18IT103/18CS103/19IS103/20AI103/19CT103 – ENGINEERING CHEMISTRY I

6 Hours
UNIT I
Optical materials for smart screen
Types - inorganic: rare earth metals [yttrium, lanthanum, cerium, praseodymium, neodymium,
europium, terbium and dysprosium] – organic : organic dielectric material [Polystyrene, PMMA]
– organic light emitting diodes [Polythiopene]

Unit I – LP 1 - Optical materials for smart screen

Energy level
 A quantum mechanical system or particle that is bound—that is, confined spatially —can
only take on certain discrete values of energy- called energy levels.
 The term is commonly used for the energy levels of electrons in atoms, ions or molecules-
which are bound by the electric field of the nucleus.
 It can also refer to energy levels of nuclei or vibrational or rotational energy levels in
molecules.
Molecular Energy Levels
Energy can be stored either as potential energy or kinetic energy, in a variety of ways including
 Rotational energy: kinetic energy associated with the rotational motion of molecules.
 Vibrational energy: the oscillatory motion of atoms or groups of atoms within a molecule.
 Electronic energy: energy stored as potential energy in excited electronic configurations.
All except the Translational energy are quantized
Emolecule = Erotational + Evibrational + Eelectronic

Ground and excited states

 If an atom, ion, or molecule is at the lowest possible energy level, it and its electrons are
said to be in the ground state.
 If it is at a higher energy level, it is said to be excited, or any electrons that have higher
energy than the ground state are excited.
 If more than one quantum mechanical state is at the same energy, the energy levels are
called degenerate energy levels

Absorbance and Emission

When a photon of energy hν strikes the atom or molecule, absorption may occur if the
difference in energy, ΔE, between the ground state and the excited state is equal to the photon’s
energy. An atom or molecule in an excited state may emit a photon and return to the ground state.
The photon’s energy, hν, equals the difference in energy, ΔE, between the two states. When an
atom or molecule absorbs electromagnetic radiation the number of photons passing through the
sample decreases. The measurement of this decrease in photons, which we call absorbance.

When an atom or molecule in an excited state returns to a lower energy state, the excess
energy often is released as a photon, a process we call emission. There are several ways in which
an atom or molecule may end up in an excited state, including thermal energy, absorption of a
photon, or by a chemical reaction. Emission following the absorption of a photon is also called
photoluminescence, and that following a chemical reaction is called chemiluminescence.
Luminescence is spontaneous emission of light by a substance not resulting from heat; or
"cold light". Luminescence occurs in some minerals when they are exposed to low-powered
sources of ultraviolet or infrared electromagnetic radiation (for example, portable UV lamps), at
atmospheric pressure and atmospheric temperatures

Phosphor materials
A phosphor, most generally, is a substance that exhibits the phenomenon of luminescence.
This includes both phosphorescent materials, which show a slow decay in brightness (> 1 ms), and
fluorescent materials, where the emission decay takes place over tens of nanoseconds.
Phosphorescent materials are known for their use in radar screens and glow-in-the-dark
materials, whereas fluorescent materials are common in cathode ray tube (CRT) and plasma video
display screens, fluorescent lights, sensors, and white LEDs. Phosphors are often transition-metal
compounds or rare-earth compounds of various types. The most common uses of phosphors are
in CRT displays and fluorescent lights
Electroluminescence
 Electroluminescence or "EL" is the non-thermal conversion of electrical energy into light
energy. This phenomenon is used in EL lamps, LEDs, and OLEDs.
 Electroluminescence (EL) is the generation of light by the application of an electric field to
crystalline materials, or resulting from a current flow through semiconductors. The most
common electroluminescent (EL) devices are composed of either powder or thin films.
 The EL of inorganic materials is classified into the two groups:
1. Injection electroluminescence, 2. High electric field electroluminescence

Common uses: nightlights, decorative luminescent clothing, watch illumination, flat wall
decorative illumination, durable waterproof displays, medical tool display screens, and most
recently computer monitors and billboards.

Mechanism
Electroluminescence is the result of radiative recombination of electrons & holes in a
material, usually a semiconductor. The excited electrons release their energy as photons - light.
Prior to recombination, electrons and holes may be separated either by doping the material to
form a p-n junction (in semiconductor electroluminescent devices such as light-emitting diodes)
or through excitation by impact of high-energy electrons accelerated by a strong electric field (as
with the phosphors in electroluminescent displays).

Examples of electroluminescent materials

Electroluminescent devices are fabricated using either organic or inorganic
electroluminescent materials. The active materials are generally semiconductors of wide enough
bandwidth to allow exit of the light. The most typical inorganic thin-film EL (TFEL) is ZnS:Mn
with yellow-orange emission.
 Examples of the range of EL material include:
 Powdered ZnS doped with Cu (producing greenish light) or Ag (producing bright blue
light)
 Thin-film ZnS doped with Mn (producing orange-red color)
 Semiconductors containing Group III and Group V elements, such as indium phosphide
(InP), gallium arsenide (GaAs), and gallium nitride (GaN) (Light-emitting diodes.)
 Certain organic semiconductors, such as [Ru(bpy)3]2+(PF6‾)2, where bpy is 2,2'-bipyridine

Introduction to smart screen

A liquid crystal display (LCD) exploits a optical property of organic compounds to pass
light and illuminate all the pixels, thus ensuring the possibility of transmitting the image. A
display of this type consists of four parts: a backlight, two polarizing filters and a layer of liquid
crystals and pixels.
Its operation is as follows: the backlight (currently LED or cold cathode fluorescent lamp:
CCFL type) produces vertical light rays, which pass through the first polarizing filter that filters
and passes only the vertical lights. Subsequently, the light rays come into contact with the layer of
liquid crystals and pixels.
 In LED display, the backlight is not required as it emits visible light readily. It is very
lighter and thinner than LCD. In low ambient temperature condition LED screen can achieve high
contrast ratio than LCD.
Inorganic optical materials
The rare-earth elements usually comprise 17 elements consisting of the 15 lanthanides from
La (atomic number 57) to Lu (atomic number 71), of Sc (atomic number 21), and of Y (atomic
number 39)
The electronic configurations of trivalent rare-earth ions in the ground states, Sc3+ is
equivalent to Ar, Y3+ to Kr, and La3+ to Xe in electronic configuration. The lanthanides from Ce3+
to Lu3+ have one to fourteen 4f electrons added to their inner shell configuration, which is
equivalent to Xe. Ions with no 4f electrons, i.e., Sc3+, Y3+, La3+, and Lu3+, have no electronic energy
levels that can induce excitation and luminescence processes in or near the visible region. In
contrast, the ions from Ce3+ to Yb3+, which have partially filled 4f orbitals, have energy levels
characteristic of each ion and show a variety of luminescence properties around the visible region.
Many of these ions can be used as luminescent ions in phosphors, mostly by replacing Y3+, Gd3+,
La3+, and Lu3+ in various compound crystals.

Sensitization of Lanthanide Luminescence

Since the dipole strengths of f–f transitions are very small, direct excitation into the 4f
excited levels rarely yields highly luminescent materials, even if the intrinsic quantum yield is
large, unless considerable excitation power is used (laser excitation, given the sharpness of the
absorption bands). Therefore, an alternative path has been worked out which is called
luminescence sensitization or antenna effect. The luminescent ion is imbedded into a matrix or an
organic environment such that the latter is a good light harvester. Energy is then transferred from
the excited surroundings onto the metal ion which eventually gives off its characteristic light.
Note, that several of the Ln(III) excited states may be implied in this process. The use of charge
transfer or 4f, 5d states for collecting and transferring energy has long been well established in
inorganic phosphors for lighting applications. On the other hand, the tuning of the electronic
properties of organic ligands to achieve the same goal starts only to be understood since the
process is more involved in view of the numerous electronic levels and mechanisms which may
be implied.
Luminescence of specific ions
Yttrium
Properties
 Yttrium is a soft, silver-metallic, lustrous and highly crystalline transition
metal in group 3.
 Less electronegative than its predecessor scandium, and less electronegative than
zirconium;
 It is more electronegative to its successor lanthanum,
 Closer in electronegativity to the lanthanides due to the lanthanide contraction.
 Yttrium is the first d-block element in the fifth period.
 The pure element is relatively stable in air in bulk form, due to passivation of a
protective oxide (Y2O3) film that forms on the surface.
 This film can reach a thickness of 10 µm when yttrium is heated to 750 °C in water
vapor.
 When finely divided, yttrium is very unstable in air; shavings or turnings of the
metal can ignite in air at temperatures exceeding 400 °C.
 Yttrium nitride (YN) is formed when the metal is heated to 1000 °C in nitrogen.
Applications
Yttrium is one of the elements that was used to make the red color in cathode ray tube
(CRT) televisions. The red component of color television cathode ray tubes is typically emitted
from an yttria (Y2O3) or yttrium oxide sulfide (Y2O2S) host lattice doped with europium (III) cation
(Eu3+) phosphors.
 The red color itself is emitted from the europium while the yttrium collects energy from
the electron gun and passes it to the phosphor. Yttrium compounds can serve as host lattices for
doping with different lanthanide cations.
Tb3+ can be used as a doping agent to produce green luminescence. As such yttrium
compounds such as yttrium aluminium garnet (YAG) are useful for phosphors and are an
important component of white LEDs.
Yttria is used as a sintering additive in the production of porous silicon nitride. It is used as
a common starting material for material science and for producing other compounds of yttrium.

Lanthanum
 Electron configuration [Xe] 5d1 6s2
 Electrons per shell: 2, 8, 18, 18, 9, 2
 Lanthanum is a chemical element with symbol La and atomic number 57.
 It is a soft, ductile, silvery-white metal that tarnishes rapidly when exposed to air and is
soft enough to be cut with a knife.
 It is the eponym of the lanthanide series, a group of 15 similar elements between
lanthanum and lutetium in the periodic table, of which lanthanum is the first and the
prototype.
 It is also sometimes considered the first element of the 6th-period transition metals and is
traditionally counted among the rare earth elements. The usual oxidation state is +3.
 Lanthanum usually occurs together with cerium and the other rare earth elements.
 Lanthanum compounds have numerous applications as catalysts, additives in glass, carbon
arc lamps for studio lights and projectors, ignition elements in lighters and torches,
electron cathodes, scintillators, GTAW electrodes, and other things.
Cerium (Ce3+ )
 Among the lanthanide ions, the 4f → 5d transition energy is the lowest in Ce3+, but the
energy gap from the 5d1 states to the nearest level (2F7/2) below is so large that the 5d
level serves as an efficient light-emitting state.
 The luminescence photon energy depends strongly on the structure of the host crystal
through the crystal-field splitting of the 5d state.
  The decay time of the Ce3+ emission is 10–7 to 10–8 s, the shortest in observed lanthanide
ions.
 This is due to two reasons: the d → f transition is both parity-allowed and spin allowed
since 5d1 and 4f 1 states are spin doublets

Praseodymium
 Electron configuration [Xe] 4f3 6s2
 Electrons per shell: 2, 8, 18, 18, 21, 8, 2.
 Praseodymium is a chemical element with symbol Pr and atomic number 59.
 It is the third member of the lanthanide series and is traditionally considered to be one of
the rare-earth metals.
 Praseodymium is a soft, silvery, malleable and ductile metal, valued for its magnetic,
electrical, chemical, and optical properties.
 It is too reactive to be found in native form, and pure praseodymium metal slowly
develops a green oxide coating when exposed to air.
 Praseodymium is used to color ceramics yellow

Neodymium
 Neodymium is a chemical element with symbol Nd and atomic number 60.
 It is a soft silvery metal that tarnishes in air.
 Certain transparent materials with a small concentration of neodymium ions can be used in
lasers as gain media for infrared wavelengths (1054–1064 nm), e.g. Nd:YAG (yttrium
aluminium garnet), Nd:YLF (yttrium lithium fluoride), Nd:YVO4 (yttrium orthovanadate),
and Nd:glass. Neodymium-doped crystals (typically Nd:YVO4) generate high-powered
infrared laser beams which are converted to green laser light in commercial diode-pumped
solid-state (DPSS) hand-held lasers and laser pointers.
 The four lower-lying levels of Nd3+ provide a condition favorable to the formation of
population inversion. For this reason, Nd3+ is used as the active ion in many high-power,
solid-state lasers (at 1.06 μm wavelength); the most common hosts are Y3Al5O12 single
crystals (yttrium aluminum garnet, YAG) or glass.
Europium
 Europium is a chemical element with symbol Eu and atomic number 63.
 Relative to most other elements, commercial applications for europium are few and rather
specialized. Almost invariably, its phosphorescence is exploited, either in the +2 or +3
oxidation state.
 It is a dopant in some types of glass in lasers and other optoelectronic devices.
 Europium oxide (Eu2O3) is widely used as a red phosphor in television sets and fluorescent
lamps, and as an activator for yttrium-based phosphors.
 Color TV screens contain between 0.5 and 1 g of europium oxide. Whereas trivalent
europium gives red phosphors, the luminescence of divalent europium depends strongly
on the composition of the host structure.
 UV to deep red luminescence can be achieved. The two classes of europium-based
phosphor (red and blue), combined with the yellow/green terbium phosphors give "white"
light, the color temperature of which can be varied by altering the proportion or specific
composition of the individual phosphors.
 This phosphor system is typically encountered in helical fluorescent light bulbs. Combining
the same three classes is one way to make trichromatic systems in TV and computer
screens.
 Europium is also used in the manufacture of fluorescent glass. One of the more common
persistent after-glow phosphors besides copper-doped zinc sulfide is europium-doped
strontium aluminate.
 Europium fluorescence is used to interrogate biomolecular interactions in drug-discovery
screens. It is also used in the anti-counterfeiting phosphors in euro banknotes.

Terbium
 Terbium is a chemical element with symbol Tb and atomic number 65.
 It is a silvery-white, rare earth metal that is malleable, ductile, and soft enough to be cut
with a knife.
 Terbium oxide is used in green phosphors in fluorescent lamps and color TV tubes.
 Sodium terbium borate is used in solid state devices. The brilliant fluorescence allows
terbium to be used as a probe in biochemistry, where it somewhat resembles calcium in its
behavior.
 Terbium "green" phosphors (which fluoresce a brilliant lemon-yellow) are combined with
divalent europium blue phosphors and trivalent europium red phosphors to provide the
trichromatic lighting technology which is by far the largest consumer of the world's
terbium supply.
 Trichromatic lighting provides much higher light output for a given amount of electrical
energy than does incandescent lighting.
Dysprosium
 Dysprosium is a chemical element with symbol Dy and atomic number 66.
 It is a rare earth element with a metallic silver luster.
 Dysprosium is never found in nature as a free element, though it is found in various
minerals, such as xenotime.
 The trivalent dysprosium ion (Dy3+) has been studied due its downshifting luminescence
properties.
 Dy-doped yttrium aluminium garnet (YAG:Dy) excited in the ultraviolet region of the
electromagnetic spectrum results in the emission of photons of longer wavelength in the
visible region. This idea is the basis for a new generation of UV-pumped white light
emitting diodes.