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18 August 1995

CHEMICAL PHYSICS LETTERS

ELSEVIER
Chemical Physics Letters 242 (1995) 310-314

Nonlinear optical properties of silver sols prepared by photoreduction method

Tomoo Sato a, Taro Ichikawa a, Tetsuya Ito a, Yoshiro Yonezawa a, Kohei Kadono b, Toru Sakaguchi b, Masaru Miya b
a Diuision of Molecular Engineering, Graduate School o/Engineering, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-01, Japan b Osaka National Research Institute, 1-8-31 Midorigaoka, Ikeda-shi, Osaka 563, Japan
Received 9 March 1995; in final form 30 May 1995

Abstract The third-order nonlinear susceptibility ( XO)) of silver sol prepared by a photochemical method was measured by the degenerate four-wave mixing method. The X(3) of the silver sol of brown-green color was larger than that of yellow-brown color. The photo-induced aggregation of silver particles affects the X(3) of the sol. It has been found that the XO) of the silver sol is proportional to the intensity of surface-enhanced raman scattering from carboxylate ions adsorbed on the silver particle. The increase of Xt3) by the enhanced local electric field due to surface plasmon resonance is proposed.

1. Introduction The colloidal gold solution (gold sol) and the gold dispersed glass show the surface plasmon band in the visible wavelength region [1,2]. They present beautiful colors from red-purple to blue color depending on the size, shape and aggregation state of the gold particles. Ricard et al. [3] have shown that those gold dispersed systems have the large third-order nonlinear susceptibility (XO)). The X (3) value of typical gold sol is of the order of 10-12-10 -11 esu. Considering that the X (3) value of a standard material CS 2 is about 10 -12 esu and that the volume fraction of the gold particles in the sol is only 10 -5 V / V , we can recognize how large X t3) the gold particle itself has. Recently, larger X C3) for gold dispersed systems has been achieved by using the ion implantation method to increase the volume fraction to more than 10 -2 V / V [4,5]. It has been suggested that the large X (3) of the gold dispersed system is caused by the

enhanced local electric field at the surface of the gold particle [3,6-8]. The enhancement of the local field is induced by the excitation of the surface plasmon. It is believed that the apparent X ~3) of the gold dispersed system is related to the third-order nonlinear susceptibility of gold metal itself, X~3),
(3) X(3) =pf2 I f 2xm ,

(1)
(2)

E L = rEin.

Here p denotes the volume fraction of small Parti cles, El, the electric field of the incident light, E L the local field at the particle. The local field enhancement factor f is expressed by the relative complex dielectric constant of the bulk metal to the surrounding medium, ,, 3

f= ,+----5"

(3)

In case of the gold dispersed systems, X t3) is apparently enhanced by 16 times at the wavelength, A =

0009-2614/95/$09.50 1995 Elsevier Science B.V. All rights reserved SSDI 0 0 0 9 - 2 6 1 4 ( 9 5 ) 0 0 7 3 8 - 5

T. Sato et al. / Chemical Physics Letters 242 (1995) 310-314

311

530 nm. On the other hand, only a few studies have been known on X (3) of silver dispersed systems [3,9,10], although it also has distinct surface plasmon band in the visible region as well as the gold dispersed systems. We have reported that the UV-irradiation (A = 253.7 nm) of the silver ion aqueous solutions in the presence of some protective agents resulted in the formation of the stable aqueous solution dispersing small silver particles (silver sol) [11,12]. In this method, color of the sol could be controlled by changing irradiation conditions. Because the change of the color is caused by the change of surface plasmon resonance of the silver particle, it is expected that the X (3) value of the silver sol should be changed correspondingly. In this study, we have measured X (3) of the silver sol prepared by the UV photolysis of the aqueous AgCIO 4 solution containing a polysaccharide, sodium alginate, as the protective agent. In this system, it is possible to control the color of the sol by UV-irradiation time.

2. Experimental
Sodium alginate (SA, Scheme 1) is a polysaccharide having carboxylate group. SA was purified according to the Konishi procedure [13]. Photolysis of the aqueous solution containing 0.2 wt% SA and 1 mM (1 M = 1 mol dm -3) mgC104 in the 10 X 10 X 40 mm 3 rectangular quartz cell was achieved by the UV light ()t = 253.7 nm) from the 200 W low-pressure mercury lamp [11]. The number of incident photons was 1.8 1016 c m - 2 s -1. If all Ag in the solution was reduced to Ag metal, the volume fraction of silver particles became 10 -s V / V . Extinction spectra of the solutions after photolysis were measured by the Simadzu photospectrometer UV260. The amount of the reduced silver was deter-

mined by atomic absorption spectrometry combined with dialysis of photolytic silver. The silver sol was dropped on the carbon coated copper grid and dried in order to observe the silver particles by a JEOL JEM-1200EX transmission electron microscope (TEM) operating at 80 keV. X (3) of the silver sol was measured by a phase conjugation degenerate four-wave mixing arrangement [14]. A frequency-doubled N d : Y A G laser (A = 532 nm, Quantel International, YG571C) was used as the light source. The pulse duration and the power were 40 ps and 8 MW cm -2, respectively. Only if the signal intensity was too weak to measure, 45 MW cm -2 powered pulse was used instead. The angle between the forward pump beam and the probe beam was 20 . The silver sol was put in the quartz cell of 1 mm in thickness. Both the phase conjugate reflection beam and the reference beam of the probe were simultaneously detected by a streak camera (Hamamatsu photonics, Temporal Photometer C1587). After the phase conjugate reflectivities from the silver sol and from CS 2 were measured, X (3) of the silver sol was calculated by the following equation:
)((3) = Q _ _

R Rcs 2

Ics2

o)

(4)

ncs ~

I Xcs2-

Here, n and ncs 2 were the refractive indices of the silver sol and CS 2, R and Rcs 2 the conjugate reflectivities from the silver sol and CS 2, I and Ics2 the power of the pump beam incident on the silver sol and on CS z, respectively. Q denotes the correction factor for the light absorption by the sample, represented by ln(1/T)/[x/T(1- T)], where T is the transmittance of the silver sol. Xcs, (3) was assumed to be 2.89 x 10 -12 esu [5]. R had been confirmed to be proportional to 12 in our colloidal system, which implying that a true X (3) process was being measured.

COONa

COONa

3. Results and discussion

H H H H H

Sodium alginate Scheme 1.

The variations of extinction spectra with UVirradiation of the aqueous solution containing SA and AgC104 are shown in Fig. 1. The transparent solution changed into yellow color after 30 min

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T. Sato et al. / Chemical Physics Letters 242 (1995) 310-314

"O

io
O

(a)
~..........~ ~ 30 mi. 0

200 nm

(b)

200 nm

Fig. 2. Transmission electron micrograph of silver sol formed by photolysis. UV irradiation time: (a) 60 min; (b) 240 min.

min 200 300 400 500 600 700

Wavelength I nm
Fig. 1. Variation of extinction spectra of aqueous solution containing 0.2 wt% sodium alginate and 10 -9 mol dm -3 AgC104 with UV irradiation time. The spectra are shifted on the ordinate axis for sake of clear presentation. Light path length = 2 mm.

irradiation. In the extinction spectrum, a colloidal extinction peak by surface plasmon resonance appeared in the vicinity of A = 400 nm, which indicates the formation of small silver particles [1,15]. The amount of reduced silver was 20%-25% of the amount of Ag which existed at the beginning. According to the TEM observation, spherical and uni-dispersed small particles whose diameter was 10-30 nm were formed (Fig. 2a). After prolonged irradiation, 80%-100% of initial Ag was reduced and the color of the solution changed from yellowbrown to green-brown after 150-240 min irradiation. At the same time, the longer wavelength tail around A = 500-600 nm appeared. It has been well known that the size, shape and aggregation state of the silver particles strongly affect the spectral line shape of the surface plasmon band [1]. The change of the extinction spectrum in Fig. 1 may be due to the aggregation of the silver particles or the formation of ellipsoidal particles [1,16]. Actually, the aggregation of small particles and the formation of ellipsoidal particles, whose axial ratio was more than 2, were ob-

served by TEM (Fig. 2b). It is important that when the irradiation was interrupted, the silver sol was stable for more than one month without further aggregation. The aggregation of the silver particles after prolonged irradiation could be an example of the photo-aggregation reported for the gold particles [17,18]. The variations of X (3) of the silver sol with the UV-irradiation time is given in Fig. 3. After 30 min irradiation, the X (3) value of the yellow-brown sol

104[
1041

i0 -Iz

lO "13

10 -14

60

120

180

240

Irradiation time I min

Fig. 3. Variation of X t3) of the solution containing 0.2 wt% sodium alginate and 10 -3 tool dm -3 AgC104 with UV irradiation.

T. Sato et al. / Chemical Physics Letters 242 (1995) 310-314

313

was less than 6 X 10-14 esu, which was almost the same as X (3) before irradiation. After 90 min irradiation when the aggregation of the silver particles started, the X ~3) value suddenly increased. After 240 min irradiation, the X ~3) value of the green-brown sol reached to 2 X 10-12 esu. Considering the different amount of the reduced silver, X (3) is increased more than 10-20 times by the growth a n d / o r aggregation of the silver particles. It is likely that the third-order nonlinear susceptibility of the silver sol has changed in the course of photolysis as a result of the variations of the size, shape and the aggregation state of the silver particles, in line with the change of the linear susceptibility which is the origin of the color. Eq. (3) has been often used to evaluate f of the metal dispersed systems containing the spherical small particle. However, Eq. (3) seems to have several intrinsic limitations, because the actual value of f depends on the shape, size and aggregation state of the metal particles. In the case of using the Eqs. (1) and (3) to evaluate X(m 3) f r o m X (3), there is the difference of 100 times or more between X(m 3) obtained by Ricard et al. [3] at A = 396 nm and X(m 3) at A = 532 nm of the our silver sol prepared by 240 min UV-irradiation. We suppose that this large difference is not due to the difference of the wavelength. The X (3) at A = 532 nm of an especially carefully made silver sol [12] which consisted of the small and spherical silver particle (volume fraction of the particle was 10 -5 V / V ) was in the order of 1 0 - ] 4 e s u . The Xm O) value calculated from this X (3) almost agreed with the result of Ricard et al. In this Letter, we assume that Xm (3) of a silver metal itself does not depend on the form and aggregation state of the small particles, as well as on the size of them [7,10]. It must be noted that even if the X~ (3) does not change, X (3) of the silver sol changes largely by the form, size and aggregation state of the small particles. Surface-enhanced Raman scattering (SERS) is a typical example of the photophysical processes whose efficiency largely changes as a result of the aggregation of the colloidal silver and gold particles [19-22]. In the electromagnetic mechanism of SERS, the local electric field which acts on the molecule at the surface of the silver particles is enhanced by surface plasmon resonance [19,22]. The SERS efficiency is

enhanced further by the aggregation of the silver particles because of the further enhancement of the local field due to the aggregation. Therefore, the SERS efficiency may be used as a monitor of the local field. Along this line, we measured the Raman spectrum of the same silver sol as used for the measurements of X (3). The Raman spectra were measured by Jobin-Yvon T64000 spectrometer equipped with a CCD detector in a backscattering (180 ) geometry. A 514.5 nm line of Ar + laser (NEC GLG3260, 17 mW) was used for the excitation. The change of the Raman intensity of the silver sol at 1405 c m - 1 with UV-irradiation time of the aqueous solution containing SA and AgC104 was monitored. The 1405 cm -1 band is assigned to a symmetric stretching vibration of carboxylate group in SA [23]. Before irradiation, Raman signals from the solution were very weak. When the small silver particles were somewhat generated by 30 min UVirradiation, the Raman intensity was increased a few times. When the silver particles started aggregation by prolonged irradiation, the Raman intensity further increased. The Raman intensity after 240 min UVirradiation amounted to more than 350 times of that before irradiation. Paying attention to the similar behavior of the Raman intensity to X (3), we have tried to plot X (3) versus the Raman intensity (Fig. 4). In this figure, the increments of the Raman intensity and X C3) from
10-11

10"12I ..................
.."
W

'"t
10- f

Io '5I."i
0.1

.................

, , , ,,,,,i ........ i
10 100 1000

Rarnan intensity I a.u.

Fig. 4. X (3) as a function of the Raman intensity of silver sol containing sodium alginate. Raman intensities at 1405 cm-1 ( O ) and 235 cm -1 ( O ) were monitored.

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T. Sato et al. / Chemical Physics Letters 242 (1995) 310-314

those before UV-irradiation were plotted. There is a striking correlation between Raman intensity and X (3) with the slope of = 1.0. In this figure, we have plotted the intensity of the Raman band at 235 c m - a, too. This band is assigned to the A g - O stretching vibration corresponding to the silver surface and oxygen of carboxylate group [24,25]. It is observed that the log-log plot concerning the Raman intensity at 235 cm-1 is also fitted to the straight line with the slope of = 1.0. These results show that there is a proportional relation between X (3) and the Raman intensity. Considering that the Raman intensity from the molecule adsorbed at the surface of the silver particle is proportional to the fourth power of f [19], it is recognized that X (3) is enhanced by the local field and the enhancement factor of X (3) is proportional to the fourth power of [. These results are not inconsistent with Eq. (1). In summary, we have measured X (3) at h = 532 nm of the silver sol prepared by the photoreduction method. This method enables us to control the aggregation state of the silver particles by changing only the UV-irradiation time. Although X (3) of the typical yellow sol free from aggregation is small, X (3) of the brown sol or green-brown sol, in which silver particles are ellipsoid or aggregate themselves, is as large as X (3) of the gold sol. Comparing with the result of the Raman scattering study, it has been concluded that the aggregation of the silver particles and the formation of the ellipsoidal particles enhances the local field at the particles, which induces the increase of X (3) as a result. X (3) has been experimentally proved to be proportional to the SERS intensity, implying a dependence on the fourth power of f if Xm (3) is assumed constant.

References
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Acknowledgement
We are grateful to Professor Z. Ogumi and Dr. M. Inaba of the Division of Energy and Hydrocarbon Chemistry, Kyoto University, for their kind help with Raman measurements, and to Professor N. Mii and Dr. K. Kuge of the Department of Imaging Science and Engineering, Chiba University, for their aid with electron microscopy.