Solid State Chemistry-4

Dr. Shaista Ali

CHEM-3207
 OPTICAL
PROPERTIES
Wave Theory of Light: Huygens, Fresnel, Hertz, Maxwell

 The light field

consists of a an
electric and a
magnetic field
component

But: The light field can take up or

transfer energy only in
packages (light quantums =
photons)
 “Wave-particle-dualism”
Proof for above hypothesis:
• Photons liberate electrons from an electrode, if their frequency
 > E/h (critical frequency)
• Derivation of Planck„s radiation law for cavity radiation is based on the
quantization of
the energy of the light field (Planck, 1900)
 Electromagnetic radiation consists of
wave packages (photons) with
discrete energy E and
momentum p
INTERACTION OF
LIGHT WITH
ATOMS
 Interaction of light with Atoms
 Atom absorbs photon of light undergoes
transition to higher energy level using
selection rules.
 3s of Na-atom can absorb and go to 3p
level not 3d or 4s, indicates the concept of
– Allowed transitions
– Forbidden transitions
 Absorption
 Spontaneous emission
 Induced or simulated emission
 Coherent- photon emitted are in same direction as
photon inducing emission resulting in beam of light
 Non-radiative Transitions: the atom may
collide with another atom, losing energy in the process or
giving energy to its surroundings in the form of
vibrational energy.
 In a crystal selection rules are modified:
electron outside a closed shell (Ti3+)
 In the free ion, the five 3d orbitals all have the same
energy.
 In a crystal, these levels are split; for example, if the
ion occupied an octahedral hole, the 3d levels would be
split into a lower, triply degenerate (t2g) level and a
higher, doubly degenerate (eg) level.
RUBY LASER
 Ruby Laser
 Ruby is Corundum (form of
Al2O3) with 0.05-0.5% Cr+3-ions.
 The three 3d electrons of Cr+3
will absorb energy and move to
higher energy level.
 In Ruby-Forbidden Transition
(doubly forbidden)
 Cr+3-ions absorb light and go to
state 3 and 4, then undergo
transition to state 2 and then to
ground state , resulting photons
will travel through ruby.
 The reflected photons induce further
emission and by this means, an appreciable
beam of coherent light is built up.
PHOSPHORS IN
FLUORESCENT
LIGHTS
 Phosphors are solids that absorb energy and re-
emit it as light.
 Impurity in host lattice.
 Application: 1) Plasma in TV
 2) Fluorescent Light blubs
 Fluorescent lights- produce radiation in the ultraviolet (254
nm) by passing an electric discharge through a low pressure of
mercury vapour. The tube is coated inside with a white powder that
absorbs the ultraviolet light and emits visible radiation.
 Most common fluorescent alkaline earth
halophosphates, such as 3Ca3(PO4)2.CaF2.
 In laser- usual dopant are transition metal or
lanthanide ions
 The incident light is of lower energy than
the emitted light and the process is known
as upconversion.
 An ion absorbs a photon of the incident
radiation and goes to an excited state.
 It then transfers most of the energy either
to another state of that ion or to the excited
state of another ion.
 If this second excited state is metastable, it
has time to absorb another photon before it
spontaneously emits radiation and returns
to a lower state.
DIRECT/INDIRECT
BAND GAPS
 If in some solids the level at the top of the
valence band and that at the bottom of the
conduction band have the same wave
vector. There is then an allowed transition
at the band gap energy. Such solids are
said to have a direct band gap.
 If the direct transition from the top of the
valence band to the bottom of the
conduction band is forbidden. These solids
are said to have an indirect band gap.
 Many metals have strong
transitions between the
conduction band and a
higher energy band, which
lead to their characteristic
metallic sheen.
 Gold and copper have
strong absorption bands due
to the excitation of d band
electrons to the s/p
conduction band. In these
elements, the d band is full
and lies some way below
the Fermi level.
LEDs
 Quantum Wells: Blue Lasers
 The active region of GaN lasers consists of GaN
containing several thin layers (3–4 nm thick) of
indium-doped GaN, InxGa1–xN. The addition of
indium reduces the band gap within the thin
layers, so that the bottom of the conduction band
is at a lower energy than that of the bulk GaN.
 The electrons in this conduction band are
effectively trapped because they need to gain
energy from an external source to pass into the
conduction band of the bulk GaN.
 The trapped electrons behave like particles in a
box and such boxes are quantum wells.
 The active region containing the quantum
wells is sandwiched between layers of n-
doped and p-doped GaN and aluminium-
doped GaN, AlyGa1–yN, which provide the
electrons entering the quantum well and
keep them confined to the active region.
 Blu-ray disks, introduced in 2006, are
DVD-like devices using blue lasers to read
the disk.
REFRACTION
 Passage of light through medium
 It depends on refractive index of medium,
as per Snell’s law radiation bend in 2
medium is
n1sin θ1 = n2sin θ2,
 In a molecule, the amount of response from
the electrons depends on how tightly bound
the electrons are to the nucleus.
 This property is called the polarisability and
is higher for large ions with low charge, for
example, Cs+ and I−, than for small, highly
charged ions such as Al3+.
 Calcite
 Calcite is stable
polymorph CaCO3.
 It is birefringence
means having different
polarisabilities in the
directions of different
crystal axes and hence
different refractive
indices for light
polarised perpendicular
to these axes.
OPTICAL FIBRES
 Optical fibres are used to transmit light in the way that
metal wires are used to transmit electricity, e.g. telephone
call.
 The intensity, the time between pulses and the length of
the pulse can be modified to convey the contents of the
call in coded form.
 The first requirement is that the laser beam keeps within
the fibre.
 The refractive index can be varied by adding selected
impurities.
 The imperfections cause scattering of the light of a type
known as Rayleigh scattering (1/λ4).
 The third source of energy loss is absorption of light by
the fibre.
PHOTONIC
CRYSTALS
 PHOTONIC CRYSTALS
 Photonic crystals have been hailed as the
optical equivalent of semiconductors.
 A photonic crystal consists of a periodic
arrangement of two materials of different
refractive indexes.
 At each boundary between the two
materials, light, or other electromagnetic
radiation, will refract and partly reflect.
 Photonic band gap.
 METAMATERIALS:
CLOAKS OF INVISIBILITY