Open access peer-reviewed chapter

Modeling the Bulk and Nanometric Dielectric Functions of Au and Ag

Written By

Brahim Ait Hammou, Abdelhamid El Kaaouachi, Abdellatif El Oujdi, Adil Echchelh, Said Dlimi, Chi-Te Liang and Jamal Hemine

Submitted: 07 January 2021 Reviewed: 20 January 2021 Published: 08 June 2021

DOI: 10.5772/intechopen.96123

From the Edited Volume

Magnetic Skyrmions

Edited by Dipti Ranjan Sahu

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Abstract

In this work, we model the dielectric functions of gold (Au) and silver (Ag) which are typically used in photonics and plasmonics. The modeling has been performed on Au and Ag in bulk and in nanometric states. The dielectric function is presented as a complex number with a real part and an imaginary part. First, we will model the experimental measurements of the dielectric constant as a function of the pulsation ω by appropriate mathematical functions in an explicit way. In the second part we will highlight the contributions to the dielectric constant value due to intraband and interband electronic transitions. In the last part of this work we model the dielectric constant of these metals in the nanometric state using several complex theoretical models such as the Drude Lorentz theory, the Drude two-point critical model, and the Drude three-point critical model. We shall comment on which model fits the experimental dielectric function best over a range of pulsation.

Keywords

  • Modeling bulk and nanometric dielectric function
  • noble metals Au and Ag
  • interband transitions
  • intraband transitions
  • UV and IR pulsations

1. Introduction

All the intrinsic effects corresponding to the process of light-matter interaction are contained in the dielectric function εω. In the case of an isotropic material, the optical response is described by following equation

εω=ε1ω+iε2ωE1

where εω is generally a complex scalar value which depends upon the pulsation ω of the field. If the medium has an anisotropy, this magnitude is in the form of a tensor. It is often convenient to describe the optical response in an equivalent way from the complex refractive index n˜=n+ as n denotes the refractive index describing the phase speed of the wave and κ denotes the extinction index describing the absorption of the wave during propagation in the material. These two indices are directly related to the dielectric constant of the material. In fact, the real and imaginary parts of the dielectric function are deduced from the relation:

ε1=n2κ2E2
ε2=2E3

Several important physical quantities can be deduced from the complex refractive index n˜ and dielectric function εω such as the reflectivity coefficient R and the attenuation coefficient α. In the fields of photonics, and plasmonics, researchers use the dielectric function in their calculations and investigations [1, 2, 3, 4, 5, 6, 7, 8].

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2. Modeling of the bulk experimental dielectric function

Here we try to model the experimental dielectric function εexpω of noble metals (Ag and Au) on a wide pulse interval ω with adequate mathematical functions. We consider the measured values of the dielectric function reported by Dold and Mecke [9], Winsemius et al. [10], Leveque et al. [11], and Thèye et al. [12] respectively. These measurements are summarized by Rakiç et al. [13] in Figure 1 (for Ag), and in Figure 2 (for Au).

Figure 1.

Real part () and imaginary part () of the dielectric function of bulk Ag ([adapted] with permission from [Ref. [13])© The Optical Society.

Figure 2.

Real part() and imaginary part () of the dielectric function of bulk Au([adapted] with permission from [Ref. [13])© The Optical Society.

2.1 Modeling the experimental dielectric function of bulk Ag

In this part, we will model the real and imaginary parts of the experimental dielectric function of Ag (Figure 1). For this we will divide the values of the pulsation ω into several intervals in order to allow us to determine the best fit to suitable mathematical functions over a certain interval. All the results will be presented in Tables 18.

ParameterεR00A1t1(rad/s)A2t2(rad/s)R-Square (COD)
Value10499.713−1300.8763.813 × 1014−9163.3201.217 × 10140.9999

Table 1.

Values of the model parameters.

ParameterεR01A1't1'(rad/s)A2't2'(rad/s)A3t3(rad/s)R-Square (COD)
Value0.30583.3921.091 × 101586.0231.091 × 101586.6391.091 × 10150,99101

Table 2.

Values of the model parameters.

ParameterεR02A1''t1'' (rad/s)A2''t2'' (rad/s)R-Square (COD)
Value5.281−0.006−9.588 × 1014−0.006−9.576 × 10140.99671

Table 3.

Values of the model parameters.

ParameterεR03AωC (rad/s)B (rad/s)R-Square (COD)
Value0.8680.735−9.816 × 10143.483 × 10140.96592

Table 4.

Values of the model parameters.

ParameterεR04ωC (rad/s)Hω1 (rad/s)ω2 (rad/s)R-Square (COD)
Value2.5397.140 × 1015−2.3996.978 × 10143.783 × 10240.99613

Table 5.

Values of the model parameters.

ParameterεI00B1ω0 (rad/s)V1 (rad/s)R-Square (COD)
Value−23218.730585.7842.267 × 10146.910 × 10130.99998
B2V2 (rad/s)B3V3 (rad/s)
306.1001.844 × 101423235.3802.514 × 1018

Table 6.

Values of the model parameters.

ParameterεI01BTD (rad/s)τ (rad/s)R-Square (COD)
Value7.076−6.3271.38101 × 10154.92416 × 10140.9983

Table 7.

Values of the model parameters.

ParameterB1'B2'pLnω01 (rad/s)h1 (rad/s)−1Lnω02 (rad/s)
Value1.2781.633−8.8119.897 × 10151.262 × 10–166.159 × 1015
h2 (rad/s)−1R-Square (COD)
3.945 × 10–150.99733

Table 8.

Values of the model parameters.

2.1.1 Modeling the real part of the bulk dielectric function of Silver εRAgexpω

For 1,899×1014rad/sω1,275×1015rad/s

εRAgexpω=εR00+A11eω/t1+A21eω/t2E4

For 1,275×1015rad/sω4,873×1015rad/s

εRAgexpω=A1'eω/t1'+A2'eω/t2'+A3eω/t3+εR01E5

For 4.873×1015rad/sω5.650×1015rad/s

εRAgexpω=A1''eω/t1''+A2''eω/t2''+εR02E6

For 5.650×1015rad/sω6.198×1015rad/s

εRAgexpω=εR03+AsinπωωCBE7

For 6.198×1015rad/sω7.605×1015rad/s

εRAgexpω=εR04+He12ωωCω12forω<ωCεRAgexpω=εR04+He12ωωCω22forωωCE8

2.1.2 Modeling the imaginary part of the bulk dielectric function of Silver εIAgexpω

For 1,900×1014rad/sω1,340×1015rad/s

εIAgexpω=εI00+B1eωω0/V1+B2eωω0/V2+B3eωω0/V3E9

For 1.340×1015rad/sω4.251×1015rad/s

εIAgexpω=εI01forω<TDεIAgexpω=εI01+B1eωTDτ forωTDE10

For 4.252×1015rad/sω7.453×1015rad/s

εIAgexpω=B1'+B2'B1'p1+10Lnω01ωh1+1p1+10Lnω02ωh2E11

2.2 Modeling the experimental dielectric function of bulk Au

In this section, we will model the real and imaginary parts of the experimental dielectric function of bulk Au (Figure 2). For this we will proceed in the same way as for bulk Ag by dividing the values of the pulsation ω into various intervals. All the results are listed in Tables 915.

Parametera0a1 (rad/s)−1a2(rad/s)−2a3 (rad/s)−3a4 (rad/s)−4R-Square (COD)
Value4835.830−8.633 × 10−12−6.930 × 10−263.779 × 10−40−8.746 × 10−55
a5 (rad/s)−5a6 (rad/s)−6a7 (rad/s)−7a8 (rad/s)−8a9 (rad/s)−90.9999
1.170 × 10−69−9.674 × 10−854.893 × 10−100−1.392 × 10−1151.710 × 10−131

Table 9.

Values of the model parameters.

Parametera1'a2'qLnω'01 (rad/s)g1 (rad/s)−1Lnω'02 (rad/s)g2 (rad/s)−1R-Square (COD)
Value7.786138.1060.8961.495 × 1015−1.388 × 10−152.641 × 1015−3.366 × 10−150.9996

Table 10.

Values of the model parameters.

Parameterb0b1 (rad/s)−1b2 (rad/s)−2b3 (rad/s)−3b4 (rad/s)−4b5 (rad/s)−5R-Square (COD)
Value−50227.4826.432 × 10−11−3.281 × 10−268.338 × 10−42−1.056 × 10−575.337 × 10−740.9997

Table 11.

Values of the model parameters.

Parameterc0c1 (rad/s)−1c2 (rad/s)−2c3 (rad/s)−3c4 (rad/s)−4R-Square (COD)
Value271340.234−4.224 × 10−102.912 × 10−25−1.167 × 10−402.995 × 10−56
c5 (rad/s)−5c6 (rad/s)−6c7 (rad/s)−7c8 (rad/s)−8c9 (rad/s)−90.99872
−5.112 × 10−725.801 × 10−88−4.220 × 10−1041.786 × 10−120−3.351 × 10−137

Table 12.

Values of the model parameters.

Parameterd0d1 (rad/s)−1d2 (rad/s)−2d3 (rad/s)−3d4 (rad/s)−4R-Square (COD)
Value9873.897−9.845 × 10−114.479 × 10−25−1.188 × 10−392.002 × 10−54
d5 (rad/s)−5d6 (rad/s)−6d7 (rad/s)−7d8 (rad/s)−8d9 (rad/s)−90.9999
−2.212 × 10−691.598 × 10−84−7.276 × 10−1001.895 × 10−115−2.152 × 10−131

Table 13.

Values of the model parameters.

Parameterf0f1 (rad/s)−1f2 (rad/s)−2f3 (rad/s)−3f4 (rad/s)−4f5 (rad/s)−5R-Square (COD)
Value115.516−1.891 × 10−131.299 × 10−28−4.538 × 10−447.892 × 10−60−5.361 × 10−760.9973

Table 14.

Values of the model parameters.

Parameterj0j1 (rad/s)−1j2 (rad/s)−2j3 (rad/s)−3j4 (rad/s)−4R-Square (COD)
Value−53432.0591.046 × 10−13−8.722 × 10−264.106 × 10−41−1.210 × 10−56
j5 (rad/s)−5j6 (rad/s)−6j7 (rad/s)−7j8 (rad/s)−8j9 (rad/s)−90.9974
2.324 × 10−72−2.918 × 10−882.316 × 10−104−1.056 × 10−1202.111 × 10−137

Table 15.

Values of the model parameters.

2.2.1 Modeling the real part ofthe bulk dielectric function of Gold εRAuexpω

For 3.319×1014rad/sω1.515×1015rad/s

εRAuexpω=a0+a1ω+a2ω2+a3ω3+a4ω4+a5ω5+a6ω6+a7ω7+a8ω8+a9ω9E12

For 1.515×1015rad/sω3.345×1015rad/s

εRAuexpω=a1'+a2'a1'q1+10Lnω'01ωg1+1q1+10Lnω'02ωg2E13

For 3.345×1015rad/sω4.271×1015rad/s

εRAuexpω=b0+b1ω+b2ω2+b3ω3+b4ω4+b5ω5E14

For 4.271×1015rad/sω7.560×1015rad/s

εRAuexpω=c0+c1ω+c2ω2+c3ω3+c4ω4+c5ω5+c6ω6+c7ω7+c8ω8+c9ω9E15

2.2.2 Modeling the imaginary part ofthe bulk dielectric function of Gold εIAuexpω

For 3.047×1014rad/sω1.511×1015rad/s

εIAuexpω=d0+d1ω+d2ω2+d3ω3+d4ω4+d5ω5+d6ω6+d7ω7+d8ω8+d9ω9E16

For 1.511×1015rad/sω4.265×1015rad/s

εRAuexpω=f0+f1ω+f2ω2+f3ω3+f4ω4+f5ω5E17

For 4.265×1015rad/sω7.560×1015rad/s

εIAuexpω=j0+j1ω+j2ω2+j3ω3+j4ω4+j5ω5+j6ω6+j7ω7+j8ω8+j9ω9E18

All the results of these different models for both bulk Ag and bulk Au are plotted in the following Figures 3 and 4.

Figure 3.

Real () and imaginary () parts of the experimental dielectric function of bulkAg (Ref. [13]). Solid colored curves represent, by pulse intervals, the different mathematical models used in the modeling.

Figure 4.

Real () and imaginary () parts of the experimental dielectric function of bulkAu (Ref. [13]). Solid colored curves represent, by pulse intervals, the different mathematical models used in the modeling.

In both cases, the experimental results can be well fitted by the models of experimental dielectric function in both its real and imaginary parts with mathematical functions with high accuracy.

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3. Highlighting the contribution of interband and intraband transitions in the expression of dielectric function

In metals, there aretwo types of contribution in the dielectric function, namely contribution of interband transitions denoted εiBω and that of the intraband transitions denoted εDω. The dielectric function can be written as the sum of two terms

εω=εDω+εiBωE19

The first term corresponds to the intraband component of the dielectric function. It is referred to the optical transitions of a free electron from the conduction band to a higher energy level of the same band. The second term corresponds to the interband component of the dielectric constant. It is referred to optical transitions between the valence bands (mainly d band and s-p conduction bands). Due to Pauli’s exclusion principle, an electron from a valence band can only be excited to the conduction band. There is therefore an energy threshold EIB for interband transitions which is placed in the visible band for Au and near the UV region for Ag. This component is often overlooked in the infrared range (this is valid only for alkali metals) where the optical response is dominated by intraband absorption. This type of transitions dominates the optical response beyond EIB.

The intraband part εDω of the dielectric function is described by the well-known free-electronorDrude Model [14]:

εDω=1ωp2ωω+E20

where γ is the collision rate (probability of collision per unit of time). εω = ε1ω + iε2ω.

We note that γ=τ1 and τ is the elastic diffusion time

τ=l0vfE21

where l0 is the mean free path of electrons and vf is the Fermi speed.

In the Drude model, there appears a pulsation called the plasmon frequency of a bulk metal given by

ωp=nce2ε0meffE22

Where ε0 is dielectric constant in vacuum.

The electronic structure of bulk noble metals such as Ag and Au, the respective values of the conduction electron density nc, the effective mass meff, the Fermi speed vf conduction electrons and the mean free path of electron l0, are listed in the following Table 16 [15]:

3.1 Contribution of intraband transitions to dielectric function

The intraband dielectric function described by the Drude model [14] as denoted εDω can be written as

εDω=εRDω+iεIDωE23

The real and imaginary parts of the relative dielectric function (intraband) are written as follows

εRDω=1ωp2ω2+γ2E24
εIDω=ωp2γωω2+γ2E25

Usually, for noble metals ωγ in the near UVrange and up to the near IR, we can write

εRDω=1ωp2ω2E26
εIDω=ωp2γω3E27

The following Table 17 shows the values of plasma frequencies and the collision rate of noble metals (Gold, Silver):

Metalnc×1028m3meffmevfnm/fsl0nm
Ag5.860.961.3955
Au5.900.991.4042

Table 16.

Electronic properties of Ag and Au.

From Phys. Review B.6. 4376(1972).

Metalωp2 (rad/s)2γ (s−1)
Ag1.9428×10322.5273×1013
Au1.8968×10323.3333×1013

Table 17.

Plasma frequency and collision rate values for Ag and Au.

The results of the calculations of the contribution of intraband effects to dielectric function are represented in their real and imaginary parts for bulk Ag (Figure 5) and for bulk Au (Figure 6).

Figure 5.

Real () imaginary part () of the intraband dielectric function of bulk Ag.

Figure 6.

Real () imaginary part () of intraband dielectric function of bulk Au.

For the noble metals (Gold, Silver), we observed that the real and imaginary parts decrease withincreasing pulsation. The further away from the pulsations corresponding to IR radiation and the closer we get to the pulsations corresponding to UV radiation, these values decrease.

3.2 Contribution of interband transitions to dielectric function

The interband dielectric function denoted εiBω is described by the following term

εiBω=εRiBω+iεIiBωE28

The real and imaginary parts of the interband dielectric function are written respectively as follows:

εRiBω=εRexpωεRDωE29
εIiBω=εIexpωεIDωE30

where

εexpω=εRexpω+iεIexpωE31

Here εexpω,εRexpω,andεIexpω are the experimental values, real and imaginary parts of the complex dielectric function, respectively.

The results of the calculations of the contribution of interband transitions to real and imaginary parts of dielectric function are represented respectively for bulk Ag (Figure 7) and for bulk Au (Figure 8).

Figure 7.

Real () and imaginary part () of the interband dielectric function of bulk Ag.

Figure 8.

Real () and imaginary part () of the interband dielectric function of bulk Au.

As shown in Figure 7, the real part of the contribution of interband effects to the dielectric function of bulk Ag decreases with increasing pulsation in the IR radiation domain then is still almost constant with small variations from ω=1.5×1015rad/s and this until the end of the UV radiation range. Concerning the imaginary part of this contribution, it is almost less important than the real part. It decreases with increasing pulsation in the range corresponding to IR radiation, then varies very little to the value of the pulsation ω=6×1015rad/s in the range of UV radiation, in this area increase from 0.4 to 1.4 and finally remains constant for the rest of the UV pulses. The imaginary part becomes superior to the real part for UV pulses higher than the value ω=6×1015rad/s.

We note that for Gold, the real and imaginary parts of the contribution of interband transitions decrease by increasing the values of the pulses in the IR domain to the value ω=4.5×1015rad/s with a real part almost higher than the imaginary part. For pulsation values in the UV range above the value ω=4.5×1015rad/s, with a slight variation the imaginary part becomes superior to the real part.

In Figures 9 and 10 (for Ag) and Figures 11 and 12 (for Au), we have presented experimental values, the contributions of intraband and interband transitions to the real and imaginary parts of the dielectric function.

Figure 9.

Real parts of the dielectric function of Ag: experimental values () ([Ref. [13]), intraband transitions (), interband transitions ().

Figure 10.

Imaginary parts of the dielectric function of Ag: experimental values () ([Ref. [13]), intraband transitions (), interband transitions ().

Figure 11.

Real parts of the dielectric function of Au: experimental values () ([Ref. [13]), intraband transitions (),interband transitions ().

Figure 12.

Imaginary parts of the dielectric function of Au: experimental values () ([Ref. [13]), intraband transitions (),interband transitions ().

Concerning the real part, we note that, the real part due to the intraband transitions noted εRDω is in very good agreement with the experimental values in the full domain corresponding to IR radiation and up to the value ω=4×1015rad/s. In this range of pulsations, we can conclude that the participation in the dielectric function due to inter-band transitions is negligible compared to that of intra-band transitions. For ω>4.5×1015rad/s in the range of UV radiation, the two contributions due to intraband and interband transitions are equivalent but differ from the experimental measurements.

Concerning the imaginary part, we note that the imaginary part due to the interband transitions noted εIiBω is practically confused with the imaginary experimental part in the whole field of pulsations from the IR domain to the end of the UV domain. This indicates that the imaginary part due to intraband transitions is negligible compared to the imaginary part due to interband transitions.

For Gold, we note that, the real part due to the intraband transitions noted εRDω is in very good agreement with the real experimental values in the whole range corresponding to IR radiation and up to the value ω=2×1015rad/s. In this range of pulsations, we can conclude that the participation in the dielectric function due to interband transitions is negligible compared to that of intraband transitions. For ω>2×1015rad/s and up to the UV radiation domain, the two contributions due to intraband and interband transitions differ significantly from the experimental measurements. These two contributions are very similar in the field of UV for ω2.5×1015rad/s.

Concerning the imaginary part, as for Silver, we see that the imaginary part due to the interband transitions noted εIiBω is practically confused with the imaginary experimental part in the whole field of pulsations from the IR domain to the end of the UV domain. This indicates that the imaginary part due to intraband transitions is negligible compared to the imaginary part due to interband transitions.

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4. Modeling the dielectric functions of nanometri cAg and nanometric Au

In this section, we study the dielectric functions of nanometric Ag and nanometric Au. They are composed of a few tens to several thousand atoms. Their very small characteristic dimensions, in the nanometer range (i.e. well under optical wavelengths), give rise to extraordinary electronic and optical properties that cannot be observed in bulk materials. These properties are clearly influenced by the size, form of the nanoparticle and the nature of the host environment. We consider the measured values of dielectric function used in the previous paragraphs, and try to model those using theoretical models for nanometals such as the Drude Lorentz (DL) model, the Drude two-point critical model DCP and the Drude three-point critical model DCP3.

The optical properties of metallic nanoparticles are dominated by the collective oscillation of conduction electrons induced by interaction with electromagnetic radiation (IR, UV).

The collective excitation of nanoparticle conduction electrons gives them new optical properties; we consider the following two effects:

  • Plasmons guided along a metallic film of nanometric cross-section (1D confinement).

  • Surface plasmons located in a metallic particle of nanometric size (0D confinement).

4.1 Drude Lorentz (DL) model

For the study of resonant nanostructures, it is important to have a good description of the permittivity of the metal in a large frequency band. For this purpose, the validity band of the Drude Model is often extended by adding Lorentzian terms [16] depending in the following form

εDLω=εωD2ω2+iγω+l=12flΩl2Ωl2ω2iΓlωE32

The dielectric function described by the Drude Lorentz model is written as follows

εDLω=εDLRω+iεDLimωE33

where:

The real part of the dielectric function according to the DL model

εDLRω=εωD2ω2+γ2+f1Ω12Ω12ω2Ω12ω22+Γ1ω2+f2Ω22Ω22ω2Ω22ω22+Γ2ω2E34

The imaginary part of the dielectric function according to the DL model:

εDLimω=γωD2ω3+γ2ω+f1Ω12Γ1ωΩ12ω22+Γ1ω2+f2Ω22Γ2ωΩ22ω22+Γ2ω2E35

The studies of Vial and Laroche [16] on the permittivity of Auand Ag metals used in their model with the parameters are listed in Table 18.

εωD
(rad/s)
γ (rad/s)f1
Au6.21371.3323 × 10161.3235 × 10143.4620
Ag1.79841.3359 × 10168.7167 × 10133.0079
Ω1
(rad/s)
Γ1
(rad/s)
f2Ω2
(rad/s)
Γ2
(rad/s)
Au4.7914 × 10152.1367 × 1015−3.48864.2111 × 10144.5572 × 1017
Ag8.1635 × 10154.3785 × 10172.34103.8316 × 10166.0574 × 1016

Table 18.

Optimized parameters of the Drude Lorentz model for noble metals (Au and Ag).

From J. Phys. D. Appl. Phys. 40,7154 (2007).

The results of modeling the experimental dielectric function in its real and imaginary parts using the DL model are shown in Figures 13 and 14 for Au(in Figures 15 and 16 for Ag).

Figure 13.

Real part of the dielectric function of nanometric Ag: experimental values () ([Ref. [13]), the DL model (),the DCP model () and the DCP3model ().

Figure 14.

Imaginary part of the dielectric function of nanometric Ag:experimental values () ([Ref. [13]), the DL model (), the DCPmodel (), and the DCP3 model ().

Figure 15.

Real part of the dielectric function of nanometric Au: experimental values () ([Ref. [13]), the DLmodel (), the DCP model (), and the DCP3 model ().

Figure 16.

Imaginary part of dielectric of nanometric Au: experimental values () ([Ref. [13]), the DL model (), the DCP model (), and theDCP3 model ().

4.2 Drude model with two critical points DCP

In order to describe the metal in the largest possible range of pulsations, another formula describing the two-point critical Drude model (DCP) [16] will appear in this paragraph.

The dielectric function of Au and Ag is can be expressed from as [17]:

εDCPω=εωD2ω2+iγω+l=12AlΩleΩlωiΓl+eΩl+ω+iΓlE36

The dielectric function described by the Drude two-critical-point model is written as follows

εDCPω=εDCPRω+iεDCPimωE37

where

The real part of the dielectric function according to the DCP model:

εDCPRω=εωD2ω2+γ2+l=12AlΩlΩlωcosϕlΓlsinϕlΩlω2+Γl2+Ωl+ωcosϕlΓlsinϕlΩl+ω2+Γl2E38

The imaginary part of the dielectric function according to the DCP model:

εDCPimω=γωD2ω3+γ2ω+l=12AlΩlΩlωsinϕl+ΓlcosϕlΩlω2+Γl2+Ωl+ωsinϕlΓlcosϕlΩl+ω2+Γl2E39

The work of Alexandre Vial’s [17] on the permittivity of the noble metals (Gold, Silver) made model with the parameters are listed in Table 19.

εωD
(rad/s)
γ (rad/s)A1ϕ1
(rad)
Ω1
(rad/s)
Au1.14311.3202 × 10161.0805 × 10140.26698−1.23713.8711 × 1015
Ag15.8331.3861 × 10164.5841 × 10131.0171−0.939356.6327 × 1015
A2ϕ2
(rad)
Ω2
(rad/s)
Γ2
(rad/s)
Γ1
(rad/s)
Au3.0834−1.09684.1684 × 10152.3555 × 10154.4642 × 1014
Ag15.7971.80879.2726 × 10172.3716 × 10171.6666 × 1015

Table 19.

Optimized parameters of the Drude two-point critical point model DCP, dielectric function for noble metals (Gold, Silver).

From Appl. Phys.B 93, 140 (2008).

The results of modeling the experimental dielectric function in its real and imaginary parts using the Drude two-point DCP critical point model are shown in Figures 13 and 14 for Au (in Figures 15 and 16 for Ag).

4.3 Drude model with three critical points DCP3

The DCP3 model describes the response of the dielectric function in a wider pulsation band, it should be noted that the DCP3 model gives a very good description of the dielectric function of noble metals; it is expressed by the relation [18]:

εDCP3ω=ε+σε0+l=13AlΩleΩlωiΓl+eΩl+ω+iΓlE40

The dielectric function described by the Drude two-critical-point model is written as follows:

εDCP3ω=εDCP3Rω+iεDCP3imωE41

Where:

The real part of the dielectric function in the DCP3 model:

εDCP3Rω=ε+l=13AlΩlΩlωcosϕlΓlsinϕlΩlω2+Γl2+Ωl+ωcosϕlΓlsinϕlΩl+ω2+Γl2E42

The imaginary part of the dielectric function in the DCP3 model:

εDCP3imω=σε0ω+l=13AlΩlΩlωsinϕl+ΓlcosϕlΩlω2+Γl2Ωl+ωsinϕl+ΩlcosϕlΩl+ω2+Γl2E43

The parameters of this model are given in Table 20.

εσε0A1ϕ1
(rad)
Ω1
(rad/s)
Γ1
(rad/s)
A2
Au1.115627.8250.55482.84634.506 × 10165.09 × 1016679.7606
Ag1.47838.71911.007−0.96216.617 × 10151.7415 × 10155377.4512
ϕ2
(rad)
Ω2
(rad/s)
Γ2
(rad/s)
A3ϕ3
(rad)
Ω3
(rad/s)
Γ3
(rad/s)
Au−0.09983.4587 × 10143.064E133.52444.65863.5832 × 10151.68784 × 1015
Ag−0.00921.3545 × 10146.56505 × 10122.6077−2.85398.1007 × 10148.7193 × 1012

Table 20.

Optimized parameters of Drude at three critical points DCP3 of the dielectric function of noble metals (Au and Ag).

From Superlattices and Microstructures 47, 67 (2009).

The results of modeling the real and imaginary parts of experimental dielectric function using the Drude three-point critical point model DCP3 are shown in Figures 13 and 14 for Au (in Figures 15 and 16 for Ag).

Concerning the real part of the dielectric function of nanometric Ag; the model that is very much in agreement with the experiment up to the value of the pulsation ω6×1015rad/s, placed in the UV region, is the DCP model. The other models are also valid up to the value of ω3×1015rad/s. This interval covers the whole pulsation zone in the IR domain.

For the imaginary part of nanometric Ag, we find that for pulsations located in the IR domain and less than ω<1.5×1015rad/s, the most appropriate model with experience in this range is the DCP3 model. For pulsation values 1.5×1015rad/s<ω<6×1015rad/s, the most suitable model to the measured values of the dielectric function is still the DCP3 model. For ω>6×1015rad/s in the UV range, the two models DCP and DCP3 are very close to the experiment. The DCP3 model is better than the DCP model.

In the case of the real part of the dielectric function of nanometric Au, the DL, DCP, and DCP3 models are allin very good agreement with the experiment up to the value of the pulsation ω5×1015rad/s; which is the beginning of the UV radiation region. Beyond this value, the three models deviate from the measured values (Figure 15). From the value of ω6.75×1015rad/s two models DCP and DCP3 agree well the experimental values.As shown in Figure 16, concerning the imaginary part of the dielectric function of nanometricAu, we note that the DCP model is in excellent agreement with the experiment over the whole domain of pulsation values including values corresponding to both IR and UV radiation. The DL model is also close to the experimental values up to the value ω5×1015rad/s.

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5. Conclusion

In this work, we modeled the dielectric function of noble metals (silver and gold) in their bulk and nanometric states. Initially, we modeled the measured dielectric functions of these two metals using explicit mathematical functions and the results are in very good agreement with the experiment. Moreover, we have decomposed these measured values of the dielectric functions; in their real and imaginary parts; into several intervals according to the pulsations that sweep the domains corresponding to IR and UV radiation via the intermediate values. The obtained results are very conclusive, and depending on the pulsation domain studied, it is possible to use the corresponding mathematical function in simulations and calculations. Then, we highlighted the importance of the contributions of intraband and interband transitions in dielectric function for both Ag and Au. For Ag, we note that the imaginary part of the dielectric function due to interband transitions denoted εIiBω is almost the same with the imaginary experimental part in the whole field of pulsations from the IR domain to the end of the UV domain. This indicates that the imaginary part due to intraband transitions is negligible compared to the imaginary part due to interband transitions. Concerning the real part of the dielectric function, we note that, the real part due to the intraband transitions noted εRDω is in very good agreement with the real experimental values in the entire range corresponding to IR radiation and up to the value ω=4×1015rad/s. In this range of pulsation, we can conclude that the contribution tothe dielectric function due to interband transitions is negligible compared to that of intraband transitions.

In the case of Au, we note that the real part of the dielectric function due for ω>4.5×1015rad/s and in the field of UV radiation, the two contributions due to intraband and interband transitions are equivalent but they differ from the experiment. to the intraband transitions denoted as εRDω is in very good agreement with the real experimental values over the whole range corresponding to IR radiation and up to the value ω=2.5×1015rad/s. In this range of pulsation, we can conclude that the participation in the dielectric function due to interband transitions is negligible compared to that of intraband transitions. For ω>2.5×1015rad/s and up to the UV radiation domain, the two contributions due to intraband and interband transitions differ significantly from the experimental results. The two contributions are very similar in the field of UV for ω2.5×1015rad/s. Concerning the imaginary part, and as for Ag, we note that the imaginary part due to the interband transitions noted εIiBω is practically the same with the imaginary experimental part in the whole field of pulsations from the IR domain to the end of the UV domain. This indicates that the imaginary part due to intraband transitions is negligible compared to the imaginary part due to interband transitions.

In the last part of this paper, we have modeled the dielectric functions of Ag and Au, using theoretical models that deal with nanometric systems such as the Drude Lorenz model, the Drude two-point critical model, and the Drude three-point critical model.In the case of nanometic Ag, the real part of the dielectric function model agrees well with the experiment up to the value of the pulsation ω6×1015rad/s, which is located in the UV radiation region, is the DCP model. The other models are also valid up to the value of ω3×1015rad/s. This interval covers the entire pulsation zone located in the IR domain. For the imaginary part of Ag, we find that for pulsation located in the IR domain and less than ω<1.5x1015rad/s, the most appropriate model is the DCP3 model. For pulsation values 1.5×1015rad/s<ω<6×1015rad/s, model that deviates the least from the measured values of the dielectric function is still the DCP3 model. For ω>6×1015rad/s in the UV domain, the two models DCP and DCP3 are very close to the experience with a better approach using the DCP3 model.

For nanometric Au, concerning the real part of the dielectric function, the three models DL, DCP, and DCP3 are all in very good agreement with the experiment up to the value of the pulsation ω5×1015rad/s; which is the beginning of the UV radiation region. Beyond this value, the three models deviate from the experiment. From the value of ω6.75×1015rad/s the two models DCP and DCP3 meet the experimental values. Concerning the imaginary part, we note that the DCP model is in very good agreement with the experiment on the whole range of pulsation values including values corresponding to both IR and UV radiation. The DL model is also very close to the experimental values up to the value ω5×1015rad/s.

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Acknowledgments

We are grateful to Professor Uwe Thumm who hosted us for three months in his James R. Macdonald laboratory at the Kansas State University in the USA, and who offered us an opportunity to collaborate on this subject, as part of the Fulbright Grant Merit Award.

References

  1. 1. M. J. Ambrosio and U. Thumm, “Energy-resolved attosecond interferometric photoemission from Ag(111) and Au(111) surfaces,” Phys. Rev. A 97, 043431 (2018).
  2. 2. M. J. Ambrosio and U. Thumm, “Electronic structure effects in spatiotemporally resolved photoemission interferograms of copper surfaces,” Phys. Rev. A 96, 051403(R) (2017).
  3. 3. S. R. Leone, C. W. McCurdy, J. Burgdörfer, L. S. Cederbaum, Z. Chang, N. Dudovich, J. Feist, C. H. Greene, M. Ivanov, R. Kienberger, U. Keller, M. F. Kling, Z.-H. Loh, T. Pfeifer, A. N. Pfeiffer, R. Santra, K. Schafer, A. Stolow, U. Thumm, and M. J. J. Vrakking,“What will it take to observe processes in ‘real time’?,” Nat. Photon. 8, 162-166 (2014).
  4. 4. F.Calegari, G. Sansone, S. Stagira, C. Vozzi, and M. Nisoli,“Advances in attosecond science,” J. Phys. B 49, 062001 (2016).
  5. 5. Yanzeng Li, Margaret Kocherga, Serang Park, Marc Lata, Micheal McLamb, Glenn Boreman, Thomas A. Schmedake, and Tino Hofmann, “Optical dielectric function of Si(2,6-bis(benzimidazol-2′-yl)pyridine)2 determined by spectroscopic ellipsometry,” Opt. Mater. Express 9, 3469–3475 (2019).
  6. 6. M. J. Ambrosio and U. Thumm, “Comparative time-resolved photoemission from the Cu(100) and Cu(111),” surfaces Phys. Rev. A 94, 063424 (2016).
  7. 7. N. Manrique and H. Riascos, “Estimation of Dielectric Constant and Thickness of Copper Thin Films Using Surface Plasmon Resonance,” in Latin America Optics and Photonics Conference, OSA Technical Digest (Optical Society of America, 2018), paper Th4A.16.
  8. 8. F. Roth, C. Lupulescu, E. Darlatt, A. Gottwald, and W. Eberhardt,“Angle resolved Photoemission from Cu single crystals; Known Facts and a few Surprises about the Photoemission Process,” J. Electron Spectrosc. 208, 2-10 (2016).
  9. 9. B. Dold and R. Mecke, “Optische Eigenschaften von Edelmetallen,Übergangsmetallen und deren Legierungen im Infrarot (1. Teil),” Optik22, 435–446 (1965).
  10. 10. P. Winsemius, H. P. Langkeek, and F. F. van Kampen,“Structure dependence of the optical properties of Cu, Ag and Au,” Physica79B, 529–546 (1975).
  11. 11. G. Leveque, C. G. Olson, and D. W. Lynch, “Reflectance spectra and dielectric functions of Ag in the region of interband transitions,” Phys. Rev. B 27, 4654–4660 (1983).
  12. 12. M. L. Thèye, “Investigation of the optical properties of Au by means of thin semitransparent films,” Phys. Rev. B 2, 3060-3078 (1970).
  13. 13. Aleksandar D. Rakić, Aleksandra B. Djurišić, Jovan M. Elazar, and Marian L. Majewski,“Optical properties of metallic films for vertical-cavity optoelectronic devices,” Applied Optics 37, 5271-5284(1998).
  14. 14. C. Kittel, “Introduction to solid states,” Wiley, New York, (1971).
  15. 15. P. B. Johnson and R.W. Christy,“Optical constants of the nobles metals,” Phys. Rev. B6, 4370-4379 (1972).
  16. 16. A.Vial and T. Laroche,“Description of dispersion proprieties of metals by means of the critical points model and application to the study of resonant structures using the FDTD method,” J. Phys. D. Appl. Phys. 40, 7152-7158 (2007).
  17. 17. A. Vial and T. Laroche, “Comparison of gold and silver dispersion laws suitable for FDTD simulations,” Appl. Phys.B 93, 139-149 (2008).
  18. 18. J.Y. Lu and Y.H. Chang, “Implementation of an efficient dielectric function into the finite difference time domain method for simulating the coupling localized surface plasmons of nanostructures,” Superlattices and Microstructures 47, 60-65 (2009).

Written By

Brahim Ait Hammou, Abdelhamid El Kaaouachi, Abdellatif El Oujdi, Adil Echchelh, Said Dlimi, Chi-Te Liang and Jamal Hemine

Submitted: 07 January 2021 Reviewed: 20 January 2021 Published: 08 June 2021