Luminescence

 When a substance absorbs

energy in some form or the
other, a fraction of the energy
may be re- emitted in the form
of electromagnetic radiation in
the visible or near visible
region of the spectrum. This
phenomenon is called Luminescent solids are
luminescence. usually referred to as
Phosphors
Two step process:
1. Excitation: of the electronic system

i. Photo luminescence : by bombardment of

photons
ii. Cathodo luminescence: by bombardment of
Electrons
iii. Chemi luminescence: by chemical reaction
iv. Electroluminescence: by application of electric
field

2. Emission: of photons
 Fluorescence : Emission of
light during excitation
 Phosphorescence or
afterglow : Emission of Scorpions are fluorescent!

light after excitation has

ceased

Generally there is a time lag of

10-8 seconds between
fluorescence and
phosphorescence.
Zinc sulfide (ZnS), a
natural phosphor. Left, in
room light. Middle, under
UV light. Right, after the
UV light is turned off.
 Activators: are reason for the occurrence of
luminescence. Eg:
i. Small concentrations of impurity atoms in the host material
ii. A small excess of one of the constituents of the host material
(self activation)

 Killers: small amounts of impurity atoms that

inhibit luminescence
Groups of luminescent crystalline solids:

i. Compounds which luminesce in “pure”

state. They usually have one ion or ion group
per unit cell with an incompletely filled shell of
electrons which is well screened from its
surroundings.

Eg: Manganous halides, gadalonium sulfate,

molybdates and platinocyanides
Groups of luminescent crystalline solids:
i. Compounds which luminesce in “pure” state.
ii. The alkali halides activated with thallium or other heavy
metals.
iii. ZnS and CdS activated with Cu, Ag, Au, Mn or with an
excess of one of their constituents (self activation).
iv. The silicate phosphors, such as zinc orthosilicate
(willemite, Zn2SiO4 ) activated with divalent
manganese, which is used as oscilloscope screens
v. Oxide phosphors such as self activated ZnO and Al2O3
or activated with transition metals.
vi. Organic crystals such as anthrcene activated with
naphtacene
Excitation and emission
 The presence of activator atoms in a crystalline
solids will give rise to localized energy levels in
the normally forbidden energy gaps. They are
classified as

i. Levels which belong to activator atoms themselves

i. Levels belonging to host atoms which are under the

influence of activator atoms. These may be associated with
host atoms in the immediate vicinity of impurity atoms but they may
also be associated with lattice defects whose existence is tied up
with the incorporation of the activator. Eg. Mn4+ ions in ZnS.
Excitation and emission
 The excitation from
ground state to excited
state excited state may
be accomplished by:
i. Direct absorption
ii. Diffusion of an exciton
(Combination of an
electron in the excited state
and the associated hole is
known as exciton)
iii. Motion of free electrons
and holes
 Thallium activated alkali halides
When “pure” alkali halides are irradiated with X-
rays a faint luminescence is observed, when
activated with Thallium they exhibit high
efficiencies for luminescence.

The absorption spectra: KCl:Tl

Due to the larger radius Tl ions occupy
substitutional positions rather than
interstitial positions of KCl crystal.
Thallium activated alkali halides
Emission spectra: Two principle emission bands at 3050Å and 4750Å
 Thallium activated alkali halides
Concentration dependence of luminescence efficiency 

is the ratio of the capture

cross section
 Electroluminescence
Luminescence when a material is subjected to an
electric field

The Gudden-Pohl effect: Emission of momentary flash of

light when an electric field is applied during the afterglow
(phosphorescence)
 Internal field which is set up due to polarisation rapidly
counteracts the external field. When the external field is
removed, the polarization field itself produces a momentary
flash and decays rapidly to zero.
Electro-photoluminescence: Luminescence associated with
the application of field during or after photo excitation.
Electroluminescence
 The Destriau effect: Emission
of light by a phosphor resulting
solely from the action of an electric
field applied to a suspension of
luminescent particles in an insulator.
 Also known as intrinsic electroluminescence
since the effect does not involve previous
photo excitation. It involves emptying of the
traps by the field, subsequent acceleration
of the electrons to the conduction band and
excitation of centeres by these electrons.
Electroluminescence
 Carrier-injection luminescence:
Emission by recombination of minority carriers
with their counterparts
The emitted radiation agrees well with the optical absorption
associated with band to band transitions.

Eg: For Ge and Si it lies in IR region.