlap signicantly with maximum eciency of near-eld plasmon enhancement. In the Raman spectrum, we observe large enhancements of the a1, b1, and b2 modes when 4-MPy molecules are adsorbed on the surface using a 514.5 nm laser for excitation, indicating strong charge-transfer contributions. An enhancement factor of (2 106) is observed comparable to that of silver nanoparticles. We believe this large enhancement factor is an indication of the coupled contribution of several resonances. We propose that some combination of surface plasmon, charge transfer, and band-gap resonances is most likely the contributing factor in the observed Raman signal enhancement because all three of these resonances lie close to the excitation wavelength.

INTRODUCTION The proximity of a metal nanoparticle to a molecule has been found to considerably enhance the Raman intensity1 by factors in the range of 106 to 1012. This phenomenon, known as surface-enhanced Raman spectroscopy (SERS), has been shown to be caused by several resonances in the molecule metal system, including the surface plasmon of the metal conduction band, various molecular resonances, as well as charge-transfer resonance between the molecule and nanoparticle.2 Recently, a considerable amount of attention has been focused on extending SERS to semiconductor substrates. In most semiconductor nanoparticles, the surface plasmon resonance due to the conduction band lies typically in the infrared. This is because of a very low electron density in the conduction band. Thus any enhancement of Raman signal is usually attributed solely to charge transfer, and enhancement factors somewhat lower than those observed on metals have been obtained. SERS has been reported on ZnO, ZnS, PbS, CdS, TiO2, CdSe/ZnBeSe, CdTe, Se nanowires, and Ge nanotubes using various molecules as probes.310 The reported enhancement factor in these semiconductors ranges between 102 and 105. However, charge transfer is not the only factor attributed to SERS in semiconductors; in addition to plasmons originating in the conduction band, the valence band (VB) can also support plasmons, and these are usually observed in the ultraviolet. Such observations are discussed in detail by Pines.11,12 The electron density of valence electrons in solids is typically around 1022 to 1024 cm3, so that the resulting bulk plasmon excitation energy is expected to be found in the ultraviolet. These resonances can be shifted to lower energies by varying the size and shape of semiconductor nanoparticles. Hayashi et al. showed dependence eciency of near-eld enhancement (Qnf) on the size of spherical GaP particles.13 Using Mie
2013 American Chemical Society

scattering theory, they found that particles in the range of 100 140 nm diameter could support a plasmon resonance in the visible region of the spectrum (514.5 nm). The authors indicated an enhancement factor of as much as 106 using copper phthalocyanine as a probe molecule. Quagliano et al. reported SERS on etched GaAs surface using pyridine molecules due to EM enhancement.14 Recently, SERS on small Cu2O nanoparticles and on 3D TiO2 nanowires have been shown.15,16 In both of these investigations, SERS enhancement factors of 105 to 106 are reported. The observed SERS in both of these cases is proposed to be caused by a combination of charge-transfer resonance and a surface plasmon resonance. In addition, a resonance in the exciton band gap spectrum has been implicated in the enhancement of molecules on MBE-grown CdSe/ZnBeSe nanoparticles.8 In this work, we report on SERS from 4-mercaptopyridine (4-MPy) molecules adsorbed on an etched zinc selenide (ZnSe) surface grown on top of a gallium arsenide (GaAs) substrate using molecular beam epitaxy (MBE). By using the Mie theory, we calculate the ZnSe particle size corresponding to the maximum eciency of near-eld enhancement Qnf. We utilize chemical etching to control the ZnSe particle size to approximately match that of the calculated value. Using laser excitation at 514.5 nm, close to the band gap of bulk ZnSe, we found a large enhancement factor (2 106). By analyzing the observed Raman spectra, we propose that in addition to charge transfer both band gap and surface plasmon resonances are most likely contributing factors in the observed Raman signal enhancement.
Received: July 31, 2013 Revised: October 6, 2013 Published: October 7, 2013
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II. METHODS Chemicals. 4-Mercaptopyridine (96%) was purchased from Acros Organics and used without further purication. Acetone was purchased from Fisher Scientic. Experimental Method. (a). Molecular Beam Epitaxial Growth of ZnSe Surface on GaAs Substrate. All of the crystalline layers were grown from elemental solid sources by an MBE system featuring two Riber 2300 growth chambers. One of the chambers is devoted to IIIV materials growth, specically GaAs in this work, and the other is devoted to the growth of IIVI materials, specically ZnSe in this work. Epiready (0 0 1) GaAs semi-insulating substrate mounted by indium to a molybdenum block was rst introduced in the III V MBE chamber, where it was heated to remove its native oxide layer under arsenic ux. The oxide desorption of the substrate was monitored by reection high-energy electron diraction. After the oxide layer was removed, a 100 nm GaAs buer layer was grown under As-rich conditions exhibiting a streaky (2 4) surface reconstruction. After the GaAs buer layer was grown, the GaAs samples were transferred into the IIVI chamber via transfer track modules in an ultrahigh vacuum. To improve the IIIV to IIVI material interface, exposure to a Zn ux for a period of 30 s, followed by a 50 growth of ZnSe was performed, all of which was done at 200 C, which is 100 C lower than the optimal IIVI materials growth. After this low-temperature buer of ZnSe, the substrate temperature was increased to 300 C for the remainder of the ZnSe growth. The thickness of the ZnSe layer was 1 m and was grown under Se-rich growth conditions. The RHEED pattern exhibited a streaky Se-terminated (2 1) surface reconstruction during the entire ZnSe growth. (b). Atomic Force Micrography. The ZnSe surface was etched using concentrated sulfuric acid (H2SO4) for 1, 2, and 3 min. At the end of the etching period, the surface was repeatedly washed for several minutes with water and then dried at room temperature. Atomic force micrograph (AFM) images were acquired using a Nanoscope III (Digital Instruments) apparatus operated in the air and at room temperature. Silicon-sharpened tips with a force constant of 0.58 N/m (purchased from Digital Instruments) and a resonance of 260 kHz were used in noncontact mode for the AFM images. At least ve images were acquired for each sample at various locations. Images were recorded in the range of 5 5 m2 area and of 1 1 m2 area with a 500 500 pixel resolution and a scan rate of 1 m/s. The dimensions of the nanostructures were measured using Nanoscope 6 image processing software. (c). Raman Spectroscopy. A solution of 4-MPy was prepared by dissolving powder 4-MPy in pure acetone at 1 mM concentration. 4-MPy molecules were adsorbed on the etched ZnSe surface by immersing the clean surface in the sample overnight and then allowing the solvent to evaporate in the air at room temperature. The surface was then rinsed with acetone for a few minutes to remove the excess molecules. The Raman spectra of 4-MPy were investigated using Spectra Pro 2750 (0.75 m triple grating monochromator 1200 gratings/ spectrograph) at the excitation wavelength of 514.5 nm obtained from an Ar+ laser (Spectra Physics). The laser was focused on the sample by using a 100 objective lens attached to a confocal microscope, and the power of the laser on stage was 0.56 mW. The laser spot size was 2 m, and the slit width was 20 m. The Raman measurement of the sample was taken
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with ve accumulations over 10 s of acquisition. To ensure that the obtained spectra were comparable, the settings, including laser power and exposure time, were all kept constant. The silicon line at 520 nm was used to calibrate the observed wavenumbers. Mie Scattering Calculations. A strong radial dependence was originally exploited by Mie17 in determining the scattering eciencies of metallic spheres. For semiconductor nanoparticles, Mie scattering can also take place, and the near-eld surface plasmon resonances are strongly size- as well as wavelength-dependent. In this regard, we examine the derivation of Mie scattering eciencies due to Messinger et al.18 as well as the MATLAB program written by Mat zler.19 The scattering eciency (Q) is the ratio of the power of the scattered light to that of the incident light. A molecule adsorbed on the surface of a sphere feels an electric eld in the near-eld limit. In the near-eld limit, the incident plane wave is distorted to satisfy the boundary conditions of the surface of the sphere. For the neareld scattering eciency (QNF), it is shown to be
(2) 2 (2) 2 Q NF = 2 {|an|2 [(n + 1)|hn 1(ka)| + n |hn + 1(ka)| ] n=1 (2) + (2n + 1)|bn|2 |hn (ka)|2 }

(1)

where an and bn are the Mie coecients and hn(2) are the Han kel functions of the second kind. The parameter a is the radius of the sphere and k (= 2/) is the wavenumber of the exciting light. The Mie scattering coe cients display resonances as a function of the parameter x = ka. The only input to the program is the real and imaginary part of the refractive index, which for ZnSe is taken to be 2.98 + 0.4i.20 The excitation wavelength is chosen to be 514.5 nm, and the scattering eciency may then be plotted as a function of particle size.

III. RESULTS Figure 1 shows (AFM) images of ZnSe surface before and after etching with acid. AFM images show that before etching (a), ZnSe surface is fairly smooth, whereas protrusions of nanoscale structures appeared on the surface when it was etched with acid for 2 min (b,c). Close observation of the surface in Figure 1c reveals that the shape of these structures appeared to be hemiellipsoidal nanoparticles. Using image-processing software (Nanoscope 6), we determined that the average radius and height of these particles are approximately 55 and 6 nm, respectively. The AFM images of ZnSe surface etched for 1 min showed average hemiellipsoidal particles sizes >1 m. Etching of the surface beyond 2 min results in considerably diminished particle size (in both height and radius) and lack of discernible Raman signal. The columns in Figure 2 show the measured distribution of hemiellipsoidal nanoparticles with dierent diameters on the ZnSe surface etched for 2 min. It can be seen from this Figure that the particle sizes have a broad distribution, while a plurality of particle sizes are in the range between 110 and 130 nm. The solid curve in this Figure represents the dependence of the eciency of near-eld enhancement Qnf on particle size. The curve is plotted by xing the wavelength of incident light at 514.5 nm and using a value of refractive index n + i = 2.98 + i(0.4). The Figure shows that the optimum particle size is 156 nm, where the near-eld enhancement Qnf reaches its
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Figure 2. Measured distribution of particle diameter of ZnSe on the etched surface. We also show here the dependence of the eciency of near-eld enhancement Qnf on the particle size calculated using the Mie scattering theory.

Figure 1. ZnSe surface (a) before and (b) after etching (5 5) m2 area. (c) ZnSe surface after etching (1 1) m2 area.

maximum. While the majority of the particles on the 2 min etched ZnSe surface are smaller than 156 nm, there is considerable overlap between the experimental distribution and the calculated plot, and it can be seen that a reasonable fraction of the particles are within the range of the optimum particle size, corresponding to the maximum near-eld Qnf enhancement. Thus it is likely that at least a fraction of the molecules encounter a plasmon eld during this experiment. In Figure 3, we show a comparison between the Raman spectrum of 4-MPy powder and that of 4-MPy adsorbed on an etched ZnSe surface. In Table 1, we list the wavenumber
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measurements of the observed lines in this work as well as those from previous works.5,6,2123 It can be seen that the spectrum of 4-MPy on an etched ZnSe surface resembles that of the powder spectrum, with some shifts in frequency but more importantly large dierences in relative intensity. This is similar to surface-enhanced Raman spectroscopy (SERS), which is normally carried out on a silver surface. For comparison, in Table 1, we list the observed SERS spectrum of 4-MPy on a Ag electrode at 0.8 V (vs SCE) and on PbS nanoparticles. As listed in the Table, the 4-MPy lines observed in this work are almost identical to those that were reported on PbS nanoparticles and on Ag electrode. In particular, it can be seen that the positions of 685, 778, 1281, and 1577 cm1 lines in ZnSe surface are very similar to those on PbS quantum dots. The most noticeable dierences in this Figure are the large enhancements of the lines at 1025, 1281, and at 1577 cm1, which are considerably weaker in the powder spectrum. Other notable enhancements are observed at 685 and at 778 cm1, which are also quite weak in the powder spectrum. The rst three lines are the most intense in the spectrum of 4-MPy on the etched ZnSe surface, while the latter two are at least comparable in intensity to the other lines of the spectrum. Referring to the assignments of the bands, it can be seen that the rst intense line at 1025 cm1 is assigned to a1 symmetry in the C2v point group, while the lines at 1281 and at 1577 cm1 are assigned to b2 symmetry. The lines at 685 and at 778 cm1 are assigned to b1 symmetry. While many of the totally symmetric a1 modes are seen to be either suppressed or reduced in relative intensity, other nontotally symmetric b1 and b2 modes are enhanced after the adsorption of 4-MPy molecules on the etched ZnSe surface. Figure 4 demonstrates the SERS spectra of 4-mpy molecules as a function of etching time on the ZnSe surface. The appearance of totally (a1) and nontotally (b1 and b2) symmetric vibrations can be observed in both spectra resulting from 4-mpy molecules adsorbed on ZnSe surfaces etched for 1 and 2 min. However, this Figure illustrates a remarkable dierence in the relative enhancement of the intensity resulting from 4-mpy molecules adsorbed on ZnSe surface. Because the mean particle size of the 1 min surface is >1 m, it is far out of range of the surface plasmon (Figure 2). This gives an indication of the
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Figure 3. Comparison of the Raman spectrum of 4-mercaptopyridine powder (black) with that of 4-mercaptopyridine molecules adsorbed on a ZnSe surface etched for 2 min (red). Excitation is at 514.5 nm.

Table 1. Spectral Lines and Assignments of 4-MPy Observed Bandsa

assignment 8a 8b 19a 14 3 ip-NH def 9 (deprotonated) 9 NH+ (protonated) 12 CS 18 1 4 6 11 CH oop
a

symmetry a1 b2 a1 b2 b2 a1 a1 a1 a1 a1 b1 a1 b1

Wang, Rothberg 1620 1580 1470 1395 12871318 1250 1220 1206 1099 10301050 1013 760 720 700

4-MPy solution 1626 1585 1487 1283 1255

4-MPy powder 1619 1583 1461 1397 1288 1248 1221 1200 1106 1044 989 789 722 647

SERS 0.8 V 1605 1576 1463 1373

PbS 514.5 nm 1645 1623 1586 1499 1464 1278 1232 1216 1107 1037 1009 780 682

ZnSe 514.5 nm 1635 1615 1577 1496 1458 1281 1237 1211 1122 1025 1011 778 685

1119 1053 1004 722 655

1213 1195 1096 1051

713

Columns 13 are the assignments of Wang and Rothberg (ref 21). Column 4 is the solution spectrum of 4-MPy from refs 6 and ref 23. Columns 5 and 8 are from this work (Figure 3b). Column 6 is the SERS on Ag electrode (ref 22), and column 7 is the SERS on PbS nanoparticles (ref 5).

importance of the plasmon resonance to the enhancement factor.

IV. DISCUSSION The observed SERS spectra of 4-MPy on etched ZnSe surfaces show several dierences from the normal Raman spectrum and are closer in some ways to the SERS observed on PbS and Ag nanoparticles. Among other things, the prominence of nontotally symmetric (b1 and b2) lines indicates a presence of charge-transfer resonance contributions to the overall enhancement. Enhancement of both these b1 and b2 modes can also be observed in PbS quantum dots (Table 1). Charge transfer most likely takes place between the VB of ZnSe and the lowest unoccupied molecular orbital (LUMO) levels of 4-MPy. The lower edge of the conducting band (CB) for ZnSe is 4.09 eV (band gap 2.67 eV), whereas the highest occupied molecular orbital (HOMO) for 4-MPy is 9.7 eV (band gap 4.0 to 4.1 eV).2426 The VB of ZnSe lies at 6.76 eV below the vacuum
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level, while the LUMO of 4-MPy is 1.1 eV above this point, well within the energy needed for a charge-transfer resonance (Figure 5). In addition, ZnSe has a band gap of 2.67 eV, which is very close to the range of interband transition using the excitation laser (2.41 eV). Our study also shows that the nontotally symmetric (b1 and b2) vibrational lines are greatly enhanced on the ZnSe surface etched for 2 min, where the particle size has been tailored to support a plasmon eld. The enhancement of these nontotally symmetric vibrational lines on the ZnSe surface etched for 1 min appears considerably weaker in comparison with that of the ZnSe surface etched for 2 min (Figure 4). At 3 min etching time, the ZnSe is almost absent from the substrate, and no enhancement is observed. We estimated the enhancement factor from the ZnSe surface etched for 2 min because the enhancement of 4-mpy molecular lines appears to be the largest from this surface. The enhancement factor (EF) is the ratio of the Raman intensity
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Figure 4. SERS spectra of 4-mercaptopyridine molecules adsorbed on a ZnSe surface etched for 1 min (black) and 2 min (red). Excitation is at 514.5 nm.

Figure 5. Energy level diagram of a ZnSe bulk surface and 4-mpy molecules. All levels are measured from the vacuum.

per adsorbed molecule divided by that of the free (or solid phase) molecules. It may be determined by the relationship
E F = Isurf Nbulk /IbulkNsurf
(2)

where I and N are the intensities and number of molecules on the surface and in the bulk powder. We consider the surface of the etched ZnSe to be composed of hemiellipsoidal nanostructures with an approximate average radius of 55 nm and an average height of 6 nm. We take for our intensity measurement the 1281 cm1 line of 4-MPy. This line is chosen because it is one the most intense lines in the spectrum and is well separated from its neighbors. After subtracting the background intensity, the intensity in the normal Raman spectrum of this line is 564 counts, while from the surfaceenhanced 4-MPy spectrum it is about 27 837 counts. In both spectra, the laser intensity and the focus were kept the same. The intensity ratio (Isurf/Ibulk) is therefore 49. Using the probe spot size of the laser (2 m in diameter) and the laser penetration depth (10 m) and from the density of 4-MPy (1.2 g/cm3), we determine that the number of Nbulk = 2.0 1011 molecules. Using the formula { r h} to calculate the area of a hemiellipsoid, we estimate the area of a hemiellipsoidal nanostructure to be 1 103 m2. Using Nanoscope 6 image processing software, we estimated the hemiellipsoidal particle density on the ZnSe surface to be 250 hemiellipsoidal particles/m2. Multiplying the particle density by the area of the laser spot, we nd that there are 785 hemiellipsoidal particles on the etched ZnSe surface that t within the laser
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spot. Multiplying the total number of particles inside the laser spot (785 particles) by its area (1 103 m2) gives a total surface area of interrogated nanoparticles of 0.785 m2 by the laser. Assuming a monolayer coverage on the surface, we nd Nsurf 3.9 106 by dividing the total surface area of interrogation by the cross-sectional area of a 4-MPy molecule. We assume that the vertical cross-sectional area of a 4-MPy molecule is about the same as that of a pyridine molecule, which is 2 107 m2.27 This results in an enhancement factor of 2 106. This value is comparable to most of the early values obtained for Ag surfaces, implying that semiconductor surfaces may be competitive with metal surfaces for surface enhancement. Although a comprehensive theory of SERS in semiconductors is not yet extant, it is unlikely that such a high value can be explained by a single eect.28 The large enhancement factor originating from the etched ZnSe surface corresponding to the maximum near-eld enhancement (Qnf) is most likely due to a combination of a charge-transfer resonance, a surface plasmon resonance, and a band gap (exciton) resonance, all of which are near our excitation source. It is impossible in this stage to make quantitative evaluations of the relative contributions of each source. Only the molecular resonances can be denitively ruled out because they are far from the exciting source.

AUTHOR INFORMATION

Corresponding Author Notes

*E-mail: lombardi@sci.ccny.cuny.edu. The authors declare no competing nancial interest.

ACKNOWLEDGMENTS We thank Dane Christie for sharing his version of the Mie scattering program and help with its implementation. We are also indebted to Joel De Jesus for technical help concerning molecular beam epitaxial growth. This work was partially supported by the Center for Exploitation of Nanostructures in Sensor and Energy Systems (CENSES) under NSF Cooperative Agreement Award Number 0833180. We are indebted to the National Science
dx.doi.org/10.1021/jp407647f | J. Phys. Chem. C 2013, 117, 2337223377

The Journal of Physical Chemistry C Foundation (CHE-1041832) for funding of this project. This project was supported by Award No. 2009-DN-BX-K185 awarded by the National Institute of Justice, Oce of Justice Programs, U.S. Department of Justice. The opinions, ndings, and conclusions or recommendations expressed in this publication/program/exhibition are those of the author(s) and do not necessarily reect those of the Department of Justice.

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