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Optical Properties of Plasmon Resonances with Ag/SiO2/Ag Multi-Layer Composite Nanoparticles View the table of contents for this issue, or go to the journal homepage for more 2010 Chines

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Optical Properties of Plasmon Resonances with Ag/SiO2/Ag Multi-Layer Composite Nanoparticles

View the table of contents for this issue, or go to the journal homepage for more

2010 Chinese Phys Lett 27 064204

(http://iopscience.iop.org/0256-307X/27/6/064204)

Home Search Collections Journals About Contact us My IOPscience

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CHIN PHYS LETT Vol 27, No 6 (2010) 064204

MA Ye-Wan(马业万)**, ZHANG Li-Hua(章礼华), WU Zhao-Wang(吴兆旺), ZHANG Jie(张杰)

School of Physics and Electric Engineering, Anqing Teachers College, Anqing 246011

(Received 8 March 2010)

Optical properties of plasmon resonance with Ag/SiO2/Ag multi-layer nanoparticles are studied by numerical simulation based on Green’s function theory The results show that compared with single-layer Ag nanoparticles, the multi-layer nanoparticles exhibit several distinctive optical properties, e.g with increasing the numbers of the multi-layer nanoparticles, the scattering efficiency red shifts, and the intensity of scattering enhances accordingly

It is interesting to find out that slicing an Ag-layer into multi-layers leads to stronger scattering intensity and more “hot spots” or regions of stronger field enhancement This property of plasmon resonance of surface Raman scattering has greatly broadened the application scope of Raman spectroscopy The study of metal surface plasmon resonance characteristics is critical to the further understanding of surface enhanced Raman scattering

as well as its applications

PACS: 42 25 −p, 42 25 Hz, 42 62 −b DOI: 10.1088/0256-307X/27/6/064204

Due to the quantum size and surface effects,

noble metal nanoparticles have different optical,

electromagnetic and chemical properties from bulk

materials.[ 1 − 4 ] All along, the unique optical

proper-ties have been important study subjects of optics,

electronics, biomedical science, and materials science

The intense optical absorption and scattering effects

induced by surface plasmon resonance, which occur

when a light wave is incident onto a metal surface,

have attracted particularly strong study in recent

years.[ 5 − 7 ]Plasmon-resonance-induced optical

absorp-tion at a metal surface is related to the movement

of free electrons When the plasmon is under

cer-tain electromagnetic disturbance, according to

metal-lic electrical theory, the charge density may not be zero

in some regions, and a restoring force will be

gener-ated to induce oscillating charge distribution When

the frequencies of the electromagnetic disturbance and

the plasma oscillation match each other, resonance

will happen The oscillation frequency is determined

by four factors: the density of electrons, the electron

mass, and the size and shape of the charge

distribu-tion In the macro scale, this resonance manifests as

optical absorption by metal nanoparticles The metal

surface plasmon resonance is the main factor in

deter-mining the optical properties of metal nanoparticles

Many unique optical properties can be achieved when

adjusting the structure, morphology, size and

compo-sition of the metal nanoparticles.[ 8 − 15 ] Consequently,

manufacturing and application of metallic

nanoparti-cles have become very active topics in materials

sci-ence By adjusting the structure and size of

nanopar-ticles, we can derive new optical properties, and

pro-duce new nano-materials to serve the needs of society

In this Letter, we present our numerical study

on a type of Ag/SiO2/Ag multi-layer nanoparti-cles The Ag multi-layer nanoparticles consist of piled Ag/SiO2/Ag nanoparticles, and provide a ref-erence for manufacturing novel nano-materials The results show that the plasmon resonances of such nanoparticles are augmented and exhibited signifi-cantly stronger light scattering at plasmon resonance wavelengths We give each component of the scat-tering intensity for clarity, in addition, the incident angles and polarizations of the wave are also studied

In order to thoroughly study the optical charac-teristics of Ag particles, we concentrate on the main features of the theoretical scattering formalism with Green’s tensor[ 16 , 17 ] on which the numerical simula-tion is based and associated with the numerical meth-ods The silver dielectric constants are taken from Ref [18] for this study, and the dielectric constants of SiO2is set to 2.25 assuming a bulk refractive index of 1.50 The Ag bulk is illuminated by incident light un-der total internal reflection on a glass substrate with

an incident angle 60∘in order to excite an evanescent wave.[ 19 ] The substrate which has significant effects

on the plasmon resonance is a homogeneous medium with a refractive index of 1.5, e.g glass Firstly the influences of the numbers of Ag multi-layer nanoparti-cles on the scattering efficiency are studied, as shown

in Fig.1 With increasing numbers of Ag-SiO2 -multi-layer nanoparticles from 1 multi-layer to 8 multi-layers, the res-onant peak wavelengths of individual nanoparticles were seen to be significantly red-shifted from 390 nm

to 430 nm The shift of these peaks can be explained

* Supported by the Scientific Research Fund of Anhui Provincial Education Department under Grant Nos 2005KJ232 and KJ2008B83ZC.

** Email: ma yewan@sohu.com

c

○ 2010 Chinese Physical Society and IOP Publishing Ltd

064204-1

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CHIN PHYS LETT Vol 27, No 6 (2010) 064204

as the variation of the near-field plasmon coupling

be-tween Ag-layers with the change of the dielectric

con-stant, thus the plasmon resonance shifts to a longer

wavelength as the dielectric constant of the

surround-ing medium increases However, the scattering

in-tensity is significantly enhanced firstly and then

at-tenuated From Fig.1 we can also find out that the

scattering coefficients have a local minimum at about

320 nm, which is because both the real and imaginary

parts of the Ag dielectric parameter almost reach zero

at that wavelength Its spectral feature is inherent to

the Ag material properties, independent of the

parti-cle’s geometries and sizes To obtain a good study

on the influence of the dielectric on plasmon

reso-nance, we also change the dielectric SiO2 thickness

from 5 nm to 30 nm while keeping the Ag thickness

constant, the resonant peak wavelengths of individual

nanoparticles are observed to shift only about several

nanometers (which are not given here) In contrast,

the resonant peak wavelengths of individual

nanopar-ticles are observed to blue shift for increasing Ag

thick-ness but keeping the dielectric constant This is equal

to change the Ag-nanoparticle height.[ 20 ] Compared

with nanoparticle growth of different sizes and

geome-tries, we could easily reach the required plasmon

res-onance frequency by the numbers of multi-layers

0

2

4

6

8

λ (nm)

1 Ag layer

2 Ag layers

3 Ag layers

5 Ag layers

8 Ag layers

Fig 1 Simulated scattering spectra for different

num-bers of Ag-metal layers with TIR Each dielectric or Ag

thickness is 20 nm.

Secondly, the scattering intensity distribution of

the Ag-layer with an 𝑥 − 𝑧 plane by TM polarization

under total internal incident angle 60∘ is calculated,

as shown in Fig.2 Compared with the dielectric, the

intensity is significantly enhanced, especially in

Ag-corner regions The top intensity is much more

supe-rior to the bottom In order to reach a better

under-standing about the contributions of each component

(𝐸𝑥, 𝐸𝑦 and 𝐸𝑧) to the scattering field, each

compo-nent of scattering intensity is also given in Fig.2(b)

It is seen clearly that the main contributions to

scat-tering are the 𝑥 and 𝑧 components, while the 𝑦

com-ponent is very small We can also find out that the

scattering intensity is almost symmetrical for both 𝑥 and 𝑧 components in the 𝑧 direction

0 25 50

0 4 6 8

Ag

x (nm)

x (nm)

x (nm)

x (nm)

0 25 50

Ag

(a)

(c)

(b)

0 25 50

0 4 6 8

0 25 50

3 5 7

0 25 50

0.05 0.10 0.15

0 25 50

0 3 6

Fig 2 Simulated scattering intensity of Ag-metal lay-ers with TIR 60∘ in the 𝑥–𝑧 plane Each Ag thickness

is 32 nm (a) Total scattering intensity distribution (|𝐸|), (b) contour of scattering intensity (|𝐸|), (c) |𝐸|, |𝐸 𝑥 |, |𝐸𝑦|, (d) |𝐸 𝑧 |.

0 100 200

0 5 10 15 20 25 30

Ag SiO 2

Ag Ag Ag

SiO 2

SiO 2

Fig 3 Scattering intensity of local electrical field distribution with nanoparticles of four Ag-layers (Ag/SiO 2 ) 3 /Ag at resonant frequency in the 𝑥 − 𝑧 plane.

It is interesting to find out the comparison of the scattering spectra and local field distribution between

Ag nanoparticles of single and multi-layers The re-sults show that by “slicing” an Ag-layer evenly into several layers, the scattering intensity can be signif-icantly enhanced The local electrical field intensity

is significantly enhanced for the multi-layer nanopar-ticles as a result of adding more sharp corners or sin-gularities which play an important role in scattering intensity, as shown in Fig.3 Furthermore, the elec-trical fields for Ag-layer nanoparticles are mainly in-tensified at its corners especially on the top, and as

a result, the electrical field within the SiO2 nanopar-ticles is also enhanced much more strongly than the 064204-2

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CHIN PHYS LETT Vol 27, No 6 (2010) 064204

single Ag-layer nanoparticle This could be explained

such that different layers are oscillating in different

multi-polar modes The local field intensity is

asym-metrical in the 𝑧 direction, as the 𝐸𝑦component plays

an important role greater than the one-layer This

unique electrical field distribution may be employed

for nonlinear optical applications, for example, a

non-linear material is used to replace SiO2, this multi-layer

nanoparticle should exhibit an enhanced nonlinear

ef-fect The scattering intensity enhances obviously with

more Ag-layers In order to obtain a stronger

enhance-ment, we should give more layers

0

2

4

6

8

10

λ (nm)

50 *

60 *

70 *

Fig 4 Spectra calculated for different total internal

re-flection angles with TM polarization.

Thirdly, the influences of the polarization and its

incident angles on plasmon resonance are also studied

The individual main peak of localized plasmon

reso-nance is shown clearly for both TE and TM waves

However, the TE wave has a second and smaller peak

This is because the field component which is vertical

to the metal protuberant film plays an important role

in the TM wave Compared with the TM wave, due

to the exponential damping of electrical field intensity

and plasmon corner or singularity enhancement, the

𝑥- and 𝑧-components are parallel to the metal

protu-berant film by the TE wave Thus there are two peaks

by the TE wave In addition, dependence on the

inci-dent angle is also studied for TM waves When

vary-ing the incident angle of light, the localized plasmon

resonance peaks, both spectral locations and shapes,

do not seem to change at all, but the electrical

inten-sity changes with the variation of the angles because

the exponential damping of electrical field intensity attenuates with light angles The larger the angles, the smaller the intensity

In summary, we have presented the optical prop-erties of plasmon resonance of a type of multi-layer nanoparticles It is observed that by changing the number of multi-layer nanoparticles, the peaks of plsmon resonance red shift, which could be tunable

to the relevant wavelength for plasmon resonance In addition, by slicing an Ag-layer into multi-layers, the scattering intensity is significantly enhanced due to the addition of more corners and singularities The manufacturing of novel metal nanoparticles and syn-thesis of new structures have opened new fields for study in material science, e.g., environmental moni-toring, medical diagnosis and treatment, Raman scat-tering and optics etc However, development in this field is still in the beginning stage, with many prob-lems waiting to be solved For example, manufactur-ing techniques are far from mature (adjustment of re-sponse time, nano-size and concentration etc.) More broad applications in related fields have occurred to meet the demands of social and scientific development

References

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[2] Barnes L W et al 2003 Nature 424 824

[3] Shuford K L et al 2005 J Chem Phys 123 114713

[4] Murray W A et al 2007 Adv Mater 19 3771 [5] Maier S A 2007 Plasmonics: Fundamentals and Applica-tion (Berlin: Springer)

[6] Kreibig U and Vollmer M 1995 Optical Properties of Metal Clusters (Berlin: Springer)

[7] Novotny L 2006 Principle of Nano-Optics (Cambridge: Cambridge University)

[8] Brioude A et al 2005 J Phys Chem B 109 23371

[9] Kelly K L et al 2003 J Phys Chem B 107 668

[10] Kottmann J P et al 2001 Opt Express 8 655

[11] Su K H et al 2006 Appl Phys Lett 88 063118

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[16] Girard C et al 1995 Phys Rev B 52 2889

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[18] Johnson P B et al 1972 Phys Rev B 12 4370

[19] Ma Y W et al 2008 Chin Phys Lett 25 2473

[20] Ma Y W et al 2009 J Appl Phys 105 103101

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