Silicon Crystal Structure and Growth

(Plummer - Chapter 3)

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Atomic Order of a Crystal Structure

Figure 4.2
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Amorphous Atomic Structure

Figure 4.3
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 Unit Cell in 3-D Structure

Unit cell

Figure 4.4
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 Miller Indices of Crystal Planes

Z Z Z

Y Y Y

X X X
(100) (110) (111)

Figure 4.9
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 Silicon Crystal Structure

Crystals are characterized by a unit cell which repeats in the x, y, z directions.

• Planes and directions are defined using x, y, z coordinates.
• [111] direction is defined by a vector of 1 unit in x, y and z.
• Planes defined by “Miller indices” – Their normal direction
(reciprocals of intercepts of plane with the x, y and z axes).
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Silicon has the basic diamond crystal structure –
two merged FCC cells offset by a/4 in x, y and z.
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Faced-centered Cubic (FCC) Unit Cell

Figure 4.5
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Silicon Unit Cell: FCC Diamond Structure

Figure 4.6
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Basic FCC Cell Merged FCC Cells

Omitting atoms
outside Cell Bonding of Atoms
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 (Extra line of atoms)

Various types of defects can exist in

a crystal (or can be created by
processing steps). In general, these
cause electrical leakage and are
result in poorer devices. EE-452 13 -
 Point Defects

Vacancy defect

Interstitial defect Frenkel defect

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Semiconductor-Grade Silicon

Steps
Step De
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 Czochralski (CZ)
crystal growing
• Si is purified from SiO2 (sand) by refining, distillation and CVD.
• It contains < 1 ppb impurities. Pulled crystals contain O (~1018
cm-3 ) and C (~1016 cm-3 ), plus dopants placed in the melt.
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 CZ Crystal Puller

Crystal puller
and rotation
mechanism Crystal seed

Single crystal Molten

silicon polysilicon

Quartz Heat shield

crucible
Carbon heating
element Water jacket

Figure 4.10
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• All Si wafers come
from “Czochralski”
grown crystals.
• Polysilicon is melted,
then held just below
1417 °C, and a single
crystal seed starts the
growth.
• Pull rate, melt
temperature and
rotation rate control
the growth

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EE-452 13 -
Silicon Ingot Grown by CZ Method

Photograph courtesy of Kayex Corp., 300 mm Si ingot

Photo 4.1
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EE-452 13 -
 An alternative process is the
“Float Zone” process which can
be used for refining or single
crystal growth.

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• In the float zone process, dopants and
other impurities are rejected by the
regrowing silicon crystal. Impurities tend
to stay in the liquid and refining can be
accomplished, especially with multiple
passes.
(See the Plummer for models of this
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 Float Zone Crystal Growth
Gas inlet (inert)

Chuck

Polycrystalline
rod (silicon) Molten zone

Traveling
RF RF coil

Seed crystal
Chuck
Inert gas out

Figure 4.11
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Dopant Concentration Nomenclature

Table 4.2
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Segregation Fraction for FZ Refining

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Basic Process Steps for Wafer Preparation

Wafer
Wafer Lapping
Lapping
Crystal
Crystal Growth
Growth and
and Edge
Edge Grind
Grind Cleaning
Cleaning

Shaping
Shaping Etching
Etching Inspection
Inspection

Wafer
Wafer Slicing
Slicing Polishing
Polishing Packaging
Packaging

Figure 4.19
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 Ingot Diameter Grind

Preparing crystal ingot for grinding

Diameter
grind

Flat grind

Figure 4.20
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 Internal Diameter Saw

Internal diameter
wafer saw

Figure 4.23
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 After crystal pulling, the boule is
shaped and cut into wafers which are
then polished on one side.

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Wafer Notch and Laser Scribe

1234567890

Notch Scribed identification number

Figure 4.22
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Polished Wafer Edge

Figure 4.24
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Chemical Etch of Wafer Surface
to Remove Sawing Damage

Figure 4.25
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Wafer Dimensions & Attributes

Diameter
(mm)
Table 4.3
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 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
Figure 4.13
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Developmental Specifications for 300-
mm Wafer Dimensions and Orientation
Some Typical
Parameter Units Nominal
Tolerances
Diameter mm 300.00 ±0.20
Thickness
µm 775 ±25
(center point)
Warp (max) µm 100
Nine-Point Thickness
µm 10
Variation (max)
Notch Depth mm 1.00 + 0.25, -0.00
Notch Angle Degree 90 +5, -1
Back Surface Finish Bright Etched/Polished
Edge Profile Surface Finish Polished
FQA (Fixed Quality Area –
radius permitted on the mm 147
wafer surface)
From H. Huff, R. Foodall, R. Nilson, and S. Griffiths, “Thermal Processing Issues for 300-mm Silicon Wafers:
Challenges and Opportunities,” ULSI Science and Technology (New Jersey: The Electrochemical Society, 1997), p. 139.

Table 4.4
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Wafer Polishing

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Double-Sided Wafer Polish

Upper polishing pad

Wafer

Slurry

Lower polishing pad

Figure 4.26
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 Improving Silicon Wafer
Requirements
Year
(Critical Dimension)
1995 1998 2000 2004
(0.35 µm) (0.25 µm) (0.18 µm) (0.13 µm)
Wafer diameter
200 200 300 300
(mm)
Site flatnessA (µm) 0.23 0.17 0.12 0.08
Site size (mm x mm) (22 x 22) (26 x 32) 26 x 32 26 x 36
MicroroughnessB of front
0.2 0.15 0.1 0.1
surface (RMS)C (nm)
Oxygen content
≤24 ±2 ≤23 ±2 ≤23 ±1.5 ≤22 ±1.5
(ppm)D
Bulk microdefectsE
≤5000 ≤1000 ≤500 ≤100
(defects/cm2)
Particles per unit area
0.17 0.13 0.075 0.055
(#/cm2)
EpilayerF thickness
(±% uniformity) (µm) 3.0 (±5%) 2.0 (±3%) 1.4 (±2%) 1.0 (±2%)

Adapted from K. M. Kim, “Bigger and Better CZ Silicon Crystals,” Solid State Technology (November 1996), p. 71.

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Quality Measures

• Physical dimensions
• Flatness
• Microroughness
• Oxygen content
• Crystal defects
• Particles
• Bulk resistivity

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 “Backside Gettering” to Purify Silicon
Polished Surface

Backside Implant: Ar (50 keV, 1015 /cm2)

The argon amorphizes the back side of the silicon. The wafer is
heated to 550oC, which regrows the silicon. However, the argon
can not be absorbed by the silicon crystal so it precipitates into
micro-bubbles and prevents some damage from annealing. The
wafer is held at 550oC for several hours, and all mobile metal
contaminants are attracted to and then captured by the argon
stabilized damage. Once captured, they never leave these sites.
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Chapter Review (Wafer Fabrication)
• Raw materials (SiO2) are refined to produce electronic
grade silicon with a purity unmatched by any other
available material on earth.
• CZ crystal growth produces structurally perfect Si single
crystals which are cut into wafers and polished.
• Starting wafers contain only dopants, and trace amounts of
contaminants O and C in measurable quantities.
• Dopants can be incorporated during crystal growth
• Point, line, and volume (1D, 2D, and 3D) defects can be
present in crystals, particularly after high temperature
processing.
• Point defects are "fundamental" and their concentration
depends on temperature (exponentially), on doping level
and on other processes like ion implantation which can
create non-equilibrium transient concentrations of these
defects.
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Measurement of Wafer Characteristics
Darkfield and Brightfield Detection
Brightfield imaging Darkfield imaging

Viewing Viewing
optics optics

Two-way mirror

Light source
Light reflected by
surface irregularities

r c e
Lens Lens
t sou
i gh
L

Figure 7.15
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Schematic of Optical System
Phase and
Phase and intensity
intensity
detection
detection
Photo detector array
Data generation,
Data generation,processing,
processing,
display are
display are networked
networked with
with
factory management
factory management software
software
Split mirror

Video camera
Lens
CRT

Light source
Viewing optics

Objective lens assembly

Three-axis
Wafer positioning stage piezo substage

Vibration isolation pad

Figure 7.16
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Principle of Confocal Microscopy
Detector
Pinhole

Beam splitter
Laser

Pinhole

Objective lens
Wafer is driven up and
down along Z-axis
+Z
Center of focus 0
-Z

Figure 7.17
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 Particle Detection by Light Scattering

Photo detector Detection of

Reflected light scattered light
Incident light
Beam scanning
Particle

Scattered light
Wafer motion

Figure 7.18
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 Measurement of Wafer
Characteristics
Hot Point Probe
The hot point probe is a simple and reliable means
to determine whether a wafer is N or P type is the
Hot Point Probe. The basic operation of this probe
is illustrated in the next slide. Two probes make
ohmic contact with the wafer surface. One is
heated 25-100°C hotter than the other. A
voltmeter placed across the probes will measure a
potential difference whose polarity indicates
whether the material is N or P type.

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Basic principle of the hot probe, illustrated
for an N-type sample, for determining N- or
P-type behavior in semiconductors.
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 Hot Point Probe
Consider an N-type sample. The majority carriers are electrons. At the hot
probe, the thermal energy of the electrons is higher than at the cold probe
so the electrons will tend to diffuse away from the hot probe, driven by the
temperature gradient. If a wire were connected between the hot and cold
probes, this would result in a measurable current, whose direction would
correspond to the electrons moving right to left. (The current by definition
would be in the opposite direction.) If we place a high-impedance
voltmeter between the probes, no current flows, but a potential difference
is measured, as illustrated. As the electrons diffuse away from the hot
probe, they leave behind the positively charged, immobile donor atoms
that provided the electrons. The negatively charged mobile electrons tend
to build up near the cold probe. This results in the hot probe becoming
positive with respect to the cold probe. By a similar set of arguments, if
the material were P type, positively charged holes would be the majority
carriers and the polarity of the induced voltage would be reversed. The
direction of the current between the two probes would also be reversed in
P-type material, if they were shorted with a wire. Thus a measurement of
either the short-circuit current or the open circuit voltage tells us the type
of the material.

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“Four-point probe” measurement method.
The outer two probes force a current
through the sample; the inner two probes
measure the voltage drop.
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Measurement of Sheet Resistance
• The most common method of measuring the wafer
resistivity is with the four-point probe. We
measure the sample resistance by measuring the
current that flows for a given applied voltage. This
could be done with just two probes. However, in that
case, contact resistances associated with the probes
and current spreading problems around the probes are
important and are not easily accounted for in the
analysis. Using four probes allows us to force the
current through the two outer probes, where there will
still be contact resistance and current spreading
problems, but we measure the voltage drop with the
two inner probes using a high-impedance voltmeter.
Problems with probe contacts are thus eliminated in
the voltage measurement since no current flows
through these contacts.

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 Four Point Probe
Constant current source
R
I
V
ρ s= x 2π s (ohms-cm) Voltmeter
I V

Wafer
Figure 7.3
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 “Van der Pauw” Sheet Resistivity
(similar to 4-point probe, but uses shapes on wafer)

(b)
V Contact
(a) Conductive material

(c) (d)

Figure 7.4
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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.

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Conceptual representation of Hall effect
measurement. The right sketch is a top view
of a more practical implementation.

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Fourier Transform Infrared
Spectroscopy (FTIR)

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 FTIR (Oxygen and Carbon Detection)
The CZ crystal growth process introduces oxygen and carbon into the silicon. These elements are not inert
in the crystal. It is important is to be able to measure them and to control them. The method is Fourier
Transform Infrared Spectroscopy. FTIR measures the absorption of infrared energy by the
molecules in a sample. Many molecules have vibrational modes that absorb specific wavelengths when
they are excited. By sweeping the wavelength of the incident energy and detecting which wavelengths are
absorbed, a characteristic signature of the molecules present is obtained. Oxygen in CZ crystals is located
in interstitial sites in the silicon lattice, bonded to two silicon atoms. Low concentrations of carbon are
substitutional in silicon since carbon is located in the same column of the periodic table as silicon and
easily replaces a silicon atom. Oxygen exhibits a vibrational mode that absorbs energy at 1106 cm-1
(wavenumber), that is at a wavelength of about 9 microns; carbon absorbs energy at 607 cm-1 .There are
other wavelengths of IR light that are absorbed by the silicon atoms themselves. By measuring the
absorption of a particular wafer at 1106 or 607 cm-1 , and comparing this absorption with an oxygen or
carbon free reference, the FTIR technique can be made quantitative.
An IR beam is split by a partially reflecting mirror and then follows two separate paths to the sample and
the detector. For pure silicon, if the movable mirror is translated back and forth at constant speed, the
detected signal will be sinusoidal as the two beams go in and out of phase. The Fourier transform of this
signal will simply be a delta function proportional to the incident intensity. If the frequency of the source is
swept, the Fourier transform of the resulting signal will produce an intensity spectrum. If we now insert the
sample, the resulting intensity spectrum will change because of absorption of specific wavelengths by the
sample. The benefit of using the Fourier transform method as opposed to simply directly measuring the
intensity spectrum is simply that the signal to noise ratio is improved and as a result, the detection limit is
reduced. With modern instruments, the detection limit for interstitial oxygen in silicon is about 2x1015 /cm3.
Carbon can be detected down to about 5x1015 /cm3. Oxygen precipitated into small SiO2 clusters can be
detected by FTIR because in the SiO2 form, the oxygen does not absorb at 1106 cm-1 . As the precipitation
occurs, the IR absorption at this wavenumber decreases.

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 Schematic of “TEM”
Transmission Electron Microscope
Electron gun
Liquid N2 Anode
Dewar
Condenser lens
X-ray detector
Sample stage

Objective
aperture
Aperture } Lenses
CRT
Displayed
sample image CCD video camera

Fluorescent screen

Wavelength of 1 MeV
Energy-loss
spectrometer Electron ~ 1Angstrom
Detector

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Electron Microscopy (TEM) of SiO 2 on
Si

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 Oxygen Contamination in Silicon
Oxygen is the most important impurity found in silicon. It is incorporated in silicon during the CZ growth
process as a result of dissolution of the quartz crucible in which the molten silicon is contained. The oxygen
is typically at a level of about 1018 /cm3. It has recently become possible to use a magnetic field during CZ
growth to control thermal convection currents in the melt. This slows down the transport of oxygen from
the crucible walls to the growing silicon interface and reduces the oxygen concentration in the resulting
crystal.
Oxygen in silicon is always present at concentrations of ~10-20 ppm (5x1017 - 1018 /cm3) in CZ silicon. The
oxygen can affect processes used in wafer fabrication such as impurity diffusion.
Oxygen has three principal effects in the silicon crystal.
(1) In an as-grown crystal, the oxygen is believed to be incorporated primarily as dispersed single atoms
designated OI occupying interstitial positions in the silicon lattice, but covalently bonded to two silicon
atoms. The oxygen atoms thus replace one of the normal Si-Si covalent bonds with a Si-O-Si structure. The
oxygen atom is neutral in this configuration and can be detected with the FTIR method. Such interstitial
oxygen atoms improve the yield strength of silicon by as much as 25%, making silicon wafers more robust
in a manufacturing facility.
(2) The formation of oxygen donors. A small amount of the oxygen in the crystal forms SiO4 complexes
which act as donors. They can be detected by changes in the silicon resistivity corresponding to the free
electrons donated by the oxygen complexes. As many as 1016 /cm3 donors can be formed, which is sufficient
to significantly increase the resistivity of lightly doped P-type wafers. During the CZ growth process, the
crystal cools slowly through ~500oC temperature and oxygen donors form. The SiO4 complexes are
unstable at temperatures above 500°C and so usually wafer manufacturers anneal the grown crystal or the
wafers themselves after sawing and polishing, to remove the oxygen complexes. These donors can reform,
however, during normal IC manufacturing, if a thermal step around 400-500°C is used. Such steps are not
uncommon, particularly at the end of a process flow.
(3) The tendency of the oxygen to precipitate under normal device processing conditions, forming SiO2
regions inside the wafer. The precipitation arises because the oxygen was incorporated at the melt
temperature and is therefore supersaturated in the silicon at process temperatures.

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 Carbon Contamination in Silicon
Carbon is normally present in CZ grown silicon crystals at concentrations on the order of
1016/cm3.The carbon comes from the graphite components in the crystal pulling machine. The
melt contains silicon and modest concentrations of oxygen. This results in the formation of SiO
that evaporates from the melt surface. Generally, the ambient in the crystal puller is Ar flowing at
reduced pressure, and the SiO can be transported in the gas phase to the graphite crucible and
other support fixtures. SiO reacts with graphite (carbon) to produce CO that again transports
through the gas phase back to the melt. From the melt, the carbon is incorporated into the
growing crystal.
Four Effects of Carbon on Silicon
(1) Carbon is mostly substitutional in the silicon lattice. Since it is a column IV element, it does
not act as a donor or acceptor in silicon. Carbon is known to affect the precipitation kinetics of
oxygen in silicon. This is likely because there is a volume expansion when oxygen precipitates
and a volume contraction when carbon precipitates because of the relative sizes of O and C.
There is thus a tendency for precipitates that are complexes of C and O to form at minimum
stresses in the crystal. Since precipitated SiO2 is crucial in intrinsic gettering, this can have an
effect on gettering efficiency.
(2) Carbon is also known to interact with point defects in silicon. Silicon interstitials tend to
displace carbon atoms from lattice sites, presumably because this can help to compensate the
volume contraction present when there is carbon in the crystal.
(3) Thermal donors (Oxygen Effects) normally form around 450°C. There is also evidence that
if C is present at ~1 ppm, these donors may also form at higher temperatures (650-1000°C).
(4) Higher concentrations of C to Si (levels of a few percent) can change the bandgap of the
silicon and may allow the fabrication of new types of semiconductor devices in the future.

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 Chapter Review (Wafer Metrology)

• Microscopic examination for particulates.

• Hot Point Probe (wafer doping)
• Four Point Probe (wafer resistivity)
• Hall Effect (carrier mobility)
• FBIR (oxygen and carbon detection)
• TEM (atomic resolution of defects / surface)
• Effects of Oxygen on IC fabrication
• Effects of Carbon on IC fabrication

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