Optical efficiency of Ag and Au nanoparticles

In this paper, we present the results of calculations aimed at the optical radiation efficiency of Ag and Au nanoparticles, which is defined by the ratio of the scattering cross-section to the extinction one. The calculations were performed using Mie theory formalism for surrounding medium of var...

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Published in:Semiconductor Physics Quantum Electronics & Optoelectronics
Date:2010
Main Authors: Dmitruk, N.L., Malynych, S.Z., Moroz, I.E., Kurlyak, V.Yu.
Format: Article
Language:English
Published: Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України 2010
Online Access:https://nasplib.isofts.kiev.ua/handle/123456789/118553
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Cite this:Optical efficiency of Ag and Au nanoparticles / N.L. Dmitruk, S.Z. Malynych, I.E. Moroz, V.Yu. Kurlyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 369-373. — Бібліогр.: 14 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-118553
record_format dspace
spelling Dmitruk, N.L.
Malynych, S.Z.
Moroz, I.E.
Kurlyak, V.Yu.
2017-05-30T16:06:29Z
2017-05-30T16:06:29Z
2010
Optical efficiency of Ag and Au nanoparticles / N.L. Dmitruk, S.Z. Malynych, I.E. Moroz, V.Yu. Kurlyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 369-373. — Бібліогр.: 14 назв. — англ.
1560-8034
PACS 78.67.Bf, 81.07.Bc
https://nasplib.isofts.kiev.ua/handle/123456789/118553
In this paper, we present the results of calculations aimed at the optical radiation efficiency of Ag and Au nanoparticles, which is defined by the ratio of the scattering cross-section to the extinction one. The calculations were performed using Mie theory formalism for surrounding medium of various refractive indexes. It has been shown that silver nanoparticles exhibit substantially larger optical efficiency in a broad spectral range as compared to gold nanoparticles. The optical efficiency for silver nanoparticles with diameters over 90 nm exceeds 90%.
We thank Prof. G. Chumanov (Clemson University, USA) for collaboration and fruitful discussions.
en
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
Semiconductor Physics Quantum Electronics & Optoelectronics
Optical efficiency of Ag and Au nanoparticles
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Optical efficiency of Ag and Au nanoparticles
spellingShingle Optical efficiency of Ag and Au nanoparticles
Dmitruk, N.L.
Malynych, S.Z.
Moroz, I.E.
Kurlyak, V.Yu.
title_short Optical efficiency of Ag and Au nanoparticles
title_full Optical efficiency of Ag and Au nanoparticles
title_fullStr Optical efficiency of Ag and Au nanoparticles
title_full_unstemmed Optical efficiency of Ag and Au nanoparticles
title_sort optical efficiency of ag and au nanoparticles
author Dmitruk, N.L.
Malynych, S.Z.
Moroz, I.E.
Kurlyak, V.Yu.
author_facet Dmitruk, N.L.
Malynych, S.Z.
Moroz, I.E.
Kurlyak, V.Yu.
publishDate 2010
language English
container_title Semiconductor Physics Quantum Electronics & Optoelectronics
publisher Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
format Article
description In this paper, we present the results of calculations aimed at the optical radiation efficiency of Ag and Au nanoparticles, which is defined by the ratio of the scattering cross-section to the extinction one. The calculations were performed using Mie theory formalism for surrounding medium of various refractive indexes. It has been shown that silver nanoparticles exhibit substantially larger optical efficiency in a broad spectral range as compared to gold nanoparticles. The optical efficiency for silver nanoparticles with diameters over 90 nm exceeds 90%.
issn 1560-8034
url https://nasplib.isofts.kiev.ua/handle/123456789/118553
citation_txt Optical efficiency of Ag and Au nanoparticles / N.L. Dmitruk, S.Z. Malynych, I.E. Moroz, V.Yu. Kurlyak // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2010. — Т. 13, № 4. — С. 369-373. — Бібліогр.: 14 назв. — англ.
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first_indexed 2025-11-25T22:46:31Z
last_indexed 2025-11-25T22:46:31Z
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fulltext Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 369-373. PACS 78.67.Bf, 81.07.Bc Optical efficiency of Ag and Au nanoparticles  N.L. Dmitruk1, S.Z. Malynych1, I.E. Moroz2, V.Yu. Kurlyak3 1V. Lashkaryov Institute of Semiconductors Physics, NAS of Ukraine, 41, prospect Nauky, 03028 Kyiv, Ukraine Phone: +38(044) 525-64-86, e-mail: s.malynych@gmail.com, dmitruk@isp.kiev.ua 2National University “Lviv Polytechnica”, 12, S. Bandery str., 79013 Lviv, Ukraine 3Ivan Franko Lviv National University, 8, Kyryla & Methodiya str., 79005 Lviv, Ukraine Abstract. In this paper, we present the results of calculations aimed at the optical radiation efficiency of Ag and Au nanoparticles, which is defined by the ratio of the scattering cross-section to the extinction one. The calculations were performed using Mie theory formalism for surrounding medium of various refractive indexes. It has been shown that silver nanoparticles exhibit substantially larger optical efficiency in a broad spectral range as compared to gold nanoparticles. The optical efficiency for silver nanoparticles with diameters over 90 nm exceeds 90%. Keywords: metal nanoparticles, optical properties, light scattering. Manuscript received 02.06.10; accepted for publication 02.12.10; published online 30.12.10. 1. Introduction Tendency towards miniaturization of various electronic devices as well as the development of experimental methods for manufacturing and characterization of nanoscale systems instigate growing interest to studying their physical properties. Metal nanoparticles, especially gold and silver are the most promising for practical applications. It is well known that visible light excites collective oscillations of free electrons inside metal particles, which are Localized Surface Plasmon Resonances (LSPR). In other words, LSPR are coupled oscillations of the electron density and electromagnetic waves. The excitation of LSPR in metal nanoparticles represents the most efficient process by which light interacts with matter and defines optical properties of nanoparticles. It is also very important that LSPR frequency could be successfully tuned within a broad spectral range by varying the refractive index of surrounding medium or by using the nanoparticles of different size and shape [1]. For gold and silver nanoparticles, the resonance falls into the visible region of electromagnetic spectrum. A striking consequence of this fact is bright colors exhibited by particles immersed into transparent matrix (e.g., aqueous suspensions or glass) both in transmitted and reflected light. Up to date, it has been proposed a number of practical applications of gold and silver nanoparticles and nanoparticle arrays for needs of photonics [2], nonlinear spectroscopy [3], submicron visualization [4], surface-enhanced Raman and infrared spectroscopy [5, 6], photovoltaics [7], and various sensors [8]. The fundamental background of all the mentioned processes is a resonant enhancement of light interaction with metal nanoparticles, and it is crucial to minimize the losses caused by absorption of incident light, wasted as heat, by the metal nanoparticles for efficient energy transfer into the active materials. It is proposed to use the ratio of the scattering cross-section to the extinction cross-section as a quantitative parameter that describes efficiency of energy transfer [9]. This ratio or optical radiation efficiency represents the fraction of the energy reradiated from the particle out from the energy of the incident light. 2. Localized surface resonances in metal nanoparticles As opposed to the surface plasmon-polaritons that are actually electromagnetic waves coupled to the electron plasma of a conductor and propagating along the metal– dielectric interface plasmons in the subwavelength metal nanoparticles are localized collective oscillations of conducting electrons. The curved surface of the particle exerts an effective restoring force on the driven electrons, so that a resonance can arise, leading to field amplification both inside and in the near-field zone outside the particle. As a consequence, there is an effective scattering of incident light by metal nanoparticles just at the LSPR frequency. It also means © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 369 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 369-373. that LSPR could be excited directly by incident light without any phase matching techniques, as it is required in the case of surface plasmon-polaritons. Light extinction by small metal nanoparticles of the spherical shape can be described using simple quasi- static approximation provided that R << λ. In that case polarizability defined as m mR ε+ε ε−ε πε=α 2 4 3 0 , where ε0 is the vacuum permittivity, α is the polarizability of particles, R – radius of the particle, ε and εm are the permittivities of the particle and surrounding medium, respectively, λ is the wavelength in vacuum. It is apparent that the polarizability experiences a resonant enhancement under the condition that the denominator is minimal, i.e. Re[ε(ω)] = –2εm (Fröhlich condition). Again, this expression is valid for very small (R << λ) particles. In this case, the phase of the harmonically oscillating electromagnetic field is practically constant over the particle volume, so that one can calculate the spatial field distribution by assuming the simplified problem of a particle in an electrostatic field. Then, the harmonic time dependence can be added to the solution, once the field distributions are known. This oscillation mode is exactly the dipole surface plasmon of metal nanoparticle. Tanabe [9] used quasi- static approximation to calculate the optical radiation efficiency of nanoparticles for a number of metals at fixed wavelengths. However, for larger particles quasi-static approximation is no longer valid due to retardation effects, so a rigorous electrodynamic approach is required. Such a theory was firstly developed by G. Mie as early as in 1908. Nowadays, that theory is widely used and is treated in a variety of books [10]. According to the Mie theory, extinction, scattering, and absorption cross-sections can be calculated by series expansion of the internal and scattered fields into a set of partial waves described by vector harmonics: ( ) ( LL L ext baL k C ++ π = ∑ ∞ = Re122 1 2 © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine ) , ( )( )22 1 2 122 LL L sca baL k C ++ π = ∑ ∞ = , scaextabs CCC −= , with ( ) ( ) ( ) ( ) ( ) ( ) ( )mxxmxm mxxxmxma LLLL LLLL L ψ′ξ−ξ′ψ ψ′ψ−ψ′ψ′ψ = ( ) ( ) ( ) ( ) ( ) ( ) ( )mxxmmx mxxmxmxb LLLL LLLL L ψ′ξ−ξ′ψ ψ′ψ−ψ′ψ = , where m = n/nm, n and nm – are he complex refractive index of the nanoparticle and real refractive index of the surrounding medium, respectively, k is the wave vector, x = ⏐k⏐R – size parameter, ψL, ξL are Riccati-Bessel cylindrical functions. The prime indicates differentiation with respect to the argument. The summation index L gives the order of the partial wave, L = 1 corresponds to dipole fields, L = 2 – to quadrupole, L = 3 – to octupole fields, and so on. Thus, by calculating the values of the extinction and scattering cross-sections one can obtain the optical radiation efficiency of nanoparticles: abssca sca ext sca opt CC C C C + ==η . 3. Results and discussion The calculations of the extinction and scattering cross- sections by Ag and Au nanoparticles where performed using the modified version of Mie solution code [11]. For many practical purposes, especially in biophysics and sensorics, it is necessary to take into account the influence of surrounding medium on optical properties of nanoparticles. Fig. 1 depicts spectral dependences of the optical radiation efficiency ηopt for spherical gold and silver nanoparticles of various diameters immersed into different surrounding media, namely: air, water, and fused silica. Note that optical efficiency of Au nanoparticles spreads over substantially narrower spectral range due to the strong interband transition at ~2.4 eV (515 nm). It is seen from Fig. 1 that the optical efficiency of Au and Ag nanoparticles has a trend to increase with increasing the particles’ diameter. It occurred firstly due to increasing of the polarizability of larger particles, secondly as a consequence of fast scaling of the scattering cross-section (~R6) as compared to R3 scaling of the absorption cross-section [12]. Calculations of the electric field distribution around the particle also confirm the size influence on the optical efficiency. In Fig. 2, the electric field distribution around Ag nanoparticles with the diameters 60 and 100 nm is shown. The curves correspond to the electric field distribution along Oy direction, while incident beam propagates along z direction with polarization plane xz. One can see that for larger particles the electric field close to the particle’s surface is more strong leading to the enhancement of the light-nanoparticle interaction. Thus, 100-nm silver nanoparticles act as more efficient scatterers. The calculations were performed employing field simulator freely available online [13]. Apparently, the size of the particles cannot be increased indefinitely where geometrical optics laws take place, while in Mie theory formalism the particles must be smaller than the optical wavelength. Quasi-static approximation also yields only rough values of the optical efficiency. From the calculations performed by Tanabe [9], it follows that the optical efficiency of silver nanoparticles in the visible spectral range exceeds 90%, 370 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 369-373. Fig. 1. Optical radiation efficiency of Ag (left-hand panel) and Au (right-hand panel) nanoparticles in air (nm = 1), water (nm = 1.33) and fused silica (nm = 1.46). The lowest curves in all the plots correspond to the particles diameter of 20 nm, while the highest ones to the diameter of 200 nm with the 10-nm step. when the particles’ diameter reaches 150 nm. This value is rather underestimated, since the corresponding diameter obtained from the Mie theory amounts 90 nm. Fig. 3 depicts the diagram particle diameter – spectral range that represents the lines of the same optical efficiency of Ag and Au nanoparticles in air at 90 and 95%. Surrounding medium constitutes another important issue, which determines optical properties of the nanoparticles. Its influence was thoroughly studied in [1, 13]. In particular, it has been shown that the extinction maxima in the wavelength scale red-shift linearly with increasing the refractive index of the medium [13]. In the cited papers, only spectral position of the extinction maxima with nm is discussed, while the absolute values of the maxima are not considered. It is established that extinction (scattering) cross-sections increase with increasing nm. Fig. 1 demonstrates that optical efficiency curves do not exhibit notable spectral changes in different surrounding media. Besides, the values of ηopt increase with increasing the refractive index of surroundings. It can be explained from the fact that metals possess the negative permittivity. In that case, the optical contrast increases with increasing nm following by domination of scattering over the absorption. In a sense, surrounding © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 371 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 369-373. medium amplifies the effect from metal nanoparticles. Augmentation of the optical efficiency due to increasing of nm is more notable for the particles with a diameter of 20-70 nm. For larger particles, the increase of the optical efficiency with the refractive index of surrounding medium is less pronounced. Fig. 2. Electric field distribution around 60-nm ( ) and 100- nm ( ) diameter silver nanoparticles embedded in air (nm = 1). R and R0 denote a distance from the surface of the particle and radius of the particle, respectively. © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine Fig. 3. The diagram diameter – spectral range representing the optical efficiency of 90-nm Ag and Au nanoparticles in air. The same intensity lines of the optical efficiency at the values of 0.9 and 0.95 are shown. 4. Conclusions The optical radiation efficiency of metal nanoparticles or energy fraction of the incident light reradiated from the particle, but not wasted as heat due to absorption is one of the important characteristic of the nanoparticles. Using the Mie theory, we calculated the extinction and scattering cross-sections of gold and silver spherical nanoparticles of various diameters and obtained optical efficiencies defined by the ratio of the scattering cross- section to the extinction cross-section. The calculations were performed for different surrounding media, namely: air, water, and fused silica. Silver nanoparticles exhibit a larger optical efficiency in a broad spectral range than the gold ones of the same diameter. The optical efficiency for both metals has a trend to increase with growing the particles’ size. For 90-nm silver nanoparticles, the optical efficiency exceeds 90% over the whole visible range. The optical efficiency of Au and Ag nanoparticles increases, when nanoparticles are embedded into the medium with higher refractive index. The obtained data might be useful for the selection of materials and sizes of nanoparticles for various photonics devices. Acknowledgments We thank Prof. G. Chumanov (Clemson University, USA) for collaboration and fruitful discussions. References 1. K.L. Kelly, E. Coronado, L.L. Zhao, and G.C. Schatz, The optical properties of metal nanoparticles: The influence of size, shape, and dielectric environment // J. Phys. Chem. B 107, p. 668-677 (2003). 2. W.L. Barnes, A. Dereux, T.W. Ebbesen, Surface plasmon subwavelength optics // Nature 424, p. 824-830 (2003). 3. H. Shen, B. Cheng, G. Lu, et al., Enhancement of optical nonlinearity in periodic gold nanoparticle arrays // Nanotechnology 17, p. 4274-4277 (2006). 4. R.J. Blaikie, D.O.S. Melville, Imaging through planar silver lenses in the optical near field // J. Opt A: Pure Appl. Opt. 7, p. S176-S183 (2005). 5. W.E. Doering, S.M. Nie, Single-molecule and single-nanoparticle SERS: examining the roles of surface active sites and chemical enhancement // J Phys Chem B 106, p. 311-317 (2002). 6. T.R. Jensen, R.P. Van Duyne, S.A. Jonson, V.A. Maroni, Surface-enhanced infrared spectroscopy: a comparison of metal island films with discrete and nondiscrete surface plasmons // Appl. Spectrosc. 54, p. 371-377 (2000). 7. K.R. Catchpole, A. Polman, Plasmonic solar cells // Optics express 16(26), p. 21793-21800 (2008). 372 Semiconductor Physics, Quantum Electronics & Optoelectronics, 2010. V. 13, N 4. P. 369-373. 8. S. Malynych, G. Chumanov, Coupled planar silver nanoparticle arrays as refractive index sensors // J. Opt. A: Pure Appl. Opt. 8, p. S144-S147 (2006). 9. K. Tanabe, Optical radiation efficiencies of metal nanoparticles for optoelectronic applications // Materials Letters 61, p. 4573-4575 (2007). 10. C.F. Bohren, D.R. Huffman, Absorption and Scattering of Light by Small Particles. John Wiley & Sons, Inc., 1983, p. 530. 11. J. Camden, G.C. Schatz, Nanosphere Optics Lab // DOI: 10254/nanohub-r1309.2 (2006). 12. S.A. Maier, Localized Surface Plasmons, Chap. 5, in: Plasmonics: Fundamentals and Applications. Springer, 223, 2007, p. 65-88. 13. B. Tejerina; T. Takeshita; L. Ausman, G.C. Schatz, Nanosphere Optics Lab Field Simulator // DOI: 10254/nanohub-r3056.2 (2007). 14. T.R. Jensen, M.L. Duval, K.L. Kelly, A.A. Lazarides, G.C. Schatz, R.P. Van Duyne, Nanosphere lithography: Effect of the external dielectric medium on the surface plasmon resonance spectrum of a periodic array of silver nanoparticles // J. Phys. Chem. B 103, p. 9846- 9853 (1999). © 2010, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine 373