Module -II Chemistry in Electronics and Semiconductor Material

Chemistry & Electronics

1. Materials for Electronic Components

2. Energy Storage

3. Manufacturing and Fabrication

Inorganic Electronics
Inorganic electronics involves the creation and application of electronic devices
that are made from inorganic materials such as Si, Ge, etc.
Organic Electronics
Organic electronics uses carbon-based molecules and polymers, instead of silicon,
to create flexible, lightweight, and potentially lower-cost electronic devices
Organic vs Inorganic electronic
Property Organic Electronics Inorganic Electronics

Semiconductors (e.g., Silicon,

Material Basis Carbon-based materials
Germanium)

Substrate Glass, silicon, or plastic Costly specific substrates

Weight Lightweight Heavyweight

Mechanical Flexibility Good flexibility Rigid, no flexibility

Chemical Modifications Possible Not possible

Easy and cheap (e.g., ink-jet

Fabrication Process Requires cleanroom laboratory
printing, spin coating)

Crystallinity Poor crystallinity Good crystallinity

Possible degradation under

Environmental Stability Stable, no degradation
environmental influences

Device Speed Low speed High speed

Organic Semiconductor
An organic semiconductor is a type of material made primarily from carbon-based molecules
or polymers that can conduct electricity under certain conditions

One good example of an organic semiconductor material is a π-conjugated (or conjugated)

molecule. Examples include 1,3-butadiene and 1,3-hexadiene, which contain alternating
single and double bonds that allow for electron delocalization.
1,3-butadiene and 2,4-hexadiene are classic examples of conjugated molecules, which are

excellent candidates for organic semiconductors. Their structure of alternating single and double

bonds allows the electrons to be delocalized across the molecule, which narrows the energy gap

between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular

orbital (LUMO). This HOMO-LUMO gap is the molecular equivalent of the band gap in

traditional inorganic semiconductors, functioning analogously to the valence band and

conduction band, respectively. The reduced energy gap facilitates the excitation of electrons,

enabling charge transport and resulting in the semiconducting properties of these materials.
Few more example
p - type semiconductor

n - type semiconductor
key applications of organic semiconductors
•Organic Light-Emitting Diodes (OLEDs): Used in high-end displays for smartphones, TVs,
and wearable devices. OLEDs offer vibrant colors, deep blacks, and energy efficiency due to
their thin, flexible layers.

•Organic Solar Cells (OPVs): These lightweight, flexible solar panels are ideal for portable
electronics, building-integrated photovoltaics, and even clothing-based energy harvesting.

•Organic Field-Effect Transistors (OFETs): Found in flexible circuits, sensors, and low-cost
RFID tags. OFETs are key components in developing bendable and stretchable electronics.

•Chemical and Biological Sensors: Organic semiconductors are sensitive to environmental

changes, making them excellent for detecting gases, biomolecules, and pollutants in wearable
health monitors and smart packaging.

•Printed and Flexible Electronics: Their solution-processability allows for inkjet or roll-to-roll
printing, enabling low-cost production of flexible displays, smart labels, and electronic skins.
Chemistry in Electronic Devices
What is LED?
LED (electroluminescence)
An LED, or Light Emitting Diode, is a semiconductor device that emits light when an electric
current passes through it.
It's widely used in everything from phone screens and TVs to streetlights and medical devices
due to its efficiency, durability, and compact size.
Some LED materials used in different applications
GaAs emits infrared
GaAsP emits red to yellow
GaN emits blue to ultraviolet
Electroluminescence
One of the application of organic electronic is Electroluminescence

Electroluminescence is an electrical and an optical phenomenon.

Electroluminescence is the characteristic of a material to emit light
when an electric current is passed through it, or when subjected to a
strong electric field. It is the principle behind the construction of LED,
OLED, QLED used in automobile displays, and night lamps.
Semiconductors are the most predominantly available electroluminescent
materials
Working of LED (electroluminescence)
Working Principle
[Link] Setup: An LED is made from a p-type semiconductor (rich in holes) and an n-type
semiconductor (rich in electrons) joined together.
[Link] Voltage: When a forward voltage is applied (positive to p-side, negative to n-side), it
pushes electrons from the n-side and holes from the p-side towards the junction between them.
[Link]: At the junction, these electrons and holes recombine.
[Link] of Light: When an electron falls into a hole, it loses energy. This energy is released
in the form of a light. The color of the light is determined by the energy released (and therefore
the material) of the semiconductor.
What is OLED (organic light emitting diode)?

OLED is light emitting diode in which organic layer is responsible for

light emission.

There are some organic molecule which exhibit light under the
influence of electric field. LED panels are made from organic materials
that emit light when electricity is applied through them
The Basic Principle
Construction and working of OLED
Basic construction of OLED are shown below;
OLED Structure
Substrate (plastic, glass, foil) - The substrate supports the OLED.
Anode (transparent) - The anode removes electrons from conducting organic polymer layer (adds electron
"holes") when a current flows through the device. One of the widely used anode material is transparent, conducting
ITO (indium tin oxide)
Conducting layer - This layer is made of organic polymer molecules like polyaniline that transport "holes”.
Emissive layer - This layer is made of organic polymer molecules like polyfluorene (different ones from the
conducting layer) that transport electrons from the cathode; this is where light is made.
Cathode (may or may not be transparent depending on the type of OLED) - The cathode injects electrons to
the emissive layer when a current flows through the device. Aluminium can be used as cathode material.
During operation, a voltage is applied across the OLED such that the anode is
positive with respect to the cathode. A current of electrons flows through the
device from cathode to anode, as electrons are injected into the LUMO of the
organic emissive layer at the cathode and withdrawn from the HOMO of the
conducting organic layer at the anode.

Electrostatic forces bring the electrons and the holes towards each other, and they
recombine forming an exciton (a bound state of the electron and hole) This
happens closer to the emissive layer, because in organic semiconductors holes are
generally more mobile than electrons. The recombination of electron – hole
creates an excited state results in a relaxation of the energy levels of the
electron, which gives out light of a certain color depending on the properties
of the organic material.

The wavelenght of this radiation depends on the band gap between the HOMO
and LUMO of the organic molecule
[Link] Applied: A voltage is applied, making the anode positive and the cathode negative.

2. Injection: Electrons are injected from the cathode into the LUMO of the emissive layer.
Simultaneously, holes (the absence of electrons) are created in the HOMO of the conducting
layer.

3. Recombination: The electrons and holes move toward each other and meet in the emissive
layer, combining to form an exciton (an excited state).

4. Light Emission: This exciton relaxes, releasing its energy in the form of light. The color of
this light is determined by the energy difference (band gap) between the HOMO and LUMO
levels.
What is QLED
QLED stands for Quantum-dot Light Emitting Diode. It's a display technology used primarily
in modern televisions and monitors, developed and popularized by companies like Samsung.
QLED TVs use a quantum dot layer . These quantum dots are tiny semiconductor particles
that emit specific colors when exposed to light.

Advantages of QLED technology

QLED several advantages over traditional LED and even some OLED displays
•Brighter images: QLED TVs can achieve higher brightness levels, creating clarity to images
•Vivid colors: Quantum dots produce more accurate and saturated colors.
•Longer lifespan: Unlike OLED, QLEDs are less prone to burn-in and degradation over time.
•Better HDR performance: High brightness and color accuracy enhance HDR (High Dynamic
Range) content. It enhances the contrast and color range of visuals
Conducting polymers
Down the years polymers (plastics) are known for their insulating properties. But
outstanding work by Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa
have changed this view that a polymer like polyacetylene, can be made conductive
almost like a metal.
Definition
Polymers with highly delocalized pi electrons having electrical conductance in the
order of metal or semiconductor are known as conducting polymers. Example:
poly aniline, poly pyrrole and polyacetylene
Example: poly aniline, poly pyrrole and polyacetylene
Applications of conducting polymers
Electronics
LEDs,
transistors,
Flexible devices

Energy storage
batteries,
Supercapacitors

Biomedical devices
biosensors,
drug delivery,
neural probes

Environmental solutions
anti-corrosion coatings,
water remediation
POLYANILINES (PANI): CONDUCTING POLYMER

Polyaniline is the most promising and most explored among conducting polymers, and
polyaniline has high stability, high processability, tunable conducting and optical properties. The
conductivity of polyaniline is dependent upon

[Link] dopant concentration,

[Link] it gives metal-like conductivity only when the pH is less than 3.

Mechanism of Conduction in Polyaniline - Oxidative doping
1. Non-conducting form of Polyaniline is known as emeraldine base. In this form polyaniline
according to band theory, the energy gap between the valence band and conduction band is large,
making it an insulator.
2. Upon doping with HCl, the electron from imine nitrogen atoms of the polymer backbone get
jerked out. This introduces positive charges (holes) into the polymer chain, forming a polaron- a
localized charge coupled and creates distortion in the polymer chain. These polarons are mobile
and initiate conductivity.
3. Further doping leads to the formation of bipolarons. Two polarons can combine to form a
bipolaron, which carries two positive charges and is more delocalized. The conjugated
backbone of polyaniline allows these charges to move freely along the chain. This delocalization
of charge carriers contributes to the electrical conductivity of polyaniline.
TYPES OF POLYMER
Other than conducting polymer as mentioned earlier, there are two main types of polymers
are present
Thermoplastics
are polymers that can be repeatedly softened when heated and hardened when cooled,
allowing them to be reshaped and remolded
Polyethylene, polypropylene, polystyrene, and PVC.

Thermosetting
These polymers, are polymers that become permanently hard and rigid when heated due
to the formation of a highly cross-linked, three-dimensional network structure
Epoxy Resin, Bakelite, Silicone
USES OF THERMOSETTING PLASTICS

o Thermosetting plastics are heat resistant, so they are used in the making of kettles, plugs,
laptop chargers, etc.
o They are used in Electrical fittings, handles, and control knobs, adhesives
o automotive appliance,
o These are used to produce construction equipment panels.
o These are used in agricultural equipment including feeding troughs and motors.
USES OF THERMOPLASTIC

packaging (bottles, films),

automotive (bumpers, dashboards),

construction (pipes, window frames),

electronics (casings, insulation),

consumer goods (toys, containers).

REMEMBER – THESE ARE THERMOPLASTIC
Inorganic Semiconductor
Doping & It’s effect
WHY DOPING?

• Pure inorganic semiconductor have low conductivity because charge carriers are
limited.

• Doping introduces extra charge carriers (holes or electrons), increasing

conductivity by several orders of magnitude.

• Doping allows tuning of color, optical absorption, and electronic properties for
specific applications.
DOPING: N- & P SEMICONDUCTORS
Definition of Doping
Doping means the introduction of impurities into a semiconductor crystal to the defined
modification of conductivity.

Example for doping materials

Two of the most important materials silicon can be doped with, are boron (3 valence electrons =
trivalent) and phosphorus (5 valence electrons = pentavalent). Other materials are aluminum,
indium (3-valent) and arsenic, antimony (5-valent).

Elements with 3 valence electrons are used for p-type doping

Elements with 5-valence electrons are used for n-doping

The conductivity of a deliberately contaminated silicon crystal can be increased by of 106.

N-DOPING

• The 5-valent dopant has an outer electron more than the silicon atoms.

• Four outer electrons combine with ever one silicon atom, while the fifth electron is free to

move and serves as charge carrier.

• This free electron requires much less energy to be lifted from the valence band into the
conduction band, than the electrons which cause the intrinsic conductivity of silicon.

• The dopant, which emits an electron, is known as an electron donor.

• Arsenic is used as an alternative to phosphorus, because its diffusion coefficient is lower. This
means that the dopant diffusion during subsequent processes is less than that of phosphorus
N doping with Phosphorus

The P atom donates its fifth valence electron. This free electron act as charge carriers
ELECTRONIC BAND STRUCTURE “N” DOPED SEMICONDUCTOR

As mentioned earlier by the introduction of an extra free electrons, in n-doped

semiconductors this extra free electron in the crystal which is not bound and
therefore can move with relatively little energy into the near conduction band
forming new energy level known as donor level as shown in the figure.

Electrons can be excited from the donor level into the conduction band by
absorbing very little energy, facilitating easier conductivity.

[***NOTE to students: while donor levels lie within the band gap, they do not
reduce the band gap itself]
P-DOPING

❖In contrast to the free electron due to doping with phosphorus, the 3-valent dopant effect is
exactly the opposite.
❖When 3-valent boron doped with Silicon, the three electrons of the boron can catch three
electrons of the silicon, thus leaving a hole (missing electron) in the valence band of silicon
atoms.
❖Therefore, the mobile hole in the valence band become mobile.
❖The holes with little energy move to the new energy level near to valence band known as
acceptor level.
 The created hole site can be filled with adjacent electron. Hence a new
hole generated. Its can be visualized as movement of holes in the crystal
lattice giving electrical conductivity.

[Note to students: from the above description, remember when holes moved means electron
also moving. Actually, holes moves opposite to the movement of electron.]
ELECTRONIC BAND STRUCTURE “P” DOPED SEMICONDUCTOR

As mentioned earlier by the introduction of a hole (missing electron), in p-doped

semiconductors & this hole in the crystal which is not bound and therefore can
move with relatively little energy into the near valence band forming new energy
level known as acceptor level as shown in the figure.

Now electrons can be excited from the valence band into the acceptor level by
absorbing very little energy, facilitating easier conductivity.
REMEMBER THIS !! Doped Silicon
1. n-type (Si doped with Phosphorus)
•Donor level: Introduced just below the conduction band
•Energy required to excite electron: ~0.045 eV
•Band gap remains: 1.12 eV
•The donor level doesn’t shrink the band gap-it just makes it easier for electrons to jump into
the conduction band.
2. p-type (Si doped with Boron)
•Acceptor level: Introduced just above the valence band
•Energy required to excite electron: ~0.045 eV
•Band gap remains: 1.12 eV
•Again, the band gap itself doesn’t change, but holes are more easily created in the VB
Effect of temperature on the Fermi level of N-type and P-type semiconductors

The Fermi level is a theoretical energy level that represents the probability of electron
occupancy in a material. At absolute zero temperature, it is the highest occupied energy
level.

In intrinsic semiconductors, the Fermi level lies approximately midway between the valence
band and the conduction band.

Its position shifts depending on doping and temperature, and it plays a crucial role in
determining the electrical properties of materials.
The Fermi level in semiconductors is influenced by temperature, especially in n-type and p-type
materials. Here's how temperature affects the Fermi level in both types:

n-type Semiconductors
Definition: n-type semiconductors are doped with donor impurities that provide extra electrons.
Effect of temperature
At Low Temperatures: The Fermi level is closer to the conduction band because there are
fewer thermally generated electrons. Most electrons occupy the donor levels.

As Temperature Increases: More electrons gain enough energy to jump from the donor levels
to the conduction band. This causes the Fermi level to shift slightly upward towards the
conduction band, but it remains closer to the conduction band than to the valence band.
p-type Semiconductors
Definition: P-type semiconductors are doped with acceptor impurities that create
holes (missing electrons).
Effect of Temperature
At Low Temperatures: The Fermi level is closer to the valence band since the
majority of charge carriers are holes created by the acceptor levels.
As Temperature Increases: More electrons can be thermally excited from the
valence band to the acceptor levels, increasing the number of holes. The Fermi
level shifts slightly downward toward the valence band but remains closer to the
valence band than to the conduction band
ROLE OF IMPURITIES IN SEMICONDUCTORS
Enhance electrical conductivity:

Impurities (via doping) introduce free charge carriers-electrons in n-type and holes in p-type
semiconductors- dramatically increasing conductivity compared to intrinsic semiconductors.

Create donor and acceptor energy levels:

Donor impurities (e.g., phosphorus) add energy levels just below the conduction band, while
acceptor impurities (e.g., boron) introduce levels just above the valence band, enabling easier
excitation of carriers.

Control semiconductor type and behavior:

By selecting specific impurities, manufacturers can precisely engineer whether a semiconductor

behaves as n-type or p-type, which is crucial for designing electronic components like diodes,
transistors, and solar cells
PASSIVATION IN SEMICONDUCTOR DEVICE

Passivation is the process of applying a protective layer to the surface of a semiconductor device
to shield it from environmental contaminants, reduce surface recombination, and enhance
device stability and performance.

For silicon-based devices, silicon dioxide (SiO₂) is one of the most effective and commonly used
passivation materials due to its excellent insulating properties and compatibility with silicon
technology.
Mechanism of Silicon passivation

When silicon is exposed to oxygen (O₂) at high temperatures (typically 800-

1100 °C), a chemical reaction occurs at the surface, forming a high-quality oxide

layer ideal for gate oxides in insulating layer of SiO₂.

Chemical reactions:

Si (solid)+O2(gas)→SiO2(solid layer)