Doping

• The process of adding an impurity to an intrinsic or pure material is called doping and the impurity is called
a dopant.
• Pure Silicon or Germanium are rarely used as semiconductors.
• After doping, an intrinsic material becomes an extrinsic material. Practically only after doping these materials become usable.
By doping conductivity can be increased by a factor of 106
• Doping process must not change the crystal structure or the bonding process. These electrons are loosely held together by
their originator atoms.
Doping can be 2 types:
Effect of Doping on N-type Material
o On addition of 5-valent elements to pure Si, crystal becomes an N-type material. Eg. N, P, As
o These impurities donate 1 electron to the crystal, so they are donor impurities.
o N-material has extra or free electrons than intrinsic material.
o N-type material is not negatively charged. They are electrically neutral.
o These extra electrons do not take part in covalent boding process. They are free to move thorough the crystal structure
o Only 0.7eV is required to move electrons of intrinsic crystal from the valence band into the conduction band.
o Electrons are considered to be the majority current carriers in this type of crystal and holes are the minority current carriers.
o The flow of current is achieved mostly by electrons in this type of material. Therefore, an extrinsic material becomes a good
electrical conductor.
 CY 110
Semi conductors
&
Green Chemsitry
 N-type doping P-type doping

Effect of Doping on P-type Material

•When a three valent atom is added to pure silicon, a P-type material is formed. Eg: Indium (In) or Gallium (Ga)
•This type of dopant material are looking for a fourth electron.
•In P type material, each hole can be filled with an electron. To fill this hole area, very less energy is required by electrons from the
neighboring covalent bonded groups.
•Silicon is typically doped with doping material in the range of 1 to 106. This means that P material will have much more holes than the
electron-hole pairs of pure silicon.
•At room temperature, there is a very determined characteristic difference in the electrical conductivity of this material.
• holes are considered to be the majority current carriers in this type of crystal and electrons are the minority current carriers. In this
case, Indium. A piece of P-type material is not positively charged. Its atoms are primarily all electrically neutral.
• When an electron moves in and fills a hole, the hole becomes void. A new hole is created in the bonded group where the electron
left. Hole movement in effect is the result of electron movement. A P-type material will go into conduction with only 0.05 eV of
energy applied.
 EPITAX
Y
Semiconductor fabrication involves 4 following general categories
• Deposition : Epitoxial growth
• Removal
• Pattering
• Doping

Epitaxy is a method to grow or deposit monocrystalline films on a structure or surface (crystalline

substrate).
Deposition of crystalline overlayer on a crystalline substance

There are two types of epitaxy:

• Homoepitaxy: Homoepitaxy is a process in which a film is grown on a substrate of the same
composition. (Substrate and film are same composition)
▪ PsuedoHomoepitaxy:
• heteroepitaxy: Heteroepitaxy is a film that is grown on a substrate, which has a different
• Epitaxial silicon is grown using vapor-phase epitaxy (VPE). This is a modification of chemical vapor
deposition (CVD). Another technology, molecular-beam epitaxy (MBE), is mainly for compound
semiconductors. MBE is a slow, line-of-sight technique, not suitable for filling trenches and other
three-dimensional structures.

• For silicon processes, epitaxy is used in source-drain and strain engineering techniques. They are
also playing a big role in the channel in chip designs.
• Using a blanket epitaxial process, chipmakers integrated silicon-germanium (SiGe) stressors, or
distortions in the crystal lattice, in PMOS transistors. This, in turn, boosted hole mobility and drive
current.
• At one time, the leading candidate was germanium (Ge) for PMOS and indium-gallium-arsenide
(InGaAs) for NMOS. (Ge has an electron mobility of 3,900cm-square-over-Vs, compared to
1,500cm-square-over-Vs for silicon. InGaAs has an electron mobility of 40,000cm-square-over-Vs.)
 Etching
• In the fabrication of semiconductor microdevices various materials have to be
etched. Either for removing an entire layer from the surface or to transfer a resist
pattern into a layer beneath.
• Etch processes can be devided into wet and dry etching while there is a further
separation into isotropic and anisotropic processes and also a separation in
chemical and physical etch characteristics.
• In an isotropic etch process the etching occurs in lateral and vertical direction. Thereby
layers are removed not only in thickness but also in their circumference.
• In anisotropic processes the layer is only removed in vertical direction. Depending on the
demands an isotropic process can be desired as well as an anisotropic.
In etch processes, selectivity is important.
The selectivity is the ratio of abrasion of the layer which should be etched (e.g. an
oxide film) and of the other layer (e.g. a resist mask).
If the selectivity is 2:1 the oxide would be etched twice as fast as the resist.

Wet chemistry processes are not only applicable for etching but also for other needs:
•wet etching: removal of doped or undoped oxide layers from the entire wafer
•wafer cleaning
•photoresist removal
•backside processing: to remove layers which were deposited as a byproduct during
other processes (e.g. thermal oxidation)
•polymer removal: to remove byproducts which occur during dry etching

The wet etching is only used very rare for structuring because of its (generally) isotropic
etch profile. An exception are micromechanical devices. Due to the atomic structure of
silicon crystals, well defined profiles with flank angles of 90° or 54.74° can be produced
using wet chemistry.
 Green Chemistry
New chemistry is required to improve the economics of chemical manufacturing and to enhance the
environmental protection.

Definition: Green chemistry is characterized as reduction of the environmental damage accompanied by the
production of materials and respective minimization and proper disposal of wastes generated during different
chemical processes to minimize hazards to humankind and the environment.

Hence, there is an essential need to improve the synthetic and engineering chemistry either by environmental
friendly starting materials or by properly designing novel synthesis routes that reduce the use and generation of
toxic substances by using modern energy sources.

12 Principles:
1. Prevention
It is beneficial to a priori prevent the generation of waste instead of later on treating and cleaning up waste
2. atom economy
Synthetic production routes have to be planned in a way maximizing the incorporation of all the compounds
used in the synthesis into the desired product
3. less precarious chemical syntheses
Wherever feasible, such synthetic methods have to be aspired, which resort to and generate compounds of
no or only insignificant noxiousness to the environment and human health
4. designing safer chemicals
Chemicals should be developed in a way affecting their desired functionality, while, at the same time,
considerably reducing their toxicity

5. safer solvents and safer auxiliaries

Expenditure of auxiliary substances, such as solvents, separation agents, and others, should be
avoided wherever possible; if not possible, harmless auxiliaries should be used

6. design for energy efficiency

The environmental and economic impact of energy demands for chemical processes should be analyzed in
terms of followed by optimizing the required energy input. Wherever practicable, chemical synthesis should
be carried out under mild process conditions, hence, at ambient temperature and pressure

7. renewable feedstocks
Whenever feasible in technological and economic terms, synthetic processes should resort to such raw
materials and feedstocks, which are renewable rather than limited

8. derivative reduction
Redundant derivatization, e.g., protection/deprotection, the use of blocking groups, or temporary
modification of physical/chemical processes, requires additional reagents and often contributes to additional
waste generation. Therefore, wherever possible, they should be avoided or reduced to a minimum
9. catalysis
Generally, catalytic reagents are intrinsically superior to
stoichiometric reagents; these catalysts should be as
selective as possible

10. degradation
Chemical products have to be designed in such a way that,
at the end of their life span, they do not resist in the
biosphere, but disintegrate into nontoxic degradation
products

11. real-time analysis for pollution prevention

Advanced analytical methods have to be developed,
which permit the real-time, in-line process monitoring
and control well before hazardous substances are
generated

12. accident prevention by inherently safer chemistry

Compounds and the compound’s formula applied in a
chemical process should be chosen in a way minimizing
the risk of chemical accidents, encompassing the release
of chemicals, detonations, or fire formation
 Atom Economy
• Atom Economy (AE) also called Atom Efficiency.
• It refers to the concept of maximizing the use of raw materials so that the final product contains the maximum
number of atoms from the reactants.
• The ideal reaction would incorporate all of the atoms of the reactants.
• The AE is measured as the ratio of the molecular weight (MW) of the desired product over the molecular
weights of all reactants used in the reaction.
• It is a theoretical value meant to quickly assess how efficient a reaction will be.

• AE = MW product/MW of reagents

Green Chemistry: Principles and Practice, Chem. Soc. Rev., 2010, 39,
In above example, A3 coupling and the Diels–Alder reaction are presented below.
This one-step multicomponent coupling reaction is more efficient and conserves atoms since 92% of the original atoms
used are found in the final product.

The Diels–Alder reaction is also an excellent example of an atom-economical reaction . Its AE is equal to 100% since all
atoms from the reactants are incorporated into the final product. Diels–Alder type reactions belong to the category
of cycloaddition which is among the greenest types of reactions in traditional chemistry.

The Grignard reaction, which received the recognition of the scientific community for its importance in organic
synthesis, is unfortunately a relatively poor atom-economical reaction due to the use of a stoichiometric amount of
metal reactant and the necessity to prepare the Grignard reagent separately.

Environmental Factor (E-factor):

E-factor is another important index to evaluate the environ-mental impact of a reaction. It enables us to estimate the
amount of waste that could be generated per kilogram of product produced. The higher the E-factor value, the more
waste will be generated.

E-factor = mass (waste)

mass (product)
Where mass (waste) and mass (product) represent the amounts of waste and product generated in the same weight
unit. Unlike the atom economy, the waste accounts for all nonrecyclable postreaction components including unreacted
starting materials, byproducts, and solvents.
For example, the oil industrial processes have a lower E-factor because they are highly optimized for their
tasks, and the various products generated from the refinery are utilized very efficiently, which minimizes
deposals.30Higher value products such as pharmaceuticals always have a higher E-factor due to the
multi-step synthesis procedures. A general description of the trend is given in Table

E-factor serves as a parameter for the chemist to achieve waste reduction that is based on the outcome of
the reaction.

Anasta, P. T. J. Chem.Educ.2019, 96,

761−765
 Conventional and Green synthesis of Ibuprofen
Every Green Chemistry research describe the big successes of the last decades in the field of new synthetic routes for
industrial chemicals. The first is the synthesis of Ibuprofen, the second is the synthesis of Adipic acid (important starting
chemical substance for Nylon and catehole and the third is the synthesis of Maleic anhydrite (starting material for
polyesters and dyes).
Conventional Method Green synthesis

Total 6 steps 3 steps

Starting materials could not be incorporated into products
Staring material is 2-methylpropylbenzene
Producing lots of biproducts and waste
6-steps consuming the chemical s and energy while
lowering the yield of product 45%
AlCl3 as catalyst had to be thrown away as waste.
Energy also was lost by the low efficiency of the reaction
method.
Atoms of starting materials could be incorporated into
products and reduced waste
Staring material is 2-methylpropylbenzene
Reduced the waste.
Final yield is 77%.
Raney Ni (Nickel, O/Pt) as catalyst. It is recyclable and
reusable
Lower energy sufficient than conventional

International Journal of Scientific Research in Chemistry (IJSRCH) | ISSN : 2456-8457