CONTENTS:

Sr. No.

Topic

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Surface Engineering in Electronic Industry Semiconductor Doping

Ratandeep Pandeya, Akshay Makhijaa, Harshul Patela, Dhrumil Prajapatia,
a

Masters Student Mechanical Engineering, University of Ottawa, 75 Laurier Ave E, Ottawa, ON

K1N 6N5 Canada

INTRODUCTION:
In electronic and I.T sector, semiconductor are extensively used in manufacturing of thermistor,
IR sensors, diodes, transistors, and so forth. The reason of such an extensive use of
semiconductor in electronic equipment is due properties such as slope of fixation for a dopant in
a substrate gives distinctive properties, for example, variable conductivity, light emanation,
warm vitality transformation, and so on. The most popular materials used in substrate are Silicon
(Si) and Germanium (Ge), which are both the elements in group IV of the table and have 4
valence electrons in their outer shell.
History & Development in Electronic and Semiconductor Industry:
With technological improvements in the telegraph industry during late 19th century industrial era
and in the radio and telephone industries during the early 20th century. World War I pushed this
development to an unprecedented scale and a lot of technological leaps were made during this
era. The modern electronic industry was born out of telephone-, radio-, and television-equipment
development and the large amount of electronic-systems development during World War II of
radar, sonar, communication systems, and advanced munitions and weapon systems. In the
interwar years, the subject was known as radio engineering. The word electronics began to be
used in the 1940s. The electronic laboratories (Bell Labs in the United States for instance)
created and subsidized by large corporations in the industries of radio, television, and telephone
equipment, began churning out a series of electronic advances. Invented in 1904 by John
Ambrose Fleming, vacuum tubes were a basic component for electronics throughout the first
half of the twentieth century.

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What is vacuum tube?

In electronics, a vacuum tube or electron tube is device that controls electric current between
electrodes in an evacuated container. Vacuum tubes mostly rely on thermionic emission of
electrons from a hot filament or a heated cathode by the filament. This type of tube is called as a
thermionic tube or thermionic valve. A phototube, though, achieves electron emission through
the photoelectric effect only. Gas-filled tubes are similar devices containing a gas, typically at
low pressure, which exploit phenomena related to electric discharge in gases, usually without a
heater.
How it works?
All modern vacuum tubes are established on the concept a heated "cathode" boils off electrons
into a vacuum; electrons pass through a grid or many grids, which control the electron current;
the electrons then strike on the anode (plate) and are absorbed into it. The tube will make a small
AC signal voltage into a larger AC voltage by designing the cathode, grid(s) and plate suitably.
Thus we can amplify it.
Figure shows a characteristic modern vacuum tube. It is a glass bulb with wires passing through
its bottom, and connecting to the various electrodes inside. A powerful vacuum pump sucks all
the air and gases out before the bulb is sealed. To make a good tube, the pump must make a
vacuum with no more than a millionth of the air pressure at sea level. The "harder" the vacuum,
the better the tube will work and it will have long life.

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Figure 1: Schematic Diagram of vacuum tube

Advantages of vacuum tube:

1)
2)
3)
4)
5)

Higher sound quality.

Highly linear without negative feedback, specifically for small-signal types.
Easily tolerate large overloads and voltage spikes.
Characteristics are highly independent of temperature, greatly simplifying biasing.
Wider dynamic range available than transistors circuits, because of higher operating

voltages and overload tolerance.

6) Device capacitances differ only slightly with signal voltages.
7) Capacitive coupling can be done with small, high-quality film capacitors, due to
inherently high-impedances of tube circuits.
8) Tubes can be comparatively easily replaced by user.

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Disadvantages of vacuum tube:

1) Bulky, hence less suitable for portable products.
2) Higher operating voltages generally required.
3) High power consumption; needs heater supply that generates waste heat and produces
lower efficiency, particularly for small-signal circuits.
4) Cathode electron-emitting materials are used up in operation.
5) Sometimes higher cost than equivalently powered transistors.
In 1948 came the transistor and in 1960 the integrated circuit, which would revolutionize the
electronic industry. Semiconductors used in integrated circuits facilitated the development of
many technologies including wireless telegraphy, radio, television, radar, computers and
microprocessors.
SEMICONDUCTOR:
A semiconductor is defined as a solid chemical element or compound that can conduct electricity
under some conditions, making it a decent medium for the control of electrical current.
Depending on the current or voltage applied to a control electrode its conductance varies, or on
the intensity of irradiation by infrared (IR), visible light, ultraviolet (UV), or X rays. Most
semiconductors are crystals made of certain materials, most commonly silicon.
A semiconductor is capable of functioning of a vacuum tube which has hundreds of times its
volume. A single integrated circuit (IC) can do the work of a set of vacuum tubes that would fill a
large building and require its own electric generating plant.
TYPES OF SEMICONDUCTOR DOPING:

N-type semiconductor:
It is created when the dopant is an element that consists of five electrons in its valence layer.
Most commonly used for this purpose is phosphorus.
The phosphorus atoms bond with the crystal structure of the silicon, each one bonding with
four adjacent silicon atoms just like a silicon atom. As phosphorus atom has five electrons in
its outermost shell, and since four of them are bonded to adjacent atoms, the fifth valence
electron is unable to form a bond.

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The extra valence electrons in the phosphorous atoms then start to behave like the single
valence electron in a regular conductor such as copper. They are free to move about. Since
this type of semiconductor has extra electrons, it's called an N-type semiconductor.

Figure 2: Microstructure arrangement of P-type semiconductor

P-type semiconductor:
This type of semiconductor is created when the dopant (such as boron) is left with three
electrons in its valence shell. When small amount of dopant is added into the crystal, the
atom is able to bond with four silicon atoms and since it has only three electrons to offer,
a hole is created. This hole behaves like a positive charge, hence semiconductors doped in
this way are called P-type semiconductors.
Just like a positive charge, holes attract electrons. But when an electron moves into a hole, a
new hole is formed at its previous location. Hence, in a P-type semiconductor, holes move
around continuously within the crystal as electrons constantly try to fill them up.

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Figure 3: Microstructure arrangement of N-type semiconductor

As voltage is applied to either an N-type or a P-type semiconductor, current flows just like it
flows in a regular conductor. The negative side of the voltage pushes electrons, and the positive
side pulls them. The outcome is that the random electron and hole movement which is always
present in a semiconductor becomes organized in one direction thereby creating measurable
electric current.
MATERIALS USED FOR SEMI CONDUCTOR DOPING:
By far, silicon is the most widely used material in semiconductor devices. Its combination of low
raw material cost, relatively simple processing and a useful temperature range make it currently
the best compromise among the various competing materials. Silicon used in manufacturing
semiconductor device is currently fabricated into boules that are large enough in diameter to
allow the production of 300mm (12 inch) wafers.
Germanium (Ge) was widely used early as a semiconductor material but it is less useful than
silicon due to its thermal sensitivity. Today, Germanium-Silicon alloy is formed for use in very
high speed devices of which IBM is the largest producer. Silicon is abundantly available in
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earth's crust so it is easily available resulting in low cost. It had a limited usable temperature
range, lower voltage operation with greater current leakage. With advancement in technology,
silicon proved to be superior, though at the highest operating frequencies, elements of group III
and group VI prove to be superior eg: Gallium Arsenide. With better physical and chemical
properties and being cheaper, Silicon ensured its progress. The only germanium components in
the age of silicon was for germanium signal diodes, where their lower voltage drop was often a
desirable feature.
Germanium is also used to overcome the losses which occur due to silicon. Finfets are currently
being used in the scaling industry (14nm) to reduce the leakage current and to develop
integration density and performance of chips. It has been established that germanium finfets give
better performance when compared to silicon and helps in reducing short channel effects to a
greater extent.
The most important reason why Si is preferred over Ge is that it forms Silicon Dioxide due to
oxidation. SiO2 has very good passivizing qualities, have high dielectric constant and can protect
the chip from hostile surroundings. It can be etched only by HF acid. On the other hand,
Germanium oxide can be easily washed away by water. In addition, Si is easily and abundantly
available and can be purified to a high degree.

Figure 4: Table describing valance electronic configuration of dopants

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POPULAR DOPING IN SEMICONDUCTOR:

Doping is a process of introducing impure atoms into a semiconductor in a controllable manner
to improve its electrical properties. The doping with donors and acceptors allows to alter the
electron hole concentration in semiconductor in a very large range from 10

cm-3 up to 10

cm

. The carrier concentration can also be varied quite accurately which is used to produce PNjunctions and built-in electric fields.

TECHNIQUES IN SEMICONDUCTOR DOPING:

ION IMPLANTATION
In the ion implantation process, charged dopants (ions) are accelerated in an electric field and
irradiated onto the wafer. The depth of penetration can be set precisely either by reducing or
increasing the voltage needed to accelerate the ions. As the process is taking place at room
temperature, previously added dopants cannot diffuse out. Masking photo resist layer can be used
to cover the regions that need not to be doped.An implanter consists of the following
components:

Ion source: To ionize the dopants which are in gaseous state (e.g. boron trifluoride BF3).

Accelerator: The ions are drawn with approximately 30 kilo electron volts out of the ion
source

Mass separation: the charged particles are deflected at 90 degrees under the influence of
magnetic field. Very light particles are deflected more and too heavy particles are
deflected less than the desired ions and are trapped with screens behind the separator

Acceleration lane: the particles are accelerated to their final velocity (200 keV accelerate
ions up to 2.000.000 m/s)

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Lenses: lenses are used to focus the ion beam

Distraction: the ions are deflected with electrical fields to irradiate the desired
destination

Wafer station: Wafers are held into the ion beam after placing them on large rotating
wheels.

Figure 5: Illustration of an ion implanter

Penetrating depth of ions in the wafer: In contrast to diffusion processes, the particles do not
penetrate into the crystal due to their high velocity. The particles are slowed down by collisions
with silicon which causes damage to the lattice. Since silicon atoms are knocked from their
places, the dopants themselves are mostly placed interstitial. There, they are not electrically
active as there are is no bonding with other atoms that may give rise to free charge carriers.
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Recovery the crystal lattice and activation of dopants: Immediately after the implantation
process, about 5 % of the dopants are still bonded in the lattice. At temperatures about 1000 C,
the dopants move on lattice sites. The lattice damage due to the collisions were already cured at
about 500 C. These steps are carried out only for a very short time because the dopants move
inside the crystal during high temperature processes
Channeling: The substrate is present as a single crystal due to which the silicon atoms are
regularly arranged and form "channels". The dopant atoms injected by ion implantation can
move parallel to these channels and are slowed down slightly, hence penetrate deeply into the
substrate. In order to overcome this, some of the possibilities are as follows:

Wafer alignment: Regarding the ion beam, the wafers would be deflected at angle of 7
degrees. Thus the radiation is not parallel to the channels and the ions are decelerated
immediately by collision.

Scattering: A parallel arrival is prevented by a thin oxide layer which deflects the ions

Figure 6: Ion Implantation Channeling Process

Characteristic:
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The precision of ion implantation is very high.

the outward diffusion of other dopants is prevented by carrying out the process at room
temperature

spin coated photo resist as a mask is sufficient, an oxide layer, , is not necessary

ion implanters are very expensive, the costs per wafer are relatively high

the dopants do not spread laterally under the mask (only minimally due to collisions)

Wide range of elements can be implanted in the crystal with highest purity

Dopants which were previously used to deposit on walls or screens inside the implanter
and later be carried to the wafer.

three-dimensional structures (e.g. trenches) cannot be doped by ion implantation

the implantation process takes place under high vacuum, which must be produced with
several vacuum pumps

There are several types of implanters for small to medium doses of ions (10 11 to 1015 ions/cm2) or
for even higher doses of 1015 to 1017 ions/cm2. The ion implantation has replaced the diffusion
mostly due to its advantages.
3.4 Advantage and Disadvantage
Advantages:
1) It is a low temperature process.
2) The dose of the ions can be controlled.
3) It is possible to control the precise depth.
4) This process can be used to implant ions through thin layers of oxide.
5) This method can be used to obtain extremely low as well as high dope.
6) It is a fast process.
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Figure 7: Different parts of ion implantation equipment

Disadvantages:
1) The major disadvantage is that ion implantation process causes physical damage to the
surface.
2) Annealing is required to relieve the stresses and remove physical damage to the material.
3) Amorphous regions are formed in the crystal lattice.
4) Channeling causing irregular distribution of ions.
5) It is an expensive process.
6) It is one of the most hazardous process tools available in the semiconductor industry.

DIFFUSION
Diffusion is defined as the molecular movement from a region of higher concentration to one of
lower concentration by random motion of molecules. The result of diffusion is a gradual mixing
of materials. For example, a drop of ink in a glass of water is evenly distributed after a certain
amount of time. The diffusion can be performed in different ways:

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Empty space diffusion: the empty spaces in the crystal are filled by the impurity atoms
which are always present, even in perfect single crystals

Inter lattice diffusion: the impurity atoms move in-between the silicon atoms in the
crystal lattice.

Changing of places: the impurity atoms are located in the crystal lattice and are
exchanged with the silicon atoms.

Figure 8: Illustration of Diffusion Process

The dopant will continue to diffuse till concentration gradient is balanced, or the temperature was
lowered, so that the atoms can no longer move. The speed of the diffusion process depends on
several factors:

Dopant

Concentration gradient

Temperature

Substrate

Crystallographic orientation of the substrate

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DIFFUSION METHODS:
Diffusion with an exhaustible source
It means that the dopant is in limited quantity. As the diffusion process continues, the
concentration at the surface decreases, hence the depth of penetration into the substrate increases.
The diffusion coefficient of a substance indicates how fast it moves in the crystal. Arsenic with a
low diffusion coefficient penetrates slower into the substrate.
Diffusion with an inexhaustible source
It means the dopant is in unlimited quantity, hence the concentration at the surface remains
constant during the process which results in continuous replenishment of the particles that have
penetrated into the substrate. In the subsequent processes the wafers are placed in a quartz tube
that is heated to a certain temperature.
Diffusion from the gas phase
A carrier gas (nitrogen, argon etc.) that is mixed with the desired dopant (also in gaseous form,
e.g. phosphine PH3 or diborane B2H6) leads to the silicon wafers, on which the concentration
balance can take place.
Diffusion with solid source
Slices containing the dopants are placed between the wafers. As the temperature in the quartz
tube is raised, the dopant from the source discs diffuses into the atmosphere. With a carrier gas,
the dopant will be distributed uniformly, hence reaches the surface of the wafers.
Diffusion with liquid source
Boron bromide BBr3 or phosphoryl chloride POCl3 are used as liquid sources. A carrier gas is led
through the liquids transporting the dopant in gaseous state. Certain areas can be masked with
silicon dioxide since the entire wafers should not be doped. The dopants cannot penetrate
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through the oxide, and therefore no doping takes place at these locations. To avoid tensions or
even fractions of the discs, the quartz tube is gradually heated (e.g. +10 C per minute) till
900 C. Subsequent the dopant is led to the wafers. To set the diffusion process in motion, the
temperature is then increased up to 1200 C.
CHARACTERISTICS:

Since many wafers can be processed simultaneously, this method is quite favorable

If there already are dopants in the silicon crystal, they can diffuse out in later processes
due to high process temperatures

Dopants can deposit in the quartz tube, and be transported to the wafers in later processes

Dopants in the crystal are spreading not only in perpendicular orientation but also
laterally, so that the doped area is enlarged in a unwanted manner

Advantages and Disadvantages

Advantages:
1)
2)
3)
4)

The diffusion process doesnt damage the surface of the parent semiconductor.
Batch fabrication is possible.
Low overall cost of the process.
Being an isotropic process, the properties in the whole Silicon crystal is same.

Disadvantages:

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1) Diffusion process is based upon solid solubility of the parent material and the impurity.
This makes the process limited to a narrow range of materials.
2) Shallow junctions are difficult to fabricate.
3) The process cannot be carried at room temperature.
4) Low dose doping is difficult to carry out.
NEW EXPERIMENTAL METHODS:
A lot of research has been carried out in field of manufacturing semiconductors to reduce the cost
of production and increase quality of semiconductor. A lot of new experimental methods have
been discovered. Once Such method which is gaining popularity is Gas immersion laser doping
(GILD).
Gas Immersion Laser Doping (GILD):
In this process a thin Silicon wafer is immersed in Boron gas while a pulsed laser repeatedly
melts and cools the wafer. The Boron atoms in the gas diffuse into the molten parts of the Silicon
and stay there when the Silicon solidifies, thus producing a P-type Silicon wafer with Boron
impurities.

Figure 10: Illustrates Laser Induced Diffusion Process

Process: GILD is performed in a high vacuum chamber (10 -7 mbar) on Si and SOI wafers, using
homogenized XeCl excimer laser (308 nm, 30 ns, 200 mJ per pulse, 125 Hz).After cleaning and
removing native oxide the substrate is introduced in the chamber. The dopant precursor gas
(BCl3) is injected and chemisorbed on the substrate before each laser pulse.

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Figure 11: Stages of GILD process.

GILD process could be an alternative to ion implantation as it uses rapid annealing for making
ultra-shallow junctions. Quantity Boron atoms incorporated per laser shot depends on the laser
energy density and temperature gradient.
Advantages:
1. GILD process can be used for large scale manufacturing and low cost manufacturing.
2. GILD provides process control over concentration as well as depth of doping process.
Future Scope of Work:
GILD still requires a lot of research to precisely determine the laser energy density and the
number of laser shots to make an ultra-thin junction. The use of GILD technique has only been
tested on a select group of semiconductor materials. This technique still requires a lot of research
to make it usable for large scale production of semiconductor

Table of Comparative Study

Parameter:

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Diffusion

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Cost:
Batch Formation:
Reproducibility:
Very High
Concentration
Doping:
Temperature:

It is relatively cheaper

It is expensive

Possible

Not Possible

Not Possible

Possible

Not Possible

Possible

It is a high temperature
process (90010000C)

It is relatively a low temperature

process

Process Type:

It is a natural process

It is a forced process

Driving Force:

Concentration
Difference

Electric Field (acceleration)

Shallow Junction:

Not Possible

Possible

Doping
Concentration:

Cannot be controlled

Can be controlled precisely

Doping Depth:

Cannot be controlled

Can be controlled easily

Parent Material
Surface:

Doesnt undergo any

damage

Damage in form of distortion may

occur

Directional:

Isotropic Process

Anisotropic Process

Post doping process:

No Annealing is
required

Annealing is required

CONCLUSION:
The driving force in the diffusion process is the difference between the concentrations of the
materials involved and is carried out at high temperature. It is a non-destructive process and
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causes no damage to the material surface. Though relatively cheaper the diffusion process has its
own drawbacks which include inability to control the junction depth and difficulty in maintaining
precise doping concentration. The Ion Implantation process offers better doping concentration
control, precise junction depth control, and easy reproducibility and doesnt require high
temperature for being carried out
In semiconductors, the doping depth and concentration decide the quality of the semiconductor.
Ion implantation process not only offers excellent doping uniformity but also precise control over
depth and profile of the ion distribution of doping. Ion implantation can also be used for both
high and low concentration doping and is carried out in a closed and controlled environment,
reducing the possibility of any unwanted contamination due to impurities. In comparison to ion
implantation process, diffusion process offers peak concentration of the dopants near surface.
Easy reproducibility of the product is also an advantage of the ion implantation process.
Although ion implantation is expensive but it produces better quality semiconductor as compared
to Diffusion Process. Ion implantation has some drawbacks like formation of amorphous regions,
physical distortion of the substance but it is preferred over diffusion process as these damages
can be removed by annealing the product. An improvement to the ion implantation process is the
plasma immersion ion implantation (PIII).

REFRENCES:
1. Carrier gas diffusion (for gas phase)
URL: http://www.powerguru.org/doping-silicon-wafers/
2. Diffusion of dopants(for gas phase and liquid)
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URL: http://www.circuitstoday.com/diffusion-of-impurities-for-ic-fabrication
3. Masking oxide(ion implantation)
URL: http://81.161.252.57/ipci/courses/technology/inde_195.htm
4. Doped semiconductor
URL: http://www.physics.udel.edu/~watson/scen103/98w/clas0128b.html
5. Ion implantation system URL:http://www.circuitstoday.com/ion-implantation
6. G.Kerrien, T.Sarnet, D.Dbarre, J.Boulmer, M.Hernandez, C.Laviron, M.-N.Semeria: Gas
immersion laser doping (GILD) for ultra-shallow junction formation; Proceedings of
Symposium H on Photonic Processing of Surfaces; Volumes 453454, 1 April 2004,
Pages 106109.
7. J D Plummer, M D Deal and P B Griffin, Silicon VLSI Technology: fundamentals,
practice and modelling, Pearson Edu. Inc., 2001
8. Razeghi and Manijeh, Technology of Quantum Devices, Springer, 2010
9. Bose D.N., Semiconductor Material and Devices, New Age Publishers, 2012
10. F.G, Tseng, IC Fabrication Process 2: Diffusion, Ion Implantation, Film Deposition,
Interconnection and contacts. Lecture conducted from National Tsing Hua University,
Taiwan. Available [online]: http://oz.nthu.edu.tw/~d9511818/10ess5850Lec%203-1.pdf
11. John (2010, June 1), Diffusion of impurities for IC fabrication [online].
Available:http://www.circuitstoday.com/diffusion-of-impurities-for-ic-fabrication
12. R.C. Jaeger (Vol.5), Introduction to Microelectronic fabrication, Pearson
Education,Inc.,New Jersey,USA ,2002
13. Advancements in ion implantation Modelling for Doping of Semiconductors, Sivaco, Inc.
Available [Online] : http://www.silvaco.com/content/kbase/ion_implantation.pdf
14. Plummer D. James, Deal Michael , Griffin D. Peter, Silicon VLSI Technology:
Fundamentals, Practise and Modelling, Prentice Hall , 2000
15. Gupta Dushyant (2011), Plasma Immersion Ion Implantation Process- Physics and
Technology, International Journal of Advancements in Technology, 2(4), (472-474).
Available [Online] : http://omicsonline.org/open-access/plasma-immersion-ionimplantation- piii-process-physics-and-technology-0976-4860-2-471-490.pdf

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