Float Zone & Bridgman

Crystal Growth Techniques

1

Abu Syed Md. Jannatul Islam

Lecturer, Dept. of EEE, KUET, BD

Department of Electrical and Electronic Engineering

Khulna University of Engineering & Technology
Khulna-9203
 Limitations of CZ Method
2
 The quartz crucible (SiO2) gradually dissolves and
releases large quantities of oxygen into the melt. More
than 99% of this is lost as SiO gas from the molten
surface, but the rest stays in the melt and can dissolve
into the single crystal silicon.

 Another impurity, however with smaller concentrations,

that is also introduced into the melt by the production
process itself is carbon. The silicon monoxide evaporating
from the melt surface interacts with the hot graphite
susceptor and forms carbon monoxide that re-enters the
melt.

 As the crystal is pulled from the melt, the impurity

concentration incorporated into the crystal (solid) is
usually different from the impurity concentration of the
melt (liquid) at the interface.
 Limitations of CZ Method
3
 Typical oxygen and carbon concentrations are [O] ≈ 5-10 10^17cm-3 and [C] ≈ 5 - 10
10^15cm-3, respectively, which lower the minority carrier diffusion length in the finished
silicon wafer.

 Low homogeneity of the axial and radial dopant concentration in the crystal caused by
oscillations in the melt during crystal growth. This makes it difficult to attain high-ohmic
CZ-wafers with a resistivity exceeding 100 Ohm cm.

 Furthermore the high oxygen concentration can lead to the formation of unwanted
electrically active defects. These are oxygen related thermal double donors (TDD) and
shallow thermal donors (STD) which can seriously change the resistivity of the material.
 Advantages of CZ Method
4

 Oxygen has also good properties. Oxygen acts as a gettering agent for trace
metal impurities in the crystal and it can pin dislocations which greatly
strengthens the crystal.

 Oxygen precipitates in the wafer core suppress stacking faults, and oxygen
makes the Si more resistant to thermal stress during processing.

 The Czochralski-technique allows big crystal diameters and lower production

cost per wafer– compared to the float-zone technique described in the following
section.

 Better compatibility with advanced CMOS processes

 wafer made by CZ used in the electronics industry to make semiconductor

devices such as integrated circuits.
 Oxygen Control Parameters
5

•Gas Flow
•Pressure
•Gas Flow Pattern
•Crucible Rotation
•Crystal Rotation
•Temperature Distribution
•Magnetic Field

A magnetic field (“Magnetic

Czochralski”, MCZ) can retard these
oscillations and improve the dopant
homogeneity in the ingot.
 Magnetic Czochralski (MCZ)
6
 The method is the same as the CZ method except that it is carried out within a strong horizontal
(HMCZ) or vertical (VMCZ) magnetic field.

 This serves to control the convection fluid flow, allowing e.g. with the HMCZ method to minimise
the mixing between the liquid in the center of the bath with that at the edge.

 This effectively creates a liquid silicon crucible around the central silicon bath, which can trap
much of the oxygen and slow its migration into the crystal.

 Compared to the standard CZ a lower oxygen concentration can be obtained and the impurity
distribution is more homogeneous.

 This method offers also the possibility to produce detector grade silicon with a high oxygen
concentration.

 Since the technology is still a very young one, it is hard to get such material with reproducible
impurity concentrations on a commercial basis. However, a first test material of 4 KΩ.cm  p-type
with an oxygen concentration of 7-8 * l017 cm-3 and a carbon concentration below 2xl016 cm-3 was
obtained.
 Magnetic Czochralski (MCZ)
7

Magnetic field changes oxygen behavior

 Thicker laminar layer next to crucible
wall => slower oxygen dissolution
 Thicker laminar layer at gas interface
=> tendency to increase oxygen in the
melt
 Balance between these two effects
defines oxygen level
 Slow crucible erosion => long crucible
lifetime, low dopant emission rate
 Price to pay: more difficult control of
radial variations! Both dopants and
oxygen
 Magnetic Czochralski (MCZ)
8

MCZ Puller
 Continuous CZ (CCZ)
9
 With the CCZ method a continuous supply of molten polycrystalline silicon is achieved by
using a double quartz crucible.

 In the first one the crystal is grown and in the second one, connected to the first one, a
reservoir of molten silicon is kept, that can be refilled by new polysilicon during the growth
process.

 This allows for larger crystal length and improves the throughput and operational costs of the
CZ grower.

 Furthermore the resulting single crystals have a uniform resistivity and oxygen concentration
and identical thermal history.

 In combination with the magnetic field method the Continuous Magnetic Field Applied CZ
technique (CMCZ) offers the possibility to grow long and large diameter CZ.

 However, silicon produced by this technology has so far not been used for radiation damage
experiments.
 Continuous CZ (CCZ)
9
 Requirements for Detectors
10
 The material requirements for the manufacturing of silicon particle detectors used for high
energy physics applications have to meet two basic demands:
 High resistivity (>1 Kohm/cm) and
 High minority carrier lifetime.

 Float Zone silicon is the best choice of material and is therefore exclusively used for
detector applications today.
 The main problem for the application as detector grade material arises from the resistivity
of CZ silicon. Due to contamination with boron, phosphorus and aluminum from the
dissolving quartz Crucible the highest commercially available resistivity is about 100 Ohm
cm for n-type and only slightly higher for p-type material. Therefore standard CZ silicon is
not suitable for detector production.
 Float-Zone Crystal Growth
11
 No need to use quartz crucible as well as hot graphite container.

 The main advantage of the float-zone technique is the very low impurity concentration in
the silicon crystal as compared to CZ silicon(Carrier concentrations down to 1011 atoms/cm3
have been achieved).

 The concentrations of light impurities, such as carbon and oxygen, are extremely low.
Another light impurity, nitrogen, helps to control micro-defects and also brings about an
improvement in mechanical strength of the wafers, and is now being intentionally added
during the growth stages.

 Additionally, the dopant concentration in the final crystal is rather homogeneous and
manageable which allows very high-ohmic (1-10 Kohm.cm) wafers as well as wafers with a
narrow specified electrical resistivity.

 Float zone silicon is typically used for power devices and detector applications. It is good
for solar cells, power electronic devices (thyristors and rectifiers) that use the entire volume
of the wafer not just a thin surface layer, etc
 Float-Zone Crystal Growth
12
 Float-zone does not allow as large Si wafers as CZ does (200mm and 300mm) and radial
distribution of dopant in FZ wafer is not as uniform as in CZ wafer.

 The main technological disadvantage of the FZ method is the requirement for a uniform,
crack-free cylindrical feed rod.  A cost premium (100% or more) is associated with such
poly rods.  

 These crystals are more expensive and have very low oxygen and carbon and thus, are
not suitable for the majority of silicon IC technology.

At the present time, FZ Si is used for premium high-efficiency cell

applications and CZ Si is used for higher-volume, lower-cost
applications.
 Float-Zone Crystal Growth
13
 Float-zone silicon is very pure silicon obtained by
vertical zone melting.

 The diameters of float-zone wafers are generally not

greater than 150 mm due to the surface tension
 limitations during growth.

 A polycrystalline rod of ultra-pure electronic grade

silicon is passed through an RF heating coil, which
creates a localized molten zone from which the
crystal ingot grows.

 The RF coil and the melted zone move along the

entire ingot.

 A seed crystal is used at one end in order to start

the growth. The whole process is carried out in an
evacuated chamber or in an inert gas purge.
 Float-Zone Crystal Growth
14
 Since most  impurities are less soluble in the crystal than
in the melted silicon, the molten zone carries the
impurities away with it. The impurities concentrate near
the end of the crystal where finally they can simply be
cut away (Dopants/impurities prefer to stay in the liquid
than in the solid).

 This procedure can be repeated one or more times in

order to further reduce the remaining impurity
concentration.

 Doping is realized during crystal growth by adding

dopant gases such as phosphine (PH3), arsine (AsH3) or
diborane (B2H6) to the inert gas  atmosphere. A variety of heating systems can be used
for floating zone technique, including
 Specialized doping techniques like core doping, pill induction coil, resistance heater or more
doping, gas doping and neutron transmutation doping recently optical heating system
are used to incorporate a uniform concentration of
impurity
 Float-Zone Crystal Growth
15
• The rod/ polycrystalline silicon ingot is clamped at
each end, with one end in contact with a single
crystal seed.

• An RF heating coil induces eddy currents (power

I2R) in the silicon, heating it beyond its melting
point in the vicinity of the coil.

• The seed crystal touches the melt zone and is

pulled away, along with a solidifying Si boule
following the seed.

• The crystalline direction follows that of the seed

single crystal.

Melt is not held in a container, it is

“float”, thus the name “float zone”.
 Doping in FZ Growth
16

Gas doping:
 Dopants are introduced in gaseous form during FZ growth.
 n-doping: PH3 (Phosphine), AsCl3
 p-doping: B2H6 (Diborane), BCl3
 Good uniformity along the length of the boule.
Pill doping:
 Drill a small hole in the top of the EGS rod, and insert the dopant.
 If the dopant has a small segregation coefficient, most of it will be carried with the melt
as it passes the length of the boule.
 Resulting in only a small non-uniformity.
 Ga and In doping work well this way.
 Float-Zone Crystal Growth
17

RF heating Optical heating

 Float-Zone Crystal Growth: Overview
18

Optical heating of the zone. Photograph of an optical FZ growth system.

 Bridgman Crystal Growth
19
 The Bridgman technique (also known as Bridgman-Stockbarger method) is one of the oldest
techniques used for growing crystals.

 The Bridgman–Stockbarger technique is named after Harvard physicist 

Percy Williams Bridgman(1882-1961) and MIT physicist Donald C. Stockbarger (1895–1952).

 Similar to Czochralski technique, the Bridgman technique employs also a crystal growth from
melt.

 The Bridgman method is a popular way of producing certain semiconductor crystals such as 

gallium arsenide, for which the Czochralski process is more difficult. The process can reliably
produce single crystal ingots, but does not necessarily result in uniform properties through
the crystal.
 Bridgman Crystal Growth
20
 In Bridgman technique, the crucible containing the molten material is translated along
the axis of a temperature gradient in a furnace, whereas in Stockbarger technique, there
is a high-temperature zone, an adiabatic loss zone and a low-temperature zone.
 These two methods are very often not specifically differed in the terminology.

 The difference between the Bridgman technique and Stockbarger technique is subtle:
 While both methods utilize a temperature gradient and a moving crucible, the
Bridgman technique utilizes the relatively uncontrolled gradient produced at
the exit of the furnace; The Stockbarger technique introduces a baffle, or
shelf, separating two coupled furnaces with temperatures above and below
the freezing point. Stockbarger's modification of the Bridgman technique
allows for better control over the temperature gradient at the melt/crystal
interface.
 Bridgman Crystal Growth
21

The method involves heating polycrystalline material in a container above its melting point and
slowly cooling it from one end where a seed crystal is located. Single crystal material is
progressively formed along the length of the container. The process can be carried out in a
horizontal or vertical geometry.
 Vertical Bridgman Crystal Growth
22
 The principle of the Bridgman technique is the
directional solidification by translating a melt
from the hot zone to the cold zone of the
furnace.

 The bridgman furnace works with three

temperature zones. The upper zone with
temperatures above the melting point of
silicon. The lower zone with a temperature
below melting point and an adiabatic zone as
a baffel between the two.

 At first the polycrystalline material in the

crucible needs to be melted completely in the
hot zone and be brought into contact with a
seed at the bottom of the crucible.

 Part of the seed will be re-melted after the

contact with the melt. This provides a fresh
interface for the crystal growth.
 Vertical Bridgman Crystal Growth
23
 The crucible is then translated slowly into the
cooler section of the furnace.

 The temperature at the bottom of the crucible

falls below the solidification temperature and the
crystal growth is initiated by the seed at the melt-
seed interface.

 After the whole crucible is translated through the

cold zone the entire melt converts to a solid
single-crystalline ingot.

 Due to a directed and controlled cooling process

of the cast, zones of aligned crystal lattices are
created.

 Merely 60% of the polycrystal silicon can be

processed to wafers for photovoltaics. The rest
gets lost in the sawing and cutting process.
 Vertical Bridgman-Stockbarger Method
24

Vertical Bridgman Tube Furnace Temperature Profile

 Horizontal Bridgman-Stockbarger Method
25

Temperature ºC

Schematics of the furnace and crucible used for GaAs growth.

 Vertical vs Horizontal Method
26
 The vertical Bridgman technique enables the growth
of crystals in circular shape, unlike the D-shaped
ingots grown by horizontal Bridgman technique.
 However, the crystals grown horizontally exhibit high
crystalline quality (e.g. low dislocation density) since
the crystal experiences lower stress due to the free
surface on the top of the melt and is free to expand
during the entire growth process.
 Instead of moving the crucible, the furnace can be
translated from the seed end while the crucible is
kept stationary.
 In this manner a directional solidification can be
achieved, too.
 A further modification is the so called gradient
freezing technique, with which neither the crucible
nor the furnace needs to be translated.