Plasmonic nanoparticles

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FDTD simulation of a pulsed plane wave interaction with plasmonic nanoparticles [1]

Plasmonic nanoparticles are particles whose electron density can couple with electromagnetic radiation of wavelengths that are far larger than the particle due to the nature of the dielectric-metal interface between the medium and the particles: unlike in a pure metal where there is a maximum limit on what size wavelength can be effectively coupled based on the material size. [2]

Contents

What differentiates these particles from normal surface plasmons is that plasmonic nanoparticles also exhibit interesting scattering, absorbance, and coupling properties based on their geometries and relative positions. [3] [4] These unique properties have made them a focus of research in many applications including solar cells, spectroscopy, signal enhancement for imaging, and cancer treatment. [5] [6] Their high sensitivity also identifies them as good candidates for designing mechano-optical instrumentation. [7]

Plasmons are the oscillations of free electrons that are the consequence of the formation of a dipole in the material due to electromagnetic waves. The electrons migrate in the material to restore its initial state; however, the light waves oscillate, leading to a constant shift in the dipole that forces the electrons to oscillate at the same frequency as the light. This coupling only occurs when the frequency of the light is equal to or less than the plasma frequency and is greatest at the plasma frequency that is therefore called the resonant frequency. The scattering and absorbance cross-sections describe the intensity of a given frequency to be scattered or absorbed. Many fabrication processes or chemical synthesis methods exist for preparation of such nanoparticles, depending on the desired size and geometry.

The nanoparticles can form clusters (the so-called "plasmonic molecules") and interact with each other to form cluster states. The symmetry of the nanoparticles and the distribution of the electrons within them can affect a type of bonding or antibonding character between the nanoparticles similarly to molecular orbitals. Since light couples with the electrons, polarized light can be used to control the distribution of the electrons and alter the mulliken term symbol for the irreducible representation. Changing the geometry of the nanoparticles can be used to manipulate the optical activity and properties of the system, but so can the polarized light by lowering the symmetry of the conductive electrons inside the particles and changing the dipole moment of the cluster. These clusters can be used to manipulate light on the nano scale. [8]

Theory

The quasistatic equations that describe the scattering and absorbance cross-sections for very small spherical nanoparticles are:

where is the wavenumber of the electric field, is the radius of the particle, is the relative permittivity of the dielectric medium and is the relative permittivity of the nanoparticle defined by

also known as the Drude Model for free electrons where is the plasma frequency, is the relaxation frequency of the charge carries, and is the frequency of the electromagnetic radiation. This equation is the result of solving the differential equation for a harmonic oscillator with a driving force proportional to the electric field that the particle is subjected to. For a more thorough derivation, see surface plasmon.

It logically follows that the resonance conditions for these equations is reached when the denominator is around zero such that

When this condition is fulfilled the cross-sections are at their maximum.

These cross-sections are for single, spherical particles. The equations change when particles are non-spherical, or are coupled to 1 or more other nanoparticles, such as when their geometry changes. This principle is important for several applications.

Rigorous electrodynamic analysis of plasma oscillations in a spherical metal nanoparticle of a finite size was performed in. [9]

Applications

Plasmonic solar cells

Due to their ability to scatter light back into the photovoltaic structure and low absorption, plasmonic nanoparticles are under investigation as a method for increasing solar cell efficiency. [10] [5] Forcing more light to be absorbed by the dielectric increases efficiency. [11]

Plasmons can be excited by optical radiation and induce an electric current from hot electrons in materials fabricated from gold particles and light-sensitive molecules of porphin, of precise sizes and specific patterns. The wavelength to which the plasmon responds is a function of the size and spacing of the particles. The material is fabricated using ferroelectric nanolithography. Compared to conventional photoexcitation, the material produced three to 10 times the current. [12] [13]

Spectroscopy

In the past 5 years plasmonic nanoparticles have been explored as a method for high resolution spectroscopy. One group utilized 40 nm gold nanoparticles that had been functionalized such that they would bind specifically to epidermal growth factor receptors to determine the density of those receptors on a cell. This technique relies on the fact that the effective geometry of the particles change when they appear within one particle diameter (40 nm) of each other. Within that range, quantitative information on the EGFR density in the cell membrane can be retrieved based on the shift in resonant frequency of the plasmonic particles. [14]

Cancer treatment

Plasmonic nanoparticles have demonstrated a wide potential for the establishment of innovative cancer treatments. [15] Despite that, there are still not plasmonic nanomaterials employed in the clinical practice, because the associated metal persistence. [15] Preliminary research indicates that some nanomaterials, among which gold nanorods [16] and ultrasmall-in-nano architectures, [17] can convert IR laser light into localized heat, also in combination with other established cancer treatments. [18]

See also

Related Research Articles

<span class="mw-page-title-main">Dielectric</span> Electrically insulating substance able to be polarised by an applied electric field

In electromagnetism, a dielectric is an electrical insulator that can be polarised by an applied electric field. When a dielectric material is placed in an electric field, electric charges do not flow through the material as they do in an electrical conductor, because they have no loosely bound, or free, electrons that may drift through the material, but instead they shift, only slightly, from their average equilibrium positions, causing dielectric polarisation. Because of dielectric polarisation, positive charges are displaced in the direction of the field and negative charges shift in the direction opposite to the field. This creates an internal electric field that reduces the overall field within the dielectric itself. If a dielectric is composed of weakly bonded molecules, those molecules not only become polarised, but also reorient so that their symmetry axes align to the field.

<span class="mw-page-title-main">Permittivity</span> Measure of the electric polarizability of a dielectric

In electromagnetism, the absolute permittivity, often simply called permittivity and denoted by the Greek letter ε (epsilon), is a measure of the electric polarizability of a dielectric. A material with high permittivity polarizes more in response to an applied electric field than a material with low permittivity, thereby storing more energy in the material. In electrostatics, the permittivity plays an important role in determining the capacitance of a capacitor.

<span class="mw-page-title-main">Plasmon</span> Quasiparticle of charge oscillations in condensed matter

In physics, a plasmon is a quantum of plasma oscillation. Just as light consists of photons, the plasma oscillation consists of plasmons. The plasmon can be considered as a quasiparticle since it arises from the quantization of plasma oscillations, just like phonons are quantizations of mechanical vibrations. Thus, plasmons are collective oscillations of the free electron gas density. For example, at optical frequencies, plasmons can couple with a photon to create another quasiparticle called a plasmon polariton.

The Faraday effect or Faraday rotation, sometimes referred to as the magneto-optic Faraday effect (MOFE), is a physical magneto-optical phenomenon. The Faraday effect causes a polarization rotation which is proportional to the projection of the magnetic field along the direction of the light propagation. Formally, it is a special case of gyroelectromagnetism obtained when the dielectric permittivity tensor is diagonal. This effect occurs in most optically transparent dielectric materials under the influence of magnetic fields.

<span class="mw-page-title-main">Drude model</span> Model of electrical conduction

The Drude model of electrical conduction was proposed in 1900 by Paul Drude to explain the transport properties of electrons in materials. Basically, Ohm's law was well established and stated that the current J and voltage V driving the current are related to the resistance R of the material. The inverse of the resistance is known as the conductance. When we consider a metal of unit length and unit cross sectional area, the conductance is known as the conductivity, which is the inverse of resistivity. The Drude model attempts to explain the resistivity of a conductor in terms of the scattering of electrons by the relatively immobile ions in the metal that act like obstructions to the flow of electrons.

<span class="mw-page-title-main">Colloidal gold</span> Suspension of gold nanoparticles in a liquid

Colloidal gold is a sol or colloidal suspension of nanoparticles of gold in a fluid, usually water. The colloid is usually either wine-red coloured or blue/purple . Due to their optical, electronic, and molecular-recognition properties, gold nanoparticles are the subject of substantial research, with many potential or promised applications in a wide variety of areas, including electron microscopy, electronics, nanotechnology, materials science, and biomedicine.

Plasma oscillations, also known as Langmuir waves, are rapid oscillations of the electron density in conducting media such as plasmas or metals in the ultraviolet region. The oscillations can be described as an instability in the dielectric function of a free electron gas. The frequency only depends weakly on the wavelength of the oscillation. The quasiparticle resulting from the quantization of these oscillations is the plasmon.

In plasmas and electrolytes, the Debye length, is a measure of a charge carrier's net electrostatic effect in a solution and how far its electrostatic effect persists. With each Debye length the charges are increasingly electrically screened and the electric potential decreases in magnitude by 1/e. A Debye sphere is a volume whose radius is the Debye length. Debye length is an important parameter in plasma physics, electrolytes, and colloids. The corresponding Debye screening wave vector for particles of density , charge at a temperature is given by in Gaussian units. Expressions in MKS units will be given below. The analogous quantities at very low temperatures are known as the Thomas–Fermi length and the Thomas–Fermi wave vector. They are of interest in describing the behaviour of electrons in metals at room temperature.

<span class="mw-page-title-main">Dielectrophoresis</span>

Dielectrophoresis (DEP) is a phenomenon in which a force is exerted on a dielectric particle when it is subjected to a non-uniform electric field. This force does not require the particle to be charged. All particles exhibit dielectrophoretic activity in the presence of electric fields. However, the strength of the force depends strongly on the medium and particles' electrical properties, on the particles' shape and size, as well as on the frequency of the electric field. Consequently, fields of a particular frequency can manipulate particles with great selectivity. This has allowed, for example, the separation of cells or the orientation and manipulation of nanoparticles and nanowires. Furthermore, a study of the change in DEP force as a function of frequency can allow the electrical properties of the particle to be elucidated.

<span class="mw-page-title-main">Surface plasmon resonance</span> Physical phenomenon of electron resonance

Surface plasmon resonance (SPR) is a phenomenon that occurs where electrons in a thin metal sheet become excited by light that is directed to the sheet with a particular angle of incidence, and then travel parallel to the sheet. Assuming a constant light source wavelength and that the metal sheet is thin, the angle of incidence that triggers SPR is related to the refractive index of the material and even a small change in the refractive index will cause SPR to not be observed. This makes SPR a possible technique for detecting particular substances (analytes) and SPR biosensors have been developed to detect various important biomarkers

<span class="mw-page-title-main">Surface-enhanced Raman spectroscopy</span>

Surface-enhanced Raman spectroscopy or surface-enhanced Raman scattering (SERS) is a surface-sensitive technique that enhances Raman scattering by molecules adsorbed on rough metal surfaces or by nanostructures such as plasmonic-magnetic silica nanotubes. The enhancement factor can be as much as 1010 to 1011, which means the technique may detect single molecules.

In materials science, effective medium approximations (EMA) or effective medium theory (EMT) pertain to analytical or theoretical modeling that describes the macroscopic properties of composite materials. EMAs or EMTs are developed from averaging the multiple values of the constituents that directly make up the composite material. At the constituent level, the values of the materials vary and are inhomogeneous. Precise calculation of the many constituent values is nearly impossible. However, theories have been developed that can produce acceptable approximations which in turn describe useful parameters including the effective permittivity and permeability of the materials as a whole. In this sense, effective medium approximations are descriptions of a medium based on the properties and the relative fractions of its components and are derived from calculations, and effective medium theory. There are two widely used formulae.

<span class="mw-page-title-main">Surface plasmon</span>

Surface plasmons (SPs) are coherent delocalized electron oscillations that exist at the interface between any two materials where the real part of the dielectric function changes sign across the interface. SPs have lower energy than bulk plasmons which quantise the longitudinal electron oscillations about positive ion cores within the bulk of an electron gas.

A plasmonic-enhanced solar cell, commonly referred to simply as plasmonic solar cell, is a type of solar cell that converts light into electricity with the assistance of plasmons, but where the photovoltaic effect occurs in another material.

<span class="mw-page-title-main">Surface plasmon polariton</span> Electromagnetic waves that travel along an interface

Surface plasmon polaritons (SPPs) are electromagnetic waves that travel along a metal–dielectric or metal–air interface, practically in the infrared or visible-frequency. The term "surface plasmon polariton" explains that the wave involves both charge motion in the metal and electromagnetic waves in the air or dielectric ("polariton").

A plasmonic metamaterial is a metamaterial that uses surface plasmons to achieve optical properties not seen in nature. Plasmons are produced from the interaction of light with metal-dielectric materials. Under specific conditions, the incident light couples with the surface plasmons to create self-sustaining, propagating electromagnetic waves known as surface plasmon polaritons (SPPs). Once launched, the SPPs ripple along the metal-dielectric interface. Compared with the incident light, the SPPs can be much shorter in wavelength.

<span class="mw-page-title-main">Localized surface plasmon</span>

A localized surface plasmon (LSP) is the result of the confinement of a surface plasmon in a nanoparticle of size comparable to or smaller than the wavelength of light used to excite the plasmon. When a small spherical metallic nanoparticle is irradiated by light, the oscillating electric field causes the conduction electrons to oscillate coherently. When the electron cloud is displaced relative to its original position, a restoring force arises from Coulombic attraction between electrons and nuclei. This force causes the electron cloud to oscillate. The oscillation frequency is determined by the density of electrons, the effective electron mass, and the size and shape of the charge distribution. The LSP has two important effects: electric fields near the particle's surface are greatly enhanced and the particle's optical absorption has a maximum at the plasmon resonant frequency. Surface plasmon resonance can also be tuned based on the shape of the nanoparticle. The plasmon frequency can be related to the metal dielectric constant. The enhancement falls off quickly with distance from the surface and, for noble metal nanoparticles, the resonance occurs at visible wavelengths. Localized surface plasmon resonance creates brilliant colors in metal colloidal solutions.

<span class="mw-page-title-main">Plasmonics</span>

Plasmonics or nanoplasmonics refers to the generation, detection, and manipulation of signals at optical frequencies along metal-dielectric interfaces in the nanometer scale. Inspired by photonics, plasmonics follows the trend of miniaturizing optical devices, and finds applications in sensing, microscopy, optical communications, and bio-photonics.

Spoof surface plasmons, also known as spoof surface plasmon polaritons and designer surface plasmons, are surface electromagnetic waves in microwave and terahertz regimes that propagate along planar interfaces with sign-changing permittivities. Spoof surface plasmons are a type of surface plasmon polariton, which ordinarily propagate along metal and dielectric interfaces in infrared and visible frequencies. Since surface plasmon polaritons cannot exist naturally in microwave and terahertz frequencies due to dispersion properties of metals, spoof surface plasmons necessitate the use of artificially-engineered metamaterials.

Emilie Ringe is an American chemist who is an Assistant Professor at the University of Cambridge. She was selected by Chemical & Engineering News as one of its "Talented Twelve" young scientists in 2021.

References

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