Plasmonics: Fundamentals and Applications

SS2012

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Plasmonics: Fundamentals and Applications
Lecture notes by Dr. E. Margapoti

Summer semester 2012 TU Mnchen

Plasmonics: Fundamentals and Applications

Introduction
The study of Plasmonics is a brunch of Nanophonics. It studies how the electromagnetic (EM) field can be confined over a dimension of the order or smaller than the wavelength. When the EM field interacts with the conductive electrons at the metal interface or in metallic nanostructures an enhanced optical near field of sub-wavelength is achieved. In this course the aim is to give a broad overview of the properties of Plasmons going from the study of volume plasmons, towards the investigation of localized surface plasmons passing through the understanding of surface plasmon polaritons and its ways of investigation. In order to achieve this insight we start by introducing the classical Maxwells equations, deriving the dielectric function by using the free electron gas theory.

1 Definition of a Plasmon
Before going in details, we should ask our self what is a Plasmon and how it can be generated. The most common definition of a Plasmon is A plasmon is a quantum of plasma oscillation The quantization of the collective longitudinal excitation of a conductive electron gas in a metal is known as Plasmon. The excitation of a Plasmon requires the interaction of an electron passing through a thin metal or by reflecting an electron or a photon from the metallic film. In Fig.1 is shown a scheme of an incident electron interacting with a thin metal film, resulting in a scattered electron and one or two plasmons.
Electron incident energy: ~ 1-10 KeV

Plasmon energy: ~ 10 eV Later we will go more in detail showing how one can detect the surface plasmon polaritons.

Plasmonics: Fundamentals and Applications

SS2012

Fig1. Creation of a Plasmon in a metal film by inelastic scattering of an electron.

Electromagnetic of a Metals
The interaction of metals with EM fields can be understood using the classical Maxwells equations. Even metallic nanostructure with a size on the order of few nanometers can be described without the need of quantum mechanics. Due to the high density of free carriers, the energy spacing between the electron energy levels is much smaller than the thermal excitation kBT. Optical properties strong dependent from frequency
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Fig.2

Plasmonics: Fundamentals and Applications

For frequency up to the visible spectrum, metals are highly reflective and no EM waves can propagate through them. At higher frequencies: in the near-infrared and visible part of the spectrum, field penetration increases, leading to an increased dissipation. In the UV-region, metals acquired a dielectric character, allowing the penetration of the EM waves. The level of attenuation depends from the electronic band structures.

Alkali metals have almost a free-electron-like behaviour, showing an ultraviolet transparency.

For noble metals (e.g. Au, Ag), transitions between electronic bands lead to strong absorption in the UV regime.

The dispersive properties of an EM waves into a metals is described by the complex dielectric function ().
Before going more in details with the optical properties of metals lets introduce the Macroscopic Maxwells equations:

electric charge is the source of the electric field there are no source of magnetic field change of B-field with time leads to a rotating E-field electric currents give rise to rotating magnetizing field

In these equation there are four macroscopic fields the dielectric displacements, the electric field, the magnetic field and the magnetic flux density. In addition density, while is the external charge

is the external current density. The total charge and current densities are written and ,

as a sum of the internal and external components, that are respectively. Lets define now the fields:

( is the polarization, the dielectric function )

( is the magnetization)

Plasmonics: Fundamentals and Applications

SS2012

Since we are dealing only with no magnetic effect, from now we will be concentrate only on the electric polarization effects. describes the sum of the electric dipole moments per unit volume 1-electron in -field is displaced by a distance and leads to n-electrons in a volume V leads to

Thanking into account last two equations we found the relationship between the polarization and internal charge density: Introducing this last equation into the displaced equation above we obtain:

Plasmonics: Fundamentals and Applications

2 Optical properties of metals

The optical properties of a metal is described via dielectric function (), as above defined. The frequency dependence of () describe the dispersive properties of metals. The dielectric function is mainly determined by: (i) (ii) The freely moving conduction electrons. Interband excitation of bound electrons if Ephot > EgapMetal

Lets consider a piece of metal:

Fig.3 In absence of an external field the valence electrons are free to move in the metal, as in gas of particles (see Drude model) If an external field is applied ( 0), the valence electrons will be displaced of an , with n the electrons amount, , leading to a macroscopic polarization , density (n = N/V). The dielectric function is connected to the polarization by: with ( ) ( ) ( )

Plasmonics: Fundamentals and Applications

SS2012

Drude Model
In the earliest 1900, Drude constructed his theory of electrical and thermal conduction by applying the kinetic theory of gasses to a metal, considered as a gas of electrons. In its simplest form the Kinetic theory treats the molecules of a gas as identical solid spheres, which move in straight lines until they collide with one another. Although there is only one type of particle in the simplest gases, in metal there must be at least two. The electrons must be compensated by positive carriers to leave the metal electrically neutral. Drude assumed that the compensating positive charge was attached to much heavier particles, which he considers to be immobile. At this time was not much knowledge of light and mobile electrons and immobile positive charges. We should simply assume that when atoms of a metallic elements are brought together to form a metal, the valence electrons become detached and wander freely through the metal, while the metallic ions remain intact and play the role of the immobile positive particles in the Drude theory (See Fig.4)

Fig.4 a) Schematic picture of an isolated atom. b) In a metal the nucleus and ion core retain their configuration in the free atom, but the valence electrons leave the atom to form the electron gas.

In a single isolated atom we have the following configuration: Nucleus of charge eZa, with Za atomic number and e the magnitude of the electronic charge,

Plasmonics: Fundamentals and Applications

-eZa is the total charge surrounding the nucleus, -eZ are the relatively weak bound valence electrons, The remaining e( Za Z) are the tightly bound electrons (known as core electrons). When these isolated atoms condense to form a metal, the core electrons remain bounded to the nucleus to form the metallic ions, but the valence electrons are free to move around and away from their parent atom. They are called conduction electrons. By calculating the electrons density in a metal one recognizes that the value is much larger than those of classical gas at normal temperature and pressure. In spite of this and in spite of the strong electronelectron and electron-ion electromagnetic interactions, the Drude model treats the dense metallic electrons by following the Kinetic theory of a neutral diluted gas. These the basic assumptions: 1. Between collisions the interactions of the electron with the others and with the ions are neglected. In absence of externally applied fields each electron is moving in a straight line. Instead in the presence of an applied field the electron will act following the Newtons law ( ) neglecting the extra fields emerging from other electrons and ions.

2. Collisions in Drudes model are taken as in Kinetic theory, which is as instantaneous events that abruptly alter the velocity of an electron. This simplest picture is visualized in Fig.5.

Fig.5 Trajectory of a conduction electron scattering off the ions according to the nave picture of Drude.

3. An electron experiences a collision with a probability per unit time 1/. With known as the relaxation time, the mean free time. We can describe the probability of an electron undergoing a collision in a time interval dt as dt/. In the Drude model, is taken to be independent of an electrons position and velocity. 4. Electrons achieve thermal equilibrium with their surroundings by collisions.

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Definition of the Dielectric Function and Plasma Optics

The equation of motion of a free electron in an electric field is: If we assume a harmonic time dependence ( ) of the driving field, the solution of . Any phase shift

this equation describing the oscillation of the electron is ( ) between the driving field and response is given as: ( )
( )

( ).

The polarization defined as the dipole moment per unit volume is: ( ) ( ).

Lets now define the dielectric function at the frequency as: ( ) Lets defining the frequency: , which is named Plasma frequency. Plasma is a medium with equal concentration of positive and negative charges, of which at least one is mobile. Therefore the dielectric function of the free electron gas can be rewritten as: ( ) where = 1/. We will define later both and . , ( ) ( ) ( ) ( )
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Plasmonics: Fundamentals and Applications

For the moment lets limit our study to the case of no damping. For larger frequencies, close to the plasma frequency, can be written again as: ( ) In Fig.6 a scheme of the dielectric function versus the frequency is shown. Electromagnetic waves propagate without damping when ( when ( ) is negative.
Fig.6 Dielectric function () of a free electron gas versus frequency in unit of the plasma frequency.

, the damping can be neglected. In this case the dielectric function

) is positive and real, while is totally reflected

In general, the dielectric function can be written as: () = 1() + i2(), where 1() is the real part and 2() the imaginary part. At optical frequencies, () can be experimentally determined via reflectivity studies. We can also define the complex refractive index as ( ) ( ) ( ) ( ) ( ), also defined as

, known as extinction coefficient and determine the optical absorption of

electromagnetic waves propagating trough the medium: ( ) Known as Beer-Lambert law.

( )

Plasmonics: Fundamentals and Applications

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The reflectivity is defined as: | | ( ( ) )

1. < p : is imaginary n = 0, R = 1 2. = p : R=1 : ( ) 3. > p : is real

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If we limit ourself in the range of low frequency, region metals are mainly absorbing. The absorption coefficient is metal as , where ( )

, hence

and

. In this

. For low frequencies the field fall off inside the .

is the skin depth,

This description is valid as long as the mean free path of the electrons the Fermi velocity.

, where

is

Plasmonics: Fundamentals and Applications

Taking into account

| | the Beer law is obtained: ( ) ( )

( )

Beer-Lambert Law

At visible frequencies the free-electron model doesnt hold anymore due to interband transitions 2 increases The Drude model describes the optical response of a metal only below the threshold of transitions between electronic bands. The figure below shows the real and imaginary part and of the

dielectric function of a silver and gold [Johnson and Christy, 1972]. The Drude model fit well the data only at lower frequency.

Plasmonics: Fundamentals and Applications

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In the case of Gold, this validity is already broken at the boundary between visible and nearinfrared. The optical properties of Gold and Silver at visible frequencies are described by the function: Interband transitions are described using the classical picture of a bound electron with resonance . Combination of Drude model and Lorentz-oscillator model generates a good agreement between theory and experiments.