Level-4, Term-1 (‘19th Batch)
EEE-475: VLSI Technology
Crystal Growth
Dr. Sampad Ghosh
Associate Professor
Department of Electrical and Electronic Engineering
Faculty of Electrical and Computer Engineering
Chittagong University of Engineering and Technology (CUET)
May 16, 2024
CHITTAGONG UNIVERSITY OF ENGINEERING AND TECHNOLOGY (CUET)
KYUSHU UNIVERSITY
Topics Reference
Crystal Growth
Silicon crystal growth, Czochralski technique, Silicon
float zone process, GaAs crystal growth technique, S.M. Sze
Material characterization
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Silicon Crystal Growth
Basic technique for Si crystal growth from melt (material in liquid form)
is the Czochralski technique.
o More than 90% of Si crystal prepared by this method.
Starting material:
Starting material for Si is pure form of sand (SiO2) called quartzite.
SiO2 placed in a furnace and reacted with various forms of carbon (coal, coke).
SiC (solid) + SiO2 (solid) Si (solid) + SiO (gas) + CO (gas)
Produced metallurgical grade Si (MGS) – purity~98%.
Si pulverized and treated with HCl at 300°C.
Si (solid) + 3HCl (gas) SiHCl3 (gas) + H2 (gas)
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Silicon Crystal Growth…
SiHCl3 (trichlorosilane) is liquid at RT, and unwanted impurities removed
by Fractional distillation method.
Purified SiHCl3 reacted with H2 and produced electronic grade Si (EGS).
SiHCl3 (gas) + H2 (gas) Si (solid) + 3HCl (gas)
EGS (polycrystalline material) is raw material used to prepare single
crystal Si (device quality).
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Czochralski Technique
Three main components:
1. Furnace (SiO2 crucible,
graphite susceptor, CW
rotation mechanism)
2. Crystal pulling mechanism
(seed holder, CCW
rotation)
3. Ambient control (gas
source, flow control,
exhaust system).
Czochralski crystal puller
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Czochralski Technique…
EGS placed in crucible, and furnace heated
above melting temp. of Si (>1400°C).
Suitably oriented seed crystal (e.g., 111)
suspended over the crucible in a seed holder.
Seed inserted into melt. Part of its melts, but
tip of the remaining seed crystal still touches
liquid surface. Its then slowly withdrawn.
Progressive freezing at solid-liquid interface
yields a large single crystal (ingot).
For large diameter ingots, external magnetic
Single crystal Si ingot field applied to basic Czochralski puller.
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Czochralski Technique…
Ingot preparation by Czochralski method
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Distribution of Dopant
A known amount of dopant is added to the melt to obtain desired doping
concentration in grown crystal.
o In Si, boron for p-type and phosphorus for n-type materials.
As crystal pulled from melt, doping concentration incorporated into crystal
(solid) is different from doping concentration of melt (liquid) at interface.
Ratio of these two concentrations is defined as equilibrium segregation
coefficient (k0).
𝐶𝑠 Cs = Equilibrium concentrations of dopant in solid
𝑘0 =
𝐶𝑙
Cl = Equilibrium concentrations of dopant in liquid
Usually, k0<1 i.e., Cl>Cs,
During growth dopants are rejected into melt.
Melt becomes gradually enriched with dopant as crystal grows.
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Distribution of Dopant…
Consider a crystal being grown from melt having initial weight M0 and doping
concentration C0 in melt (i.e., dopant by weight per 1g of melt)
At a given point of growth when a crystal of weight M has been grown, amount
of dopant remaining in melt (by weight) is S.
For an incremental amount of crystal weight dM, corresponding reduction of
dopant (-dS) from melt is CsdM.
−𝑑𝑆
𝐶𝑠 = (1) Cs = doping concentrations in crystal (by weight)
𝑑𝑀
Remaining weight of melt is (M0-M) and doping concentration in liquid (by wt.)
Cl is
𝑆
𝐶𝑙 = (2)
𝑀0 − 𝑀
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Distribution of Dopant…
Dividing eq. (1) and (2)
ln 𝑠 − ln 𝐶0 𝑀0 = 𝑘0 [ln 𝑀0 − 𝑀 − ln 𝑀0 ]
𝐶𝑠 −𝑑𝑆 𝑀0 − 𝑀
= 𝑆 𝑀0 − 𝑀
𝐶𝑙 𝑑𝑀 𝑆 ln( ) = 𝑘0 ln( )
𝐶0 𝑀0 𝑀0
𝑑𝑆 𝑑𝑀 𝑀0 − 𝑀 𝑀 𝑘
= −𝑘0 [k0 = Cs/Cl] [putting S from eq.2]
𝑆 𝑀0 − 𝑀 𝐶𝑙 = (1 − ) 0
𝐶0 𝑀0 𝑀0
𝑆
𝑑𝑆 𝑀
−𝑑𝑀 𝐶𝑠 𝑀 𝑀 𝑘
න = 𝑘0 න (1 − ) = (1 − ) 0 [k0 = Cs/Cl]
𝐶0 𝑀0 𝑆 0 𝑀0 − 𝑀
𝑘0 𝐶0 𝑀0 𝑀0
C0M0 = initial weight of dopant 𝑀 𝑘 −1 When k0=1, Cs=C0
𝐶𝑠 = 𝑘0 𝐶0 (1 − ) 0 i.e., uniform impurity
𝑀0
distribution
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Example
A Si ingot, which should contain 1016 B atoms/cm3, is to be grown by the CZ
technique. What concentration of B atoms should be in the melt to give the
required concentration in the ingot? If the initial load of Si in the crucible is 60 kg,
how many grams of B (atomic wt. 10.8) should be added? The density of molten Si
is 2.53 g/cm3 and k0 for B is 0.8.
Solution: Assuming Cs=k0Cl throughout the growth
Initial concentration of B in melt Cl = Cs/k0 = 1016/0.8 = 1.25x1016 atoms/cm3
Volume of 60 kg Si = mass/density = (60x103)/2.53 = 2.37x104 cm3
Total no. of B atoms in melt = 1.25x1016 x 2.37x104 atoms = 2.96x1020 atoms
Amount of B required = 2.96x1020 x 10.8 = 3.2x1021 g atoms/mol
In gram, amount of B required = (3.2x1021)/NA = (3.2x1021)/(6.02x1023) = 5.31 mg
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CT-1
Date: 21/5/2024
Time: 8:30am
Syllabus: Last two lecture
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