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Bridgman method - Bridgman furnace - crystal growth

The Bridgman technique is a method of growing single crystal ingots or boules. It is a popular method
of producing certain semiconductor crystals, such as gallium arsenide, II-V Crystals (ZnSe, CdS,
CdTe) and BGO, where the Czochralski process is more difficult

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.

 the Bridgman method melts poly silicon in a high-pressure furnace.

 A crucible containing the silicon mold is moved from hot to cold, in order to enable crystal
growth.
 The Bridgman furnace works with three temperature zones.
 The upper zone with temperatures above the melting point.
 The lower zone with a temperature below the melting point.
 An adiabatic zone as a muffle between the two.
 The ampoule containing silicon is raised into the upper zone until only the lower portion of
the single crystal seed remain unmelted in the lower zone.
 After the temperature stabilizes, the ampoule is lowered slowly into the lower zone to initiate
crystal growth from the seed.
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 Bridgman technique
 The Bridgman technique is one of the oldest techniques used for growing crystals.
 The Bridgman technique employs a crystal growth from melt.
 In Bridgman technique the crucible containing the molten material is translated along the
axis of a temperature gradient in a furnace.
 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.
 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.
 This seed is a piece of single crystal and ensures a single-crystal growth along a certain
crystallographic orientation.
 Part of the seed will be re-melted after the contact with the melt. This provides a fresh
interface for the crystal growth.
 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.
 The Bridgman technique can be implemented in either a vertical (vertical Bridgman
technique) or a horizontal system configuration (horizontal Bridgman technique).
 The vertical Bridgman technique enables the growth of crystals in circular shape.
 Unlike the D-shaped ingots grown by horizontal Bridgman technique.
The crystals grown horizontally exhibit high crystalline quality (e.g. low dislocation density)
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 Czochralski technique
 Czochralski method is one of the major melt-growth techniques.
 It is widely used for growing large-size single crystals for a wide range of commercial and
technological applications.
 One of the main advantages of Czochralski method is the relatively high growth rate.
 The material to be grown is first melted by induction or resistance heating under a
controlled atmosphere in a non-reacting crucible.
 The melt is kept for a certain time at a temperature above the melting point and the
temperature is then reduced to a value slightly above the freezing point.
 The freezing point is judged by cooling the melt until crystals start to appear on the surface.
 After a further lowering of the temperature a seed (cut in the appropriate orientation) is
inserted into the melt.
 By pulling and rotating the seed simultaneously a crystallization center form.
 The diameter of the pulled crystal is controlled by manipulating the temperature of the melt
and the pulling rate.
 Suitable engineering of both axial and radial temperature gradients is needed to grow single
crystals of desired dimensions reliably.

 Czochralski technique
 Step 1: Preparation of high purity of molten silicon
In Czochralsky process, high purity of silicon, it’s encouraged to be use as molten to fume
single crystal silicon. Silicon Di oxide can be used to prepare high purity of molten silicon,
then the substance or be heat it to its molten point to in crucible melt of quartz. The
supersaturated molten solution will become the so’s of silicon wafer.
 Step 2: dipping seed crystal
Small piece of single crystal material known as seed crystal will be dip into the saturated
molten silicon solution. Seed crystal is created use to grow a lot crystal of same material,
the lot crystal will grow when the seed crystal dip into the molten which will then be cold.
 Step 3: Pulling the seed upwards
The seed crystal will extract from the molten silicon pull in the rod will be pull upward in
rotated on the same time. During this time, the rod in the crucible, rotate opposite direction
to minimize the effects of convention in the molt, in manufacturing single crystal silicon,
the temperature gradient, pulling rate and rotation speed influences deices of the single
crystal as a seed crystal slowly raised upward. The molten silicon will be solidified as same
as the seed that is why this process is known as growing which is producing in neural of
single crystal silicon from molten silicon. The blotch cylindrical crystal silicon is called
ingot aboil which can be grown 200 to 400 mm diameter.
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 Crystal growth, in principle, as we know today, involves control of a phase change.

 Three crystal growth processes
 Solid growth – S→S process involving solid- solid phase transitions.
 Melt growth – L→S process involving liquid-solid phase transitions.
 Vapor growth – V→S process involving gas - solid phase transitions.
 Three crystal growth methods
 Growth from melt
 Growth with crucible
 Verneuil Flame fusion method
 Float Zone method
 Chemical dissolution
 Zone movement
 Many growth methods known by their inventors
o Czochralski
o Bridgemann-Stockbarger
o Kapitza
 By the methodology involved in the system
o Float zone
o Vertical gradient freeze
o Zone-refining
o Liquid phase epitaxy
o Directional solidification
o Growth under micro
o Hyper-gravity
 Growth without crucible
 Growth from solution
 Growth from vapor
 For a monocomponent system, S→S processes are rarely used except for
 Certain metals where strain annealing, sintering, devitrification, polymorphic phase change
occurs.
 The L→S processes are two types
 Conservative
 Directional solidification (Stockbarger-Bridgemann)
 Cooled seed (Kyropoulos)
 Pulling (Czochralski)
 Nonconservative
 Zoning (horizontal, vertical, float zone, growth on a pedestal)
 Verneuil (flame fusion, plasma and arc discharge)
 The V→S process is based on sublimation-condensation
 For a polycomponent system, S→S processes involve precipitation from solid solution(exsolution).
 The L→S processes are two types: (1)
 Growth from solution (evaporation, slow cooling, temperature differential, and solution
transport – thermal gradient zone melting) by use of aqueous solutions, organic solutions
or molten salt solutions.
 Growth by reaction (chemical reaction or electro-chemical reaction)
 In the V→S category crystal grows by reaction-van Arkel, Epitaxial and Gas phase growth of
inorganic substances.