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Photo-assisted control of gold and silver nanostructures on silicon and its SERRS effect

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2013 J. Phys. D: Appl. Phys. 46 275303 (http://iopscience.iop.org/0022-3727/46/27/275303) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING J. Phys. D: Appl. Phys. 46 (2013) 275303 (7pp)

JOURNAL OF PHYSICS D: APPLIED PHYSICS doi:10.1088/0022-3727/46/27/275303

Photo-assisted control of gold and silver nanostructures on silicon and its SERRS effect
Abhishek Lahiri1,6 , Rui Wen1 , Surasak Kuimalee2 , Anirban Chowdhury3,5 , Shin-ichiro Kobayashi4,6 , Lisheng Zhang1 , Peijie Wang1 and Yan Fang1,6
1 The Beijing Key Laboratory for Nano-Photonics and Nano-structure, Capital Normal University, Beijing 100048, Peoples Republic of China 2 Department of Industrial Chemistry and Textile Technology, Faculty of Science, Maejo University, Chiang Mai 50290, Thailand 3 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai, 980-8577, Japan 4 Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, 6-6-04 Aoba, Sendai 980-8579, Japan

E-mail: fangyan@mail.cnu.edu.cn, kshin@atom.che.tohoku.ac.jp and lahiri.abhishek@gmail.com

Received 5 February 2013, in nal form 16 May 2013 Published 19 June 2013 Online at stacks.iop.org/JPhysD/46/275303 Abstract A facile approach to control the growth of gold nanostructures on n-type silicon by galvanic displacement was demonstrated previously. It was observed that in the presence of light and red laser, at initial stages, gold nano-needles were formed, which then grew perpendicular to the substrate with time. However, the growth process has not yet been understood completely. Here, we have attempted to understand the galvanic displacement phenomena in the presence and absence of light by characterizing the growth process using transmission electron microscopy, atomic force microscopy and x-ray diffraction. Furthermore, we also evaluated the effect of laser on the deposition of silver on silicon wherein the use of green laser resulted in the formation of dendrites, whereas spherical nanoparticles were formed in dark. To further evaluate the benets of the metalsemiconductor hybrid structure, we also evaluated the surface enhanced resonance Raman spectroscopy (SERRS) of the hybrid substrates and give evidence of the importance of the semiconductor substrate/metalsemiconductor interface in enhancing the SERRS activity. (Some gures may appear in colour only in the online journal) S Online supplementary data available from stacks.iop.org/JPhysD/46/275303/mmedia

1. Introduction
Metalsemiconductor hybrid structures are greatly desired as they possess good optoelectronics [1], sensoric [2] and catalytic properties [3] and therefore can be applied in photocatalysis [3] and solar energy applications [4]. Numerous attempts have been made on developing metal semiconductor structures, for example, AuCdSe [5], AuPbS [6], AuCdSe/CdS [7], AuFe2 O3 [8] and AuTiO2 [9] to
5 Present address: Research and Development, Tata Steel, Jamshedpur, 831001, India 6 Authors to whom any correspondence should be addressed.

name a few. A common strategy to synthesize these structures is to rst produce the semiconductor nanoparticles and then deposit the metal onto the semiconductor using different techniques [10]. The galvanic displacement process is a versatile technique to deposit metal on a semiconductor surface and has been applied to deposit gold and silver nanostructures on Si [1113] , Ge [14], Al [15], Cu [16] or GaAs [17]. However, controlling the metal morphology deposited on the semiconductor is difcult. Such electroless deposition processes were also used to deposit other metals such as Pt and Ni [18, 19]. Carbone et al [20] rst showed the possibility of fabricating gold nano-domains of 15 nm in size by exciting
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CdS or CdSe quantum rods. Li et al [21] further exploited this strategy to control the gold morphology on CdSe wherein the UV light generated electrons on the CdSe nanorods and led to the deposition of Au from a gold chloride solution by a photoreduction process. They could also fabricate Pd/Au alloy by this technique on the semiconductor nanorods [21]. We had previously shown that the gold morphology can be controlled by the simple galvanic displacement process on illuminating the semiconductor by light and laser [22]. In the presence of diffused light and red laser, the growth of nano-needle structure took place, whereas in dark irregular morphology was obtained [22]. In this paper, we show that even silver morphologies can be controlled by the same technique. Also, we further investigated the growth of the gold nanostructures using atomic force microscope (AFM), transmission electron microscope (TEM) and x-ray diffraction (XRD). From TEM analysis the growth direction of the nanoneedles was found to be along the 1 1 2 direction. We also propose a growth mechanism for the formation of gold needle structure on illumination.

Figure 1. (a ) Low magnication of gold deposition performed in red laser. (b) High resolution image of (c) showing the formation of mostly needle shaped structure. (c) Low magnication of gold deposition performed in dark and (d ) high resolution image of gure showing irregular structure.

2. Experimental section
For sample preparation, the n-type silicon (Nilaco, <0.02 cm) was cut to approximately 1 cm2 and sonicated in pure acetone solution for 10 min. The substrate was then removed and washed in Milli-Q water and dried in nitrogen. The silicon was then dipped in a hot solution of 1 : 4 H2 O2 /H2 SO4 for 10 min and again washed in Milli-Q water and dried in nitrogen. Finally, the silicon was dipped in 1% HF solution for 30 s and after the washing and drying process was left in 0.06M NH4 F solution for 10 min. After the nal washing and drying process, it was introduced into a solution of 11M HF + 10mM HAuCl4 in the presence and absence of red laser (635 nm). The sample was placed at the bottom of a teon beaker and the laser pen was placed about 5 cm above the substrate making sure that the laser spot could be seen reecting from the silicon substrate. The laser power density was about 32 mW cm2 . For silver deposition, the silicon was introduced into a solution of 11M HF + 10mM AgNO3 in the presence of green laser (532 nm) and in dark. Green laser was used for silver as the surface plasmon of silver nanoparticles is around 410 nm. Previous studies have shown that the maximum plasmon enhancement is usually obtained when the excitation wavelength is red shifted to about 120 nm [23]. Therefore although the SP was found to be 410 nm for Ag nanoparticles, we excited it with 532 nm laser. However, further experiments need to be carried out to clarify the issue regarding the mismatch in the wavelength between the surface plasmon resonance and laser. At present it remains an open question. For SEM (Hitachi) characterization, the silicon substrate was placed onto a carbon tape which was attached to the SEM sample holder and introduced into the SEM chamber. The sample for TEM was prepared by sonicating the silicon substrate containing gold in ethyl alcohol solution for 10 min. The solution containing gold was then transferred to the copper grid. TEM experiments were carried out in TOPCON EM-002B at accelerating voltage of 200 kV. 2

For the Raman experiments, one drop of Rhodamine 6G (5 106 M) was dropped onto the silver/silicon substrates and dried in natural atmosphere. The Raman spectrum was recorded by a RENISHAW via Raman microprobe with a 50 objective, and the excitation line was at 532 nm.

3. Results and discussion

3.1. Crystal growth The galvanic displacement of gold and silver on n-type silicon was performed by dipping a clean silicon substrate in a solution of gold chloride/silver nitrate and hydrouoric acid (HF). The deposition takes place according to reactions (1), (2) and (3) [24]:
Si + 6F SiF2 6 + 4e o ESiF = 1.2 V versus NHE, 2 /Si
6

(1)

AuCl 4 3e Au(s) + 4Cl o EAu 3+ /Au = 1.42 V versus NHE ,

(2)

Ag + e Ag

o EAg /Ag+ = 0.799 V versus NHE. (3)

The deposition was performed in dark as well as in the presence of red laser (635 nm). It was shown previously [22] that in the presence of light and laser, needle-like gold nanostructures were formed along with the formation of some dendrites. In comparison, the gold deposited in dark formed a lot of irregular shaped clustered particles. An example of the microstructure formed in the presence of red laser (635 nm) and in dark is demonstrated in gure 1. Dendrites are observed on illumination with red laser (gure 1(a )). However, the base structure (excluding the dendrites) contains only gold nanoneedles of around 50 nm in diameter and 400 nm in length which protrude perpendicularly to the substrate as observed in gure 1(b). In contrast, the gold deposited in dark in gure 1(c)

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Figure 2. (a ) Low magnication image of silver on silicon by galvanic displacement in dark. (b) Galvanic displacement of silver on silicon in the presence of green laser (532 nm).

Figure 3. (a ) TEM image of gold needle in the presence of light. The inset shows the SAED pattern of the leaf. (b) Lattice fringe of the dendrite leaf showing the lattice distance of 2.4 . (c) TEM image of gold particles formed in dark. The inset shows the SAED from the area which conrms the polycrystalline gold formation. (d ) XRD of gold on silicon in dark and in the presence of light.

formed a lot of irregular shaped clustered particles. Higher magnication shows irregular gold particles are of 100200 nm in size. Few pillars (gure 1(d )) are also observed with diameter of around 100 nm with about 1 m in length. This might be due to some experimental error which is difcult to avoid as during introducing and removal of the silicon sample from the solution, a light source is needed and it is not always easy to introduce and remove the sample quickly due to the presence of hazardous HF solution. However, similar formation of needle structure in the presence of light/laser was not observed on using p-type silicon and only an increase in the gold deposition could be seen [22]. On performing the same technique during the galvanic deposition of silver on silicon, a similar phenomenon was observed. Figure 2 compares the microstructure of silver deposited on silicon in dark and in the presence of green laser (532 nm). From gure 2(a ), it is evident that silver nanoparticles are formed in dark, whereas in the presence of green laser (gure 2(b)), formation of silver nanorods is seen. Some of these nanorods have also shown the formation of dendrites. The transmission electron microscopy (TEM) image of the gold needle which is in the process of forming a dendrite is presented in gure 3(a ). The needle has a length of about a micron 3

with a sharp tip having a diameter of around 10 nm. The selection area electron diffraction (SAED) pattern conrms that the needle is a single crystal and the d spacing corresponds well to the face-centred cubic structure of gold (JCPDS 04-0784). The SAED pattern corresponds to the 1 1 0 crystallographic zone axis suggesting that the growth direction is along 1 1 2 . The high resolution image in gure 3(b) shows well developed lattice fringes and the interplanar spacing was calculated to be 0.24 nm which is in good agreement with the d values of the Au (1 1 1) plane (0.235 nm). However, the gold deposition performed in dark shows agglomerated particles (gure 3(c)) and the SAED conrms the polycrystalline state of gold. The XRD pattern of the gold deposited in the presence of illumination and in dark is shown in gure 3(d). Comparing the XRD plots, it is evident that in the presence of illumination, the growth of the Au (1 1 1) peak (38.19 ) is almost twice that grown in the dark and reects sharp cubic gold formation (JCPDS 04-0784). This is in agreement with the TEM analysis and suggests that the growth of Au in the presence of light has a strong preferential (1 1 1) orientation. A detailed pole gure analysis should be conducted on these gold samples in future to shed more light on this issue. However, there are four additional peaks at 39.08 , 41.7 , 42.15 and 58.8 . The rst three peaks correspond well to the formation of SiAu alloy [25] which might have been present at the interface. The fourth peak at 58.78 could be due to the presence of oxygen in the silicon substrate [26]. Thus, the formation of gold needles, dendrites and silver nanorods in the presence of light and laser suggests that the energy provided by illumination plays an important role. At the initial stage of the deposition, the light excites the n-type silicon surface and generates electrons at the conduction band which in turn produces more surface electrons. Consequently, the hole generated in the n-type Si might have oxidized the silicon to silica [27, 28]. The silica formed immediately gets dissolved in HF. We believe that because of this phenomena, the requirement of hole acceptors such as ethanol was not required as mentioned by other investigators [20, 21, 29]. The surface electrons result in the formation of gold or silver nuclei with particle size of around 5 nm [30] at initial stages of the deposition process. On illumination, it has been shown that the charges generated on semiconductor are transferred to the metal and used to promote further redox reactions [29, 31]. In our experiments, the nuclei start to grow along a particular direction and we believe that it is due to the surface plasmon eld on the gold nuclei as well as the electrons generated on the silicon surface. The presence of electric eld at both sides of the gold or silver nuclei appears to have resulted in preferential growth of gold particles perpendicular to the silicon surface. The microstructure in gure 4(a ) shows the morphology of the gold at places where there was no dendrite formation. Large gold nano-needles which are present in abundance are evident which support the directional growth process and some of these needles show a corrugated edge, an indication that they may nally form dendrites. In comparison, the microstructure of gold deposited in the dark (gure 4(b)) shows irregular morphology which follows the VolmerWeber (VW) growth modes shown previously [32], wherein gold

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Figure 4. (a ) Formation of gold needle structure in the presence of torch light on performing experiment for 10 min where dendrite was not present (b) formation of irregular gold structure in dark. Experiment carried out for 10 min. (c) In the presence of red laser. Experiment carried out for 10 min.

Figure 6. (a ) AFM image of gold deposits on Si (1 1 1) for 30 s under illumination with a scan size of 1 m2 and (b) 250 nm2 . (c) The cross-sectional prole along the indicated line AA in (b) and (d ) 3D AFM image of (b).

Figure 5. (a ) High resolution image of gold deposition performed for 10 s in the presence of illumination. The inset shows the UVvis spectra of Au on n-type silicon. (b) Deposition performed in dark for 10 s. The inset shows the damage of sample during SEM. (c) Microstructure of Ag in the presence of green laser (532 nm). (d ) Deposition performed in dark.

nuclei is initially formed and then grows to form island structure. However, mostly gold needle structures are observed in gure 4(c) on using red laser (635 nm) as it generates the maximum plasmon resonance effect. To conrm our proposed theory, we carried out deposition experiments for 10 and 30 s in the presence and absence of illumination. Figures 5(a ) and (b) compare the microstructure of gold after 10 s of the displacement reaction process. Needle shaped gold nanostructure (gure 5(a )) is clearly seen in the presence of illumination whereas three-dimensional irregular morphology (gure 5(b)) is observed when experiment was carried out in dark. One or two gold nano-needles are also observed in dark and could occur due to high concentration of HF as observed in previous investigations [30, 33]. UVvisible analysis of the 4

thin lm in the presence of light (see the inset in gure 5(a )) showed a broad and shallow peak from 495 to 700 nm. This peak could be related to the surface plasmon of gold nanoneedles. As the needles shape and size are not exactly the same, the surface plasmon peak is broad. However, in the case of gold deposited in the dark, no clear absorption peak was observed. The high resolution images were very difcult to focus in the SEM as the gold layers were very thin and was affected by the interaction with electron beam even at low electron volts. The inset in gure 5(b) shows the effect of electron beam. Figures 5(c) and (d ) compare the deposition of silver on silicon in the presence of green laser and in dark, respectively. It is evident from gure 5(c) that nanorods (marked by red arrow) are present. In comparison, experiments carried out in the dark resulted in the formation of spherical nanoparticles, indicating the plasmon-induced growth phenomena. The directional growth was also conrmed by atomic force microscopy (AFM) on the gold sample deposited for 30 s as seen in gure 6(a ). From gure 6(b) and the line height prole along AA in gure 6(c), it is evident that the base gold particles have an average diameter of 10 nm and height of 1.1 nm. Some vertical growth of particles with average height of 3.5 nm and base diameter of 17 nm are also observed and correspond well to the growth of nano-needle observed by SEM (gure 5(a)). The three-dimensional AFM image in gure 6(d ) gives an insight into the progressive growth of nano-needle from the spherical gold nuclei which further supports the explanation of vertical growth in the presence of electric eld. However, the growth from gold nuclei to nano-needle is not the same everywhere (gure 6(d)) which might due to non-uniform power density in the area and complex dynamics of the redox reaction.

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Figure 7. An illustration for the formation of irregular gold particles and dendrites in the absence and the presence of illumination, respectively.

It is known that gold and silver nanorods have longitudinal plasmon resonance as well as transverse oscillation [34]. With time, these nano-needles grow due to the higher plasmon resonance at the two ends of the needle [35] and, therefore, we nd a lot of needle structure (gures 1(d ) and 3(c)). Thus, from the above characterizations, we can illustrate a model for the gold deposition process on n-type silicon as demonstrated in gure 7. In dark, the gold ions take electrons from the etched silicon and form gold nuclei which progressively grow to form clusters. In the presence of light, an electronhole pair is created. The electrons from reaction (1) as well as from the light source help in nucleating gold atoms on the silicon surface. The light source further creates a surface plasmon resonance on the gold nuclei trapping it between two electric elds and forcing it to grow along a particular direction. The electric eld generated by the plasmon resonance effect results in fast deposition rate of gold which increases the growth of the structure rapidly. This results in the creation of gold nano-needles. As the growth of nano-needles take place, there is longitudinal plasmon resonance as well as transverse oscillation [33] which might have resulted in higher electric eld and the growth of the dendrite. The growth mechanism of silver appears to be similar to that of gold.

4. SERRS
As metalsemiconductor hybrid nanocrystals have recently been shown to enhance the surface enhanced Raman spectroscopy signal [2, 37], we analysed the silversilicon substrate for the detection of the R6G molecule. Figure 8 compares the Raman spectra of the R6G molecule at concentration of 5 106 M on the silversilicon substrate fabricated in the presence and the absence of laser. Prominent peaks of the R6G molecule are evident in both the spectra which is consistent with the literature data [38]. An indication of charge transfer process can be highlighted by analysing the peak at 233 cm1 in gure 8(a ), which corresponds to the AgN stretching of the Ag-R6G complex. Also, an additional shoulder peak at 272 cm1 is observed. Furthermore, we nd two peaks at 121 and 155 cm1 , both of which correspond to the vibration induced by chemical 5

bonding between the R6G and Ag atoms [37]. However, the intensity of the peaks is less on silver deposited on silicon in dark compared with that deposited in the presence of laser. The 772 cm1 peak was enhanced 4 times in the case of depositing silver in the presence of laser. In addition, peaks at 552, 567, 978, 1012 cm1 and at higher wavenumbers at 1713, 1796, 1885, 1932, 1979 cm1 are also observed in gure 8(a ). The high wavenumber peaks, especially between 1700 and 1750 cm1 which correspond to carboxyl groups have not been observed in previous SERRS measurements on using even Ag colloid [3840]. It was also observed that this metalsemiconductor substrate could detect concentrations as low as 1 1012 M (see the online supplementary le, gure S1 (stacks.iop.org/JPhysD/46/275303/mmedia)). Clearly, the Raman spectrum of R6G on silver deposited in the presence of laser is much more enhanced compared with that in dark. The enhancement could be attributed to the nanorods and dendritic silver nanostructures obtained in the presence of 532 nm laser. Interestingly, prominent peaks at 519 cm1 which relates to the rst-order Raman active optical phonon of symmetry 25 of silicon [40, 41] was observed in the presence of 532 nm laser. The Raman peak for bulk silicon lies at 520 cm1 . As the spectral resolution of inVia Renishaw Raman instrument is better than 1 cm1 , the shift by 1 cm1 can be assigned to the formation of silicon nanowire during galvanic displacement reaction which is in agreement with previous literature data [42, 43], Furthermore, we observed that bulk silicon gave Raman peak at 520 cm1 before and after the sample measurement, thus emphasizing the formation of nanowires. On comparing the Raman spectra of the silicon peak at 519 cm1 in gure 8(b) before and after deposition of the R6G molecule on silversilicon couple, a peak broadening and an 18 times increase in the intensity of the peak was observed. The full-width at half-maxima (FWHM) for the silicon peak after addition of the molecule increased from 6 to 15 cm1 . The increase in intensity and the peak broadening of silicon peak indicates the possibility of an interaction between the silicon substrate and the moleculeAg interface. It is further observed that a shoulder peak at 528 cm1 exists on the 519 cm1 peak, which could be from the torsional or ring bending mode of the R6G molecule [38] (see gure 8(b)). The unexpected enhancement of 519 cm1 band drives us to understand the possible mechanism and its effect factor. It was previously reported that during the galvanic displacement reaction, concentric ringed structures were formed in distinct places on the silicon substrate [44]. In such regions we found that the Ag/Si system had different structures corresponding to the different regions in the ring pattern which gave an insight into the crystal growth process with time. Three concentric rings can be clearly distinguished in one ring pattern in the optical image on the Ag/Si substrate from the inset in gure 9 wherein the innermost region shows the formation of the nanoporous layer, followed by nanoparticles (second ring) and growth of nanoparticles (outermost ring) [44]. Figure 9 demonstrates the SERRS spectra of R6G at ring patterns from the innermost area (a ) to the outermost area (c) on the Ag/Si substrate, respectively. Interestingly, it is observed that even through the SERRS

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Figure 8. SERRS spectra of 5 106 M R6G on (a ) spectra obtained on deposition of silver in 532 nm laser light (blue line) and in dark (black line). Florescence background was subtracted and the sample was exposed to 5 mW 532 nm laser radiation for 10 s. (b) Raman spectra of on the bare silversilicon substrate (red line) and after addition of the R6G molecule (black line).

90000 75000

Raman Intensity / a.u.

60000 45000 30000 15000 0 300 600 900 1200 1500

c
a

Raman Shift / cm

-1

1800

Figure 9. SERRS spectra of 5 106 M R6G on ring pattern on deposition silver on silicon at (a ) the inner most area of pattern; (b) the outer concentric pattern and (c) the outmost area of pattern. Inset: the optical image of the ring pattern.

Figure 10. Comparison of Raman spectra of R6G on the silversilicon substrate without dipping in NH4 F solution (black line) and after dipping in 11M NH4 F solution for 20 s (red line).

active of R6G gradually decreases from the inner to outer region due to the difference in Ag morphology, in contrast, it is evident that the 519 cm1 peak is gradually enhanced. This suggests that the enhancement of the 519 cm1 peak is independent of SERRS enhancement of R6G, but related to the interface between Si and Ag as the interaction between SiAg is gradually enhanced from inner area to outer area. We have shown before that the concentric circles are formed with an increase in the reaction time which might have increased the etching of Si and therefore the enhancement of the interaction between SiAg. It was reported that the intensity of Raman scattering of TO-520 cm1 mode of Si is related to the geometrical structure of Si gratings [45]. This phenomenon is similar to the previous report about the 520 enhancement which was related to the geometrical structure of Si grating. However, in our Ag/Si system, if only Si grating would have enhanced the 520 cm1 peak, we should have observed the Raman enhancement of 519 cm1 also on 6

the pure Ag/Si surface without the addition of any molecule. However, from gure 8(b), no enhancement of 519 cm1 on pure surface is observed. In comparison, the enhancement occurs only in the presence of the R6G molecule. This suggests the possibility of charge transfer under laser excitation from the silicon nanowire to the Agmolecule interface which then enhances the 519 cm1 vibration. Thus, the increase in 519 cm1 peak may be due to the combined processes of the geometrical structure of the Si nanowire interface as well as the excitation of electron by the Si nanowire which is then transferred to the Agmolecule interface. At present, we do not have a conclusive proof for the above explanation and further experiments using spectroelectrochemical setup need to be done to establish the exact reaction mechanism. To further conrm that the SiAg interface contributes to the Raman signal enhancement in the 519 cm1 peak, we destroyed the interface by dipping the silver deposited sample into 11M NH4 F for 20 s. The Raman spectrum of R6G on the NH4 F dipped and without dipping is compared in gure 10.

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SEM conrmed that the morphology of the silver deposited on silicon did not change. Figure 10 shows that the AgN stretching at 233 cm1 has diminished and a red-shift of 4 cm1 was observed on dipping the silver silicon substrate in NH4 F solution. Additionally, the 519 cm1 peak diminished, thus further indicating that the property of metalsemiconductor interface plays an important role in the 519 cm1 enhancement.

5. Conclusions
We have shown a simple galvanic displacement process wherein the deposit morphology can be controlled using a particular wavelength of light. It appears from our study that during initial deposition of gold on silicon , the presence of light induces surface plasmon eld on the gold nanoparticles. As the gold nanoparticle is trapped between the plamon eld and the electrons on n-type silicon, a directional growth of gold needles is achieved. However, in the absence of light the growth of irregular morphology take place. Similarly, the growth of silver nanorods and dendritic structure was observed in the presence of 532 nm laser and formation of spherical nanoparticles was observed in dark. The simple control of morphology using light can be exploited further in developing new hybrid structures for catalytic and solar applications. We have further shown that Ag/Si system acts as a high activity SERRS substrate. In particular, the enhancement of 519 cm1 from the rst-order TO mode of Si could be observed in Ag/Si system suggesting the possibility of charge transfer process. Also, it appears from the increase in silicon peak that that the metalsemiconductor interface is an important criterion to improve the SERRS activity.

Acknowledgments
The authors thank Syun Ito (IMR, Tohoku University) for his help in using TEM. The authors would also like to thank Professor Torranin Chairuangsri (Chiang Mai University) for useful discussion regarding TEM analysis.

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