MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

SILICON WAFER

1. SILICON CRYSTAL STRUCTURE

2. SILICON CRYSTAL GROWTH

3. CZOCHRALSKI CRYSTAL GROWTH METHODS

4. FLOAT ZONE PROCESS

5. EXCERCISES

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY 1

 The Structure Of Crystalline Solids
A crystalline material is one in which the atoms are situated in
a repeating or periodic array over large atomic distances.

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY 2

 UNIT CELLS

Body-centered cubic (BCC):Alkali, Face-centered cubic

Cr, W, Fe (α), Molybdenum… (FCC):Al, Cu, Au, Ag, Pt…

Hexagonal close-packed (HCP):Be, Mg,

Zn, Cd, Ti…
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 UNIT CELLS

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 Unit Cells Of Inorganic Semiconductors

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 Silicon properties

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 Miller Indices
Miller Indices

Silicon Wafer flats

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 Miller Indices

6" Silicon Wafer Texas Instruments TMS371

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 IMPERFECTION IN SOLIDS
Point defects

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 IMPERFECTION IN SOLIDS
Linear defects

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 IMPERFECTION IN SOLIDS

Interfacial
defects

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 SILICON CRYSTAL GROWTH
Forms of Silicon

- Naturally occurs in the form of

silica (Quartz, sand, flint) and
silicate rocks (SiO4 combined with
Al, Mn, Ca, Na, K, Fe,...)
- 2nd to oxygen in abundance
(80 % of the Earth crust)
- Essential to the manufacture of
Sand Dune
glass
- Early use in electronics: vacuum
tubes (Silica), capacitors (Mica),
resonators and filters (Quartz)

Quartz 12
 Wafer Parameters

• Silicon Wafers Basic processing unit

• 150, 200, 300 mm disk, 0.5 mm thick
• Newest ones 300 mm (12 inches)
• Typical process 25 - 1000 wafers/run
• Each wafer: 100 - 1000's of microchips (die)
• Wafer cost $10 - $100's
• 200 mm wafer weight 0.040 Kg
• Typical processing costs $1200/wafer (200 mm)
• Typical processed wafer value $11,000
(all products, modest yield)
• Value/Mass of processed wafer $275,000/Kg

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 SILICON CRYSTAL GROWTH
Process sequence from starting material to polished wafer

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 SILICON CRYSTAL GROWTH
Raw material preparation

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 Steps to Obtaining Semiconductor Grade Silicon

Step Description of Process Reaction

Produce metallurgical grade

1 silicon (MGS) by heating SiC2SiO
(s) +2SiO
(s) +2 (s)  Si(l)Si(liquid)
2C(s) + SiO(g) ++ 2CO(g)
CO (g)
silica with carbon
Purify MG silicon through a
chemical reaction to produce
2 Si (s) + 3HCl (g)  SiHCl3 (g) + H2 (g) + heat
a silicon-bearing gas of
trichlorosilane (SiHCl3)
SiHCl3 and hydrogen react in
a process called Siemens to
3 2SiHCl3 (g) + 2H2 (g)  2Si (s) + 6HCl (g)
obtain pure semiconductor-
grade silicon (SGS)

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 Metallurgical Grade Silicon
Quartzite (sand, SiO2) is placed in a hot (1800oC) furnace with carbon
releasing materials, and reacts as shown, forming metallurgic grade silicon
(MGS):
2SiO2(solid) + 2C(solid)  Si(liquid) + 2CO(gas)

Metallurgical grade silicon (~98% pure) production and typical impurity

levels.
Over 50% MGS is used to make Al alloys.
The fraction used for semiconductors is very small.
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 Electrical Grade Silicon (EGS or SGS) (Polycrystalline)
Basically, the solid Si is first converted into a liquid form
(SiHCl3) for purification, then converted back into solid Si.
Both reactions occur at high temperatures.
Metallurgical grade silicon is treated with hydrogen chloride to
form trichlorosilane:
Si + 3HCl  SiHCl3(g) + H2(g) (use catalyst)
SiHCl3 is liquid at room temperature, boiling point 32oC.
Multiple distillation of the liquid removes the unwanted
impurities (99.9999% pure).
The purified SiHCl3 is then used in a hydrogen reduction
reaction to prepare the electronic grade Si (EGS):
SiHCl3(g) + H2(g)  Si(s) + 3HCl(g)
(this is the reverse reaction of the above reaction)
EGS is the raw material for Si single crystal production.
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 SILICON CRYSTAL GROWTH
Metallurgical Grade Silicon into Polycrystalline Silicon

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 Si single crystal growth
Two methods used: Czochralski (CZ) and float zone (FZ).
Jan Czochralski (cho-HRAL-skee) (1885 -
1953) was a Polish chemist who invented
the Czochralski process, which is used to
grow single crystals and is used in the
production of semiconductor wafers.
He discovered the Czochralski method in
1916 when he accidentally dipped his pen
into a crucible of molten tin rather than his
inkwell. He immediately pulled his pen out
to discover that a thin thread of solidified
metal was hanging from the nib. The nib
was replaced by a capillary, and Czochralski
verified that the crystallized metal was a
single crystal.
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 CZOCHRALSKI CRYSTAL GROWTH METHODS
• It is widely employed for Si, GaAs, and InP.
• The EGS is broken into small pieces and placed in an SiO2 crucible.
• In an argon ambient, the crucible is heated to just above 1417oC.
• Dopant is added to the melt to intentionally dope the resulting crystal.
• A single crystal seed is then lowered into the melt (crystal orientation and wafer
diameter determined by seed orientation and pull rate), and withdrawn slowly.
• Melt flows up the seed and cools as crystal begins to grow.
• Seed rotated about its axis to produce a circular cross-section crystal. The
rotation inhibits the natural tendency of the crystal to grow along certain
orientations to produce a faceted crystal.
• Long ingots (boules) 100 kg, with very good circular cross-section are
produced.
• The oxygen and carbon (from graphite furnace components), contribute about
1017-1018/cm3 contaminants.

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 CZOCHRALSKI CRYSTAL GROWTH METHODS

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 CZOCHRALSKI CRYSTAL GROWTH METHODS

A commercial CZ puller Early in the growth process Later in the growth

process

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 Growth Rate And Dopant Incorporation For CZ Method

We wish to find a relationship between pull rate and crystal diameter.

Heat balance: Seed

latent heat of fusion heat heat

C
(i.e. crystalization) conducted radiated dx
= =
+ through the away
B Isotherm X2
heat conducted from crystal (C). Solid Si

melt to crystal (B) A

(A)
Liquid Si Isotherm X1

L  latent heat of fusion

Freezing occurs between isotherms X1
and X2. dm
 amount of freezing per unit time
dt
dm dT dT
(1) L  kL A1  k S A2 k L  thermal conductivity of liquid
dt dx 1 dx 2 dT
 thermal gradient at isotherm x1
dx 1
(A) (B)
k S  thermal conductivity of solid
dT
A1,2 = Cross-sectional area  thermal gradient at x 2
dx 2
24
MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY 24
 CRYSTAL GROWTH RATE
The rate of growth of the crystal is dm (2)
 v P AN
dt
where vP is the pull rate and N is the density.
k S dT
v
Neglecting the middle term in Eqn. (1) we have: PMAX  (3)
LN dx 2
In order to replace dT/dx2, we need to consider the heat transfer processes.
Seed
Heat radiation from the crystal (C)
is given by the Stefan-Boltzmann law*:
C
dx

dQ  2 rdx  T 4  (4)

B Isotherm X2
Solid Si
Heat conduction up the crystal is
A

Isotherm X1
given by
 
Q  k S r2
dT
dx
(5)
Liquid Si
2πrdx = radiation surface.
σ = Boltzman constant (NOT kB)
kS = thermal conductivity of the solid.
=1 for perfect blackbody.
<1 for “grey-body”. 25

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

 Czochralski process - crystal growth rate
2 2
• Differentiating (5), we have dQ
dx
 k S r  
2 d T

dx 2
 r  
2 dT dk S
dx dx
 k S r  
2 d T

dx 2
(6)

d 2 T 2 4 (7)
• Substituting (6) into (4), we have 2
 T 0
dx k Sr

• kS varies roughly as 1/T, so if kM is the TM

kS  kM (8)
thermal conductivity at the melting point, T

d2 T 2
  T5  0 (9)
dx 2 k M rTM

• Solving this differential equation, evaluating it at x = 0 and substituting the

result into (3), we obtain (see text):
5
1 2k M TM (10)
v PMAX 
LN 3r

Vpmax = maximum pull rate, inversely proportional to the square root of crystal
26
radius.
MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY
 Crystal growth rate: example

For perfect blackbody: =1

For “grey” body: <1

4 hours to pull one meter long boule.

However, this equation is not so accurate, and in practice feedback is used to
27
adjust the pulling rate in order to maintain constant diameter.
MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY
 Dopant incorporation during crystal growth
• Dopants are added to the melt to provide a controlled N or P doping level in the
wafers.
• However, the dopant incorporation process is complicated by dopant segregation.
• Generally, impurities “prefer to stay in the liquid” as opposed to being incorporated
into the solid.
• This process is known as segregation. The degree of segregation is characterized
by the segregation coefficient, ko, for the impurity.
CS
kO 
CL

CS and CL are the impurity

concentration just on the either
side of the solid/liquid interface.
VS, CS
CS

VO, IO, CO
CL IL, CL

28

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

 Dopant behavior during crystal growth

CS
kO 
CL

Most k0 values are <1 which means the impurity prefers to stay in the liquid.
Thus as the crystal is pulled, dopant concentration will increase.
In other words, the distribution of dopant along the ingot will be graded.
29

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

 Distribution coefficient: example

=1.019×10-4mol
30

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

 Dopant incorporation during crystal growth
VO = initial volume
IO = number of impurities
CL = impurity concentration in the melt
VS, CS
C0 = initial impurity concentration in the
melt C0 = I0/V0
By definition: CS/CL=k0
VO, IO, CO IL, CL

If during growth, an additional volume dV freezes, the impurities

incorporated into dV are given by:

k0
I 0 1  S 
V
I 0 1  f  0
k
IL  V0 
 C0 1  f  0
k 1
CL   
VL V0  VS V0 1  f

The impurity level in the crystal (Cs) f = Vs/Vo, the ratio of solid
kO  1 silicon to the initial liquid
 C S  C O k O 1  f volume. 31

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

 Doping concentration versus position along the
grown CZ crystal for common dopants in silicon

10

Boron
1
CS/CO

Phosphorus, Arsenic

0.1

Antimony

0.01
0 0.2 0.4 0.6 0.8 1
Fraction of Melt Solidified

Note the relatively flat profile produced by

boron with a ko close to 1.
Dopants with ko << 1 produce much more Doping concentration in a solid as a
doping variation along the crystal. function of the fraction solidified.
(but no dopant has ko>1) 32

MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY

FLOAT ZONE CRYSTALLIZATION
• For CZ-grown Si, impurities (O and C) can be
introduced from the melt contacting the SiO2
crucible and from graphite susceptor/supporter.
• It is good for solar cells, power electronic devices
that use the entire volume of the wafer not just a thin
surface layer, etc.
• Float Zone (FZ) produces smaller wafers (4”).
• Start with polycrystalline Si rod
• Touch rod to seed crystal
• Heat with moving Radio Frequency (RF) coil
• Melts road near coil
• Move melt front from crystal to end and back
• Leaves single crystal rod behind
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 FLOAT ZONE CRYSTALLIZATION

Poly-Si

c-Si

RF coil

Concentration (Atoms/cm3)

Dopant
Material < 1014 1014 to 1016 1016 to 1019 >1019
Type (Very Lightly Doped) (Lightly Doped) (Doped) (Heavily Doped)

-- - +
Pentavalent n n n n n
-- - +
Trivalent p p p p p
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 BASIC PROCESS STEPS FOR WAFER PREPARATION

Wafer Lapping
Crystal Growth and Edge Grind Cleaning

Shaping Etching Inspection

Wafer Slicing Polishing Packaging

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 BASIC PROCESS STEPS FOR WAFER PREPARATION
Step 2: Shaping_ Ingot diameter grind Step 3: Wafer slicing

Preparing crystal
Internal diameter
ingot for grinding
wafer saw

Diameter
grind
Flat grind

After crystal pulling, the boule

is shaped and cut into wafers
which are then polished on
one side.

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 BASIC PROCESS STEPS FOR WAFER PREPARATION
Step 4: Wafer Lapping and Edge Grind
Wafer Notch and Laser Polished Wafer Edge
Scribe

Scribed Identification
Notch
number

Step 5: Etching
Chemical Etch of Wafer Surface
to Remove Sawing Damage

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37
 BASIC PROCESS STEPS FOR WAFER PREPARATION
Wafer Dimensions & Attributes
Diameter Thickness Area Weight Weight/25
(mm) (m) (cm2) (grams/lbs) Wafers (lbs)
150 675  20 176.71 28 / 0.06 1.5
200 725  20 314.16 53.08 / 0.12 3
300 775  20 706.86 127.64 / 0.28 7
400 825  20 1256.64 241.56 / 0.53 13

Increase in Number of Chips

on Larger Wafer Diameters
(Assume large 1.5 x 1.5 cm
microprocessors)
88 die
200-mm wafer 232 die
300-mm wafer

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 BASIC PROCESS STEPS FOR WAFER PREPARATION
Step 6: Wafer polishing

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 BASIC PROCESS STEPS FOR WAFER PREPARATION
Step 6: Wafer polishing

Double-Sided Wafer Polish

Upper polishing pad

Wafer

Slurry
Lower polishing pad

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 BASIC PROCESS STEPS FOR WAFER PREPARATION
Step 8: Inspection_quality measures

 Physical dimensions

 Flatness

 Microroughness

 Oxygen content

 Crystal defects

 Particles

 Bulk resistivity

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 Hot point probe
Hot point probe is a simple method to determine whether a semiconductor is
N or P type. Principle of operation:
Two probes touches the wafer, one is warmer than the other
 A voltmeter reads the potential between the probes
 If the warmer probe is more positive than the colder probe than it is a
semiconductor type N
 If the warmer probe is more negative than the colder probe than it is a
semiconductor type P

Pn is thermoelectric power
either (-) for e- or (+) for h+

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 Thermoelectric refrigeration and power generation

Peltier
effect

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 “Four-point probe” measurement method

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 Hall Effect Measurements

 The Hall effect was discovered more than 100 years ago when Hall
observed a transverse voltage across a conductor subjected to a magnetic
field.
 The technique is more powerful than the sheet resistance method
described above because it can determine the material type,
carrier concentration and carrier mobility separately.
 The basic method is illustrated in the next slide. The left part of the figure
defines the reference directions and the various currents, fields and
voltages; the right part of the figure illustrates a top view of a practical
geometry that is often used in semiconductor applications.
MA4023 - MATERIALS AND LITHOGRAPHY TECHNOLOGY 45
 Hall Effect Measurements
D. Neamen, Semiconductor
p-type semiconductor
physics and devices 4th e Hall voltage:

Hole concentration:

Hole mobility

n-type semiconductor
Hall voltage:

electron concentration: electron mobility

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 Example

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 PROBLEMS

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