SIC3039 - MATERIAL CHEMISTRY

Module 7 -Optical properties

Introduction
Visible light is a form of EM radiation

Light can be regarded as a travelling wave that propagates through space as a

Combination of mutually perpendicular oscillating electric and magnetic fields

It extends from the lower energy, red end of the visible spectrum with wavelength ∼700 nm and
energy ∼1.7 eV to the higher energy, violet end, ∼400 nm and 3.3 eV, Fig. 10.1(a).

Light from sodium street-lamp is yellow, the embers of a fire may be orange–red and the sunlight is
white. What affects the colour emitted by an object or lamp?
It is associated with the existence of allowed energy levels for the electronic structure of atoms,
molecules and solids

In a hot body, there is a continual process of electrons moving between the various levels and by
adjusting the experimental conditions it is possible to determine either absorption spectra or
emission spectra.

For a given temperature, an equilibrium develops between the absorption and emission processes
which occur spontaneously in the absence of any external stimuli

Provided that there are vacancies in energy levels at E0, electrons in level E1 spontaneously drop
back to the lower levels, emitting energy E in the process. This is known as spontaneous emission.
Under normal circumstances, an electron will remain in an upper energy level for only a few
nanoseconds before it spontaneously relaxes to a lower level

If the energies involved fall within the visible range of

energies, the transitions are known as optical transitions
Phosphor and luminescence

Luminescence is the emission of light by a material after it has absorbed energy.

It can be claasified into different types depending on the source of excitation.

(i) Photoluminescence – uses photons or light (often UV)
(ii) Electroluminescence - uses an electrical energy input
(iii) Cathodoluminescence uses cathode rays or electrons.

Photoluminescence can be further distinguished based on the time-lapse between excitation and
emission.
(a) For a short time-lapse, ≤10–8 s, the process is known as fluorescence. Fluorescence effectively
ceases as soon as the excitation source is removed.
(b) For much longer decay times, the process is known as phosphorescence. It may continue long
after the excitation source has been removed
Photoluminescent materials generally require a host crystal structure, ZnS, CaWO4, Zn2SiO4, etc.,
which is doped with a small amount of an activator, a cation such as Mn2+, Sn2+, Pb2+ or Eu2+.
Sometimes, a second dopant is added to act as a sensitiser.

The energy of the emitted light is usually less than that of the exciting radiation and is, therefore, of
longer wavelength. This increase in wavelength is known as the Stokes shift.
Working principle of fluorescent lamp
In fluorescent lamps, the exciting radiation is UV light from a mercury discharge.
Phosphor materials absorb this UV radiation and emit ‘white’ light.

The construction of a fluorescent lamp, consists of a glass tube lined on the inside with a coating of
phosphor material and filled with a mixture of Hg vapour and Ar.
On passage of an electric current through the lamp, the atoms of Hg are bombarded by electrons,
excited into upper electronic energy states and then return to the ground state, accompanied by the
emission of UV light of two characteristic wavelengths, 2540 and 1850 A.
This light irradiates the phosphor which subsequently emits white light
Explaining luminescent with PE diagram

First, excitation raises the active centre from its ground state, level A, into a higher vibrational level,
B, of the excited state.

Second, energy is dissipated as the ion quickly relaxes to a lower level, C, in the excited state. This
energy is lost as heat to the host lattice.
Third, the active centre returns to its ground state, level D or A, and, in so doing, emits light.

Since the energy of excitation A → B is greater than that

of emission C → D, the emitted radiation is of longer
wavelength than the exciting radiation, which accounts
for the Stokes shift
Anti-Stokes Phosphors
The anti-Stokes phosphors exhibit the remarkable property of emitting light or photons of higher
energy (shorter wavelength) than the incident exciting radiation.
Using these, it is possible, for instance, to upconvert IR radiation into higher energy, visible light.

But how is this possible without violating the law of conservation of energy?
What happens is that the process of excitation takes place in two or more stages
The most studied anti-Stokes
phosphors to date are host structures
such as YF3, NaLa(WO4)2 and α-NaYF4,
doubly doped with Yb3+ as a
sensitiser and Er3+ as an activator

During irradiation, Yb3+ ions transfer

two IR photons to nearby Er3+ ions,
which are raised into a doubly excited
state and decay by the emission of
visible light.
Types of light scattering
In addition to absorption and emission, a range of other scattering processes occur when light
interacts with matter
• Light scattering can be thought of as the deflection of a ray from a straight path, for example by
irregularities in the propagation medium, particles, or in the interface between two media.

• Scattering of light depends on the wavelength or frequency of the light being scattered.

• Most objects that one sees are visible due to light scattering from their surfaces. Hence, objects
much smaller than the wavelength of the light cannot be seen, even with the aid of a microscope

• Interaction of light with matter give important information about the structure and dynamics of
the material being examined

• A study of the scattered light intensity as a function of scattering angle gives information about
the structure, spatial configuration, or morphology of the scattering medium
(I) Tyndall scattering

• is light scattering by particles in a colloid or particles in a fine suspension

• This type of scattering is observed when light scattering particulate-matter is dispersed in a light-
transmitting medium, and the cross section of an individual particulate is the range of roughly
between 40 and 900 nanometres; overlaps with the wavelength of visible lights.

• Intensity of the scattered light depends on the frequency of the light, where blue light is scattered
much more strongly than red light.

• Under the Tyndall effect, the longer-wavelength light is more transmitted while the shorter
wavelength light is more reflected via scattering
Application of Tyndall scattering

Commercially exploited to determine the size and density of particles in aerosols and other colloidal
matter
Can be used to confirm colloidal nature of a sample

The visible beam of headlights in fog is caused by the Tyndall effect. The water droplets scatter the
light, making the headlight beams visible.
(II) Mie scattering
Light scattered by spherical particles that have a diameter similar to or larger than the wavelength of the
incident light.

The Mie signal is proportional to the square

of the particle diameter.

Mie scattering is less wavelength-dependent

Hence, this kind of scattering does not differentiate individual wavelength colors and therefore scatters
all wavelength colors the same.

The common particles causing the Mie scattering are dust, pollen, smoke, and microscopic water
droplets, that form clouds

Related phenomenon:
(i) White or gray appearance of clouds.
(ii) Haze
Mie scattering occurs when
the wavelengths of visible
light are approximately,
equally scattered.

Water droplets, in even

small clouds, effectively
scatter all wavelengths of
visible light in all directions,
thus making clouds appear
white
• Visibility and haze: Mie scattering also plays a role in the visibility of objects at a distance, especially in
hazy or foggy conditions. The suspended particles in the air, dust, or water droplets, can scatter light
and reduce the contrast between objects and their background, impairing visibility
(III) Rayleigh scattering

Rayleigh scattering refers to the scattering of light by particulate matters which are much smaller in
size compared to the λ of the light.
E.g. scattering of sunlight by the molecules of the air
In general, this scattering can be extended to scattering from particles up to about a tenth of the
wavelength of the light.

Intensity of Rayleigh scattering is inversely proportional to the fourth power of the wavelength of
the light.
Since blue colour has the shortest wavelength, it is scattered more than other lights in the sunlight,
and this explains the blue appearance of the sky.
(Sunlight of all colors passes through air, the blue part causes charged particles to oscillate faster
than does the red part. The faster the oscillation, the more scattered light is produced, so blue is
scattered more strongly than red.)
Due to Rayleigh scattering, most of the light of shorter wavelengths – the blue, violet, and green – are
scattered away multiple times, leaving only lights of longer wavelength – the red, orange, and yellow – to
pass straight through to the observer.
Application of Rayleigh scattering
Dynamic light scattering (DLS), which is also known as photon correlation spectroscopy (PCS) or quasi-
elastic light scattering (QLS), is a spectroscopy method used in the fields of chemistry, biochemistry,
and physics to determine the size distribution of particles (polymers, proteins, colloids, etc.) in solution
or suspension.

In the DLS experiment, normally a laser provides the monochromatic incident light, which impinges
onto a solution with small particles in Brownian motion.

And then through the Rayleigh scattering process, particles whose sizes are sufficiently small compared
to the wavelength of the incident light will diffract the incident light in all direction with different
wavelengths and intensities as a function of time.

Since the scattering pattern of the light is highly correlated to the size distribution of the analyzed
particles, the size-related information of the sample could be then acquired by mathematically
processing the spectral characteristics of the scattered light.
According to the Rayleigh scattering, when a sample of particles with diameter smaller than the
wavelength of the incident light, each particle will diffract the incident light in all directions, with
intensity related to the equation:

where Io and λ refer to the intensity and wavelength of the unpolarized incident light
R is the distance to the particle,
θ is the scattering angel,
n is the refractive index of the particle,
r is the radius of the particle

If that diffracted light is projected as an image onto a screen,

it will generate a “speckle" pattern
Dark areas represent regions where the diffracted light from
the particles arrives out of phase interfering destructively, and the
bright area due to constructive interference.
Will the speckle image remain static?
Particles are in constant random motion @ Brownian motion

As a result of the Brownian motion, the distance between particles is constantly changing and this
results in a Doppler shift between the frequency of the incident light and the frequency of the
scattered light.

Since the distance between particles also affects the phase overlap/interfering of the diffracted
light, the brightness and darkness of the spots in the “speckle” pattern will in turn fluctuate in
intensity as a function of time when the particles change position with respect to each other

How are this related to the size of the particles?

Diffusion constant, D of the particles is expressed by Stokes-Einstein equation:

Where kB = Boltzman constant, T = temperature, µ = viscosity, and a = hydrodynamic radius

Based on the above, small particles can diffuse faster than bigger ones.
As the rate of these intensity fluctuations
depends on how fast the particles are moving
(smaller particles diffuse faster), information
about the size distribution of particles in the
solution could be acquired by processing the
fluctuations of the intensity of scattered light.

Hypothetical fluctuation of scattering

intensity of larger particles and smaller
particles.
(iv) Raman scattering
Inelastic scattering
When light is irraidated on molecules, the light is scattered by molecules. Most of scattered light
have the same frequency with incident light but some fraction of light have different freqency due
to interaction between oscillation of light and molecular vibration.

The phenomenon that the light is scattered with frequency change is called Raman scattering.
Because this frequency modulation is specific to molecular vibration and phonon in crystal, it is
possible to analyze composition of material or crystal lattice information by anayzing spectrum of
Raman scattered light. This analysis method is Raman spectroscopy.

The photons are inelastically scattered, which means that the kinetic energy of an incident particle
is either lost or increased and is composed of Stokes and anti-Stokes portions.

Raman scattering depends on the polarizability of the molecules.

When radiation in the near infrared (NIR) or visible range interacts with a molecule, several types of
scattering can occur
Stokes Scattering

The molecule is excited to any virtual state.

The molecule relaxes back to a higher
vibrational state than it had originally.
The photon leaves with energy hν-ΔE and
has been scattered inelastically.

Anti-Stokes Scattering

The molecule begins in a vibrationally

excited state.
The molecule is excited to any virtual state.
The molecule relaxes back to a lower
vibrational state than it had originally.
The photon leaves with energy hν+ΔE, and
has been scattered superelastically.
Why Rayleigh scattering is not important / utilized in Raman
Spectroscopy?

Why Anti-stoke Raman scattering is not commonly used in Raman

measurement?
Raman spectroscopy observes the change in energy between the incident and scattered photons
associated with the Stokes and anti-Stokes transitions.

This is typically measured as the change in the wavenumber (cm-1), from the incident light source.
Because Raman measures the change in wavenumber, measurements can be taken using a source
at any wavelength; however, near infrared and visible radiation are commonly used. \\

Photons with ultraviolet wavelengths could work as well, but tend to cause photodecomposition of
the sample.

Raman spectroscopy sounds very much like infrared (IR) spectroscopy; however, IR examines the
wavenumber at which a functional group has a vibrational mode, while Raman observes the shift in
vibration from an incident source.

The Raman frequency shift is identical to the IR peak frequency for a given molecule or functional
group. As mentioned above, this shift is independent of the excitation wavelength, giving versatility
to the design and applicability of Raman instruments.