U.S. patent number 3,675,619 [Application Number 04/813,374] was granted by the patent office on 1972-07-11 for apparatus for production of epitaxial films.
This patent grant is currently assigned to Monsanto Company. Invention is credited to John W. Burd.
United States Patent |
3,675,619 |
Burd |
July 11, 1972 |
APPARATUS FOR PRODUCTION OF EPITAXIAL FILMS
Abstract
A vertically extending reaction system has seriatim, reaction,
mixing and deposition chambers. The substrate support forms the
bottom wall of the deposition chamber, is rotating, pyramidal in
form and includes a flange extending laterally from the bottom
thereof.
Inventors: |
Burd; John W. (Chesterfield,
MO) |
Assignee: |
Monsanto Company (St. Louis,
MO)
|
Family
ID: |
25212198 |
Appl.
No.: |
04/813,374 |
Filed: |
February 25, 1969 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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602242 |
Dec 16, 1966 |
3511723 |
|
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Current U.S.
Class: |
118/719;
118/730 |
Current CPC
Class: |
C23C
16/00 (20130101) |
Current International
Class: |
C23C
16/00 (20060101); C23c 011/00 () |
Field of
Search: |
;118/48-49.5,500,320,323
;117/106,107.1 ;148/174,175 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kaplan; Morris
Parent Case Text
This application is a division of U.S. Pat. application Ser. No.
602,242, filed Dec. 16, 1966 and now Pat No. 3,511,723.
Claims
Having thus described my invention, what I desire to claim and
secure by Letters Patent is:
1. An epitaxial deposition reaction system for deposition of an
epitaxial film on a substrate, said reaction system comprising:
a. a vertically disposed reaction vessel having seriatim a reaction
chamber, a mixing chamber and a deposition chamber,
b. means for creating an epitaxial reactant gas mixture in said
reaction chamber comprising a source means disposed therein and
feeding means connected to said reaction chamber for introducing a
gas therein to thereby contact and volatilize said source, and gas
feed means for adding doping material to said mixing chamber and
causing contact with the gas mixture from said reaction
chamber,
c. means permitting fluid passage between said reaction, mixing and
deposition chambers so that said epitaxial reactant gas mixture is
admitted to said deposition chamber,
d. a substrate supporting element in said deposition chamber
opposed from the means permitting fluid passage so that the gas
admitted to said deposition chamber passes over said substrates in
said deposition chamber, causing the epitaxial film to be deposited
on said substrates,
1. said supporting element being pyramidal in form, the apex of
which extends towards and is in alignment with said means
permitting fluid passage,
2. a flange extends laterally from the base of the pyramid whereby
substrates may be supported on said flange and inclined against
each associated facet of said pyramid, and
3. said support forms substantially the bottom wall of said
deposition chamber,
e. motive means operatively associated with said vessel for
rotating said supporting element with respect to said deposition
chamber, and
f. heating means surrounding said reaction vessel, said heating
means being adapted to maintain said chambers at temperatures
different from one another.
2. The epitaxial deposition reaction system of claim 1 further
characterized in that said supporting element is in the form of a
pyramid having eight side walls.
3. The epitaxial deposition reaction system of claim 1 further
characterized in that said heating means is designed to produce
three temperature zones and wherein the first temperature zone is
created in said reaction chamber, the second temperature zone is
created in said mixing chamber at a higher temperature than said
first zone and the third zone is created in said deposition chamber
at a lower temperature than said first and second zones.
Description
This invention relates in general to the production of
semiconductor materials, and more particularly to an improved
apparatus for the production of epitaxial films of large single
crystals.
A large number of problems have been encountered in the growing of
epitaxial crystals of a semiconductor for diverse electronic
applications. These problems are generally more severe in those
areas which employ a ternary system. Generally, the production of
semiconductor devices must be performed under the most carefully
controlled conditions. The rate of crystal growth must be
controlled exactly to insure a desired and uniform epitaxial layer.
Moreover, the reactant composition and reaction conditions must be
stabilized to attain uniform composition of the mixed crystal.
Utmost purity of the semi-conductor is necessary which necessitates
starting materials of the highest purity and reaction conditions
which insure a minimum of contaminations. It is also necessary to
have controlled and uniform doping of the crystals over wide ranges
of doping levels.
The technique of epitaxial deposition for binary and ternary
systems involves thermally reversible reactions in a carrier gas.
In the region of the source material, the equilibrium of the
reversible region is toward the more volatile constituents of the
system and is thermally shifted toward the less volatile
constituents in the region of the substrates. Thus, semiconductor
material is transported from the source region and is deposited on
a substrate. When the substrate is a single crystal, the same
crystalline orientation and the periodicity of the substrate is
maintained. This technique is practiced both in sealed or so-called
"closed" systems and in systems involving a steady flow of reactant
gas.
The majority of the current reactors for the production of the
epitaxial films to be used in the manufacture of semiconductor
devices are of the so-called "open-tube" design in which the
reactant gases flow into one end of a reactor tube, through the
tube, and exit from the opposite end thereof. The flow rates are
sufficiently low to be classified as laminar-type flow. Upon
entering the reaction tube, the reactant gas mixture first
encounters a source material at a relatively high temperature where
the source may be converted to a volatile halide and another
volatile constituent. The halide is generally a Group III halide
and the volatile constituent is generally a Group V element. This
mixture then passes along the reaction tube to the region of the
wafer substrates at a relatively lower temperature. The reactant
mixture becomes saturated with respect to the quantity of the
volatile Group III halide and the Group V constituent and epitaxial
deposition occurs on the substrate wafers. However, the wafers are
generally longitudinally aligned with respect to the entering
reactant gases and as soon as deposition occurs on the first wafer
in the path of the gas, the composition of the gas stream is
altered. Therefore, the thermodynamic driving force of the reaction
is different with respect to subsequent wafers in the downstream
position.
In order to overcome the change of composition with respect to
subsequent wafers in the stream of gas, alteration of the
temperature should occur along the length of the reaction tube so
that those wafers at the distal end of the tube with respect to the
entering reactant gases would have a lower temperature than the
wafers or substrates which were located at the proximate end of the
tube. However, this type of temperature gradient is difficult to
maintain accurately and reproducibly in order to compensate for the
depleted reactants in the stream of gas. Consequently, uniform
growth rate and, therefore, thickness control from wafer to wafer
was poor. Furthermore, the variation in gas composition and
deposition temperatures with substrate position introduces
variations in compositions for ternary alloy systems and in
impurity concentration from wafer to wafer. Consequently, it was
often very difficult to maintain composition and desired doping
levels in each of the epitaxial films.
It is, therefore, the primary object of the present invention to
provide an apparatus for producing epitaxial films on single
crystal structures.
It is another object of the present invention to provide an
apparatus of the type stated which overcomes the non-uniformity of
conventional film deposition by controlling crystal growth to
insure a desired and uniform epitaxial layer.
It is a further object of the present invention to provide an
apparatus of the type stated where reactant composition and
reaction conditions are stabilized to attain a uniform composition
of mixed crystal.
It is also another object of the present invention to provide an
apparatus of the type stated where controlled and uniform doping of
the crystals is achieved over a wide range of doping levels.
It is another salient object of the present invention to produce an
apparatus of the type stated which can be economically constructed,
and a method of the type stated which can be performed in a minimal
amount of time.
With the above and other objects in view, our invention resides in
the novel features of form, construction, arrangement and
combination of parts presently described and pointed out in the
claims.
In the accompanying drawings:
FIG. 1 is a vertical sectional view showing in side elevation an
apparatus for the production of epitaxial films constructed in
accordance with and embodying the present invention;
FIGS. 2 and 3 are vertical sectional views taken along lines 2--2
and 3--3, respectively of FIG. 1;
FIG. 4 is a vertical sectional view similar to the view of FIG. 1
and showing a modified form of apparatus constructed in accordance
with and embodying the present invention;
FIG. 5 is a perspective view of a wafer support tray forming part
of the apparatus of FIG. 4;
FIG. 6 is a perspective view of a modified form of wafer support
tray constructed in accordance with and embodying the present
invention;
FIG. 7 is a diagrammatic view showing the temperature gradient
employed across the apparatus of the present invention and the
operation thereof;
FIG. 8 is a graphic illustration showing the percentage of
deviation from a normal value of layer thickness by devices
constructed in accordance with prior art methods and devices
constructed in accordance with the present invention; and
FIG. 9 is a graphic illustration showing the percentage of
deviation from a normal value of doping level by devices
constructed in accordance with prior art methods and devices
constructed in accordance with the present invention.
GENERAL DESCRIPTION
Generally speaking, the present invention relates to a modified
form of open ended epitaxial deposition reactor. The reactor is
subdivided into three chambers which also serve as three
temperature zones. For the purposes of the present invention, the
first chamber generally serves as a reaction chamber, the second
chamber generally serves as a mixing chamber and the third chamber
serves as a deposition chamber. The reactant gas mixture used in
the reactor of the present invention can be prepared in any of a
number of conventional ways. One of the preferred methods used in
the practice of the present invention is the introduction of a
reactant gas preferably containing a Group V halide into the
reaction chamber where it reacts with a source material preferably
containing a Group III element. This source material is then
converted to a volatile Group III halide and the volatile Group V
elements. This mixture is then passed into the mixing chamber where
a dopant may be admixed with the reactant gas.
The deposition chamber is preferably an isothermal chamber and is
designed so that each of the wafers disposed therein is directly
located in the stream of entering gas. The substrate holder is
preferably in the shape of a regular octagon having a flat bottom
wall which is slightly annularly spaced from the interior of the
deposition chamber. Furthermore, a plurality of eight side walls
converge inwardly and upwardly to an apex which is in direct
alignment with a gas port formed in the wall separating the
deposition chamber and the mixing chamber. It should be recognized
that the substrate holder is not limited to the shape of a regular
octagon and a holder with any number of side walls may be employed.
The gases enter into the deposition chamber through this port,
preferably at a laminar flow and are spread evenly across all of
the eight faces of the substrate support. A ledge is provided on
each of the eight walls for holding the wafers disposed thereon.
Furthermore, the substrate support is rotated at a relatively low
rate of speed in order to obtain uniform heat distribution and
thermal symmetry across each of the wafers. The discharge tube is
also connected to the deposition chamber for removal of the spent
gases in the deposition chamber. A three zone furnace surrounds the
reactor and provides the desired temperature conditions in each of
the three zones.
The previously described reactor is a vertically disposed reactor
where the reaction chamber is located at the upper end and the
deposition chamber is located at the lower end. It is also possible
to provide a horizontally disposed reactor substantially similar to
the previously described vertical reactor. However, in the
horizontal reactor a slightly different type of wafer support is
provided. In this latter modification, a series of forks are
provided so that either one or a pair of wafers may be disposed
between each of the forks. Again, the forks are connected to a
shaft which is powered by a conventional motor for rotating the
forks and the wafers disposed thereon.
These types of reactors uniquely lend themselves to the preparation
of multilayer structures which are required in one continuous
operation. This type of continuous operation for preparing
multiconfigurations in preferred over a stepwise method where
layers of one conductivity type are grown in one operation and
where layers of different conductivity types are grown in another
operation.
DETAILED DESCRIPTION
Referring now in more detail and by reference characters to the
drawings which illustrate practical embodiments of the present
invention, A designates an apparatus for the production of
epitaxial deposition films and generally comprises a vertically
disposed reaction vessel or tube 1 which is preferably constructed
of quartz or any other gas-tight material which is capable of
withstanding the high temperature of operation, which is inert to
the gaseous reactants, and which does not emit impurities at such
temperatures. Other suitable materials are boron nitride, a
refractory aluminum oxide and similar refractory materials. The
reaction vessel is schematically illustrated in FIG. 1 and is
flared outwardly in the provision of a tapered upper end 2, with an
annular flange 3 for accommodation of an end plug 4, the latter
having an aperture 5. The reaction vessel 1 is also provided
intermediate its ends with a pair of axially spaced discs 6,7
thereby dividing the reaction vessel 1 into a reaction chamber 8, a
mixing chamber 9 and a deposition chamber 10.
The reaction chamber 8 or the upper chamber, reference being made
to FIG. 1, is provided with a gas inlet tube 11 which extends
through the plug 4 and terminates above a container 12 of source
material which is preferably a Group III element, such as gallium.
The feed gas admitted through the tube 11 is a halogen-containing
gas and preferably a chlorine-containing gas in the form of
hydrogen chloride, phosphorus trichloride or arsenic trichloride,
for example. The feed gas may contain the Group V element and
reacts with the source material to form a volatile Group III
halide. The epitaxial growth of III-V compounds is based on the
departure of the equilibrium of a reversible reaction between the
Group III halides and Group V elements such as for example:
3GaCl + 1/2 As.sub.4 .revreaction. 2GaAs+GaCl.sub.3
The basic principle of the transfer reaction is that the
equilibrium shifts towards the left with increasing temperature and
towards the right with decreasing temperature. This reaction is
surface catalyzed by seed crystals so that deposition occurs on
seed crystals more readily than on surrounding surfaces at the same
temperatures. It should be understood that the present invention is
not limited to this reaction described above.
The reactant gases are then passed into the mixing chamber 9
through a port 13 formed in the disc 6. Also entering the mixing
chamber 9 and terminating in close proximity to the terminal end of
the discharge port 13 is a dopant feed tube 13'. Any conventional
doping material may be used and may be introduced by any
conventional means. For example, the dopant may be introduced in
elemental form or as a volatile compound of the dopant element. The
quantity of dopant employed is generally controlled by the
electrical properties desired in the final product. Suitable
amounts contemplated herein are those sufficient to produce
concentrations in the range approximately from 1 .times. 10.sup.15
to 5 .times. 10.sup.20 atoms per cubic centimeter of product.
As an alternative to the precess of introducing the Group V element
with the feed gas into the reaction chamber in the manner
described, the inlet gas may contain only the halide carrier in the
form of hydrogen and hydrogen halide. The halide carrier will then
react with the Group III element in the container 12 forming a
volatile Group III halide. The Group V element containing gas is
then admitted to the mixing chamber 9 with the dopant through the
tube 13'. The gas carrying the volatilized Group III element will
then mix with the gas containing the Group V element in the mixing
chamber 9.
It has been found to be desirable to employ a chloride transport
system in the practice of the present invention. This system is far
preferable to systems which employ an oxide intermediate as the
oxide systems generally require higher temperatures than a halide
system. These higher temperatures increase the contamination
through reaction of the volatile species with the reactor
materials. Furthermore, appreciable amounts of undesired oxides may
be incorporated in the epitaxial film when an oxide transport is
employed. The other halides, such as bromides and iodides require
lower deposition temperatures which may not be suitable in all
cases and it has also been found that some substrate orientations
do not grow suitable in iodide or bromide systems. However while
chlorides present the preferable transport media, it should be
recognized that the other halides may be used in most cases.
The reactant gases which have been thoroughly mixed in the mixing
chamber 9 are then passed into the deposition chamber 10 through an
inlet port 14 formed in the disc 7. In my copending application
Ser. No. 521,240, filed Jan. 3, 1966 and now U.S. Pat. No.
3,441,000, the gas was admitted to the deposition chamber at a
relatively high velocity causing turbulence and rapid mixing in the
deposition chamber. These velocities created in the deposition
chamber were a wide departure from the laminar flows which were
previously employed. However, through the structure of the present
reactor, it is possible to again admit the reactant gases into the
deposition chamber in the slower laminar flows. In fact, it is
possible to admit the reactant gases into the deposition chamber at
flow rates which range form 60 to 600 centimeters per second. The
deposition chamber 10 is open ended at its lower end and fits
within a drive housing 16, the latter being more fully illustrated
in FIG. 1. The drive housing 16 generally comprises a supporting
cup 17 having a bottom wall 15, an annular side wall 18 and an
intermediate supporting shoulder 19. The lower end of the
deposition chamber 10 is sized to fit snugly within the annular
side wall 18 and rests against the intermediate supporting shoulder
19, in the manner as illustrated in FIG. 1. The interior surface of
the annular side wall 18 is milled away along its upper end and is
threaded to accommodate an upper gland nut 20. The gland nut 20 is
also tapered at its lower end and is spaced from a matching taper
on the side wall 18 for accommodation of an "0" ring seal 21, the
latter preferably being formed of viton. The side wall 18 is
further cut away in the provisions of a fluid duct 22 and covered
by an annular sleeve 23. The sleeve 23 is integrally formed with an
outwardly extending fluid port 24 for connection to a suitable
source of cooling fluid (not shown). The side wall 18 is also
provided with a discharge port 25, the latter connecting with a
discharge pipe 26 secured to the lower end of the drive housing 16.
In this manner, the spent gases from the deposition chamber 10 can
exit through the discharge pipe 26 and through the discharge port
25 formed in the housing 16. The sleeve 23 is also provided with an
outwardly extending fluid port 27 for discharge of the fluid which
enters through the port 24.
The bottom wall 15 is centrally apertured to accommodate an
upwardly extending boss 28 formed on a bearing hub 29 in the manner
as illustrated in FIG. 1. And bearing hub is also provided wit with
a downwardly extending diametrally reduced boss 30 for
accommodating a bearing cap 31. The boss 30 and the bearing cap 31
are internally bored to accommodate conventional bearings 32,33 for
journaling a vertical drive shaft 34. Furthermore, the bearing cap
31 is held rigidly in place and secured to the earing hub 29 by
means of a series of cap screws 35.
A central bore or relief 36 is formed between the lower end of the
boss 30 and the bearing cap 31 and being disposed in the relief and
also be operatively mounted on the shaft 34 for rotation therewith
is a pulley 37. The pulley 37 cooperates with a similar pulley 38
operatively mounted on the upper end of a connecting shaft 39. At
its lower end, the connecting shaft is, in turn, connected to a
conventional speed reducer 40 which is, in turn, operable by a
conventional electric motor 41. A drive belt 42 is trained around
each of the cooperating pulleys 37,38 in the manner as illustrated
in FIGS. 1 and 3. Furthermore, it can be seen that the housing 16
serves as a mechanism for holding the reactor 1 in a substantially
vertical upright position in the manner as illustrated in FIG.
1.
The bearing hub 29 is annularly grooved to accommodate a pair of
vertically spaced sealing rings or so-called "0" rings 43. The
upper end of the main drive shaft 34 extends upwardly into the
deposition chamber 10. The drive shaft 34 is also preferably
constructed of a quartz material or similar material which is inert
to the reaction taking place in the deposition chamber or to any of
the gases which are admitted to the deposition chamber. It is
possible to construct the drive shaft 34 of a metal material up to
the point where it enters the deposition chamber 10. At this point,
a conventional coupling can be employed to connect a quartz
extension to the lower end of the main drive shaft and where the
quartz extension would extend upwardly into the deposition chamber
10.
At its upper end, a wafer support tray 44 is formed with or rigidly
secured to the upper end of the main drive shaft 34. The wafer
support tray 44 generally comprises a bottom plate 45 which is
circular in horizontal cross section and is slightly spaced from
the interior wall of the deposition chamber 10, thereby forming a
gas passage 46 circumferentially therearound. The wafer support
tray 44 is also in the form of a regular octagon having eight
upwardly and inwardly converging side walls 47, which converge at
an apex 48. The walls 47 are slightly spaced inwardly from the
peripheral margin of the plate 45, thereby providing a ledge 49 at
the base of each of the walls 47 for supporting a wafer w disposed
thereon.
In essence, the rotating tray 44 also serves as an end wall in the
deposition chamber 10 with an apex 48 directed toward the inlet
port formed in the disc 7. The tray 44 is preferably rotated at a
speed of approximately 10-15 rpm. In connection with the present
invention, it has been found that the tray 44 should be rotated at
a speed within the range of 10 rpm and 15 rpm. The gases should be
introduced into the deposition chamber 10 in a condition of laminar
flow so that a condition of high turbulence is not created in the
deposition chamber 10. The gas which enters the chamber 10 will
move evenly at a relatively uniform rate of speed across each of
the wafers w supported on the tray 44. Since all of the wafers are
located in the same transverse plane with respect to the entering
gas, substantially even deposition will occur across each of the
wafers w supported thereon.
Since any portion of the gas stream contacts substrates in only one
plane, the effect of changing gas composition from wafer to wafer
in the prior art devices has been eliminated. Furthermore, a much
shorter isothermal zone is required. For the purpose of the present
invention, the substrate tray 44 is designed to hold 8 wafers with
a maximum diameter of approximately 20 millimeters. The angle of
inclination of the wafers from the vertical should be within
10.degree. to 50.degree. with a preferred angle of 30.degree. with
respect to the vertical.
A conventional three zone furnace F, preferably of the radiant
energy type is disposed about the reaction vessel 1 in the manner
as illustrated in FIG. 1. The furnace F is designed to produce a
temperature gradient of the type illustrated in FIG. 7 across the
reaction vessel 1. Thus, it can be seen that the temperature
initially rises to the desired reaction temperature in zone 1,
which is preferably in the range of 400.degree. to 1100.degree. C.
Thereafter, the temperature is increased substantially to a
temperature within the range of 500.degree. to 1200.degree. C in
the mixing zone or chamber 9. This higher temperature level is
maintained substantially constant for the greater portion of zone
2. Thereafter, the temperature is markedly dropped in zone 2
immediately prior to the deposition zone or deposition chamber
10.
It is desirable, though not at all necessary, to maintain the
entire deposition chamber 10 at an isothermal temperature for
purposes of creating deposition of the epitaxial film on the wafers
w. The isothermal temperature is preferably in the range of
400.degree. to 1100.degree. C in order to produce the deposition of
the epitaxial film in the deposition chamber 10. It should be
understood that this temperature range is varied for the different
compositions of the epitaxial film and for the different gas flow
rates. As indicated above, the reaction is also surface catalyzed
so that deposition occurs more readily on the wafers w than on the
surrounding surfaces at the same temperature. Furthermore, the gas
phase mass transfer and crystallographic orientation also have
significant effects on the deposition rate.
It can also be seen that the unique reactor design readily lends
itself to an ability to prepare a multilayered structure in one
continuous operation. As indicated previously, this type of
operation for preparing the multilayer configuration is preferred
over a stepwise method where layers of one conductivity type are
grown in one operation and layers of a different conductivity type
are grown in another operation. Such a "stepwise" procedure
necessarily lengthens the production cycle and increases the
probability of contamination of the grown layers. A stepwise method
also adds difficulty in the controlled growing of the graded
junction. In accordance with the procedures of the present
invention, it is now possible to change doping agents by ceasing
the flow of dopant into the mixing chamber, flushing the entire
system with an inert gas such as hydrogen and changing dopant
gases. The gas flows into the reaction vessel are maintained at
sufficiently high velocity so that backflow into the source of the
Group III element is prevented and contamination thereof is thereby
prevented. Accordingly, it is now possible to switch dopant gases
without fear of contaminating the source of Group III material.
This present method thereby avoids the difficulty previously
employed in the stepwise growing of graded junctions.
It should also be recognized that this apparatus and method is
particularly adaptable for use with gallium phosphide and gallium
arsenide systems. If a gallium arsenide-phosphide epitaxial layer
is to be formed on the wafer w, the reactant gases in the inlet
tube 11 are preferably phosphorus trichloride, arsenic trichloride
and hydrogen. Consequently, the dopant admitted in the dopant tube
would contain pure hydrogen and would contain the dopant plus
hydrogen. However, if the carrier gas is merely hydrogen and
hydrogen chloride; phosphine, arsine, the hydrogen and dopant are
added through the dopant tube 13'. In either case, gallium
arsenide-phosphide alloy is formed and deposited on the wafers
w.
It should also be recognized that epitaxial films formed in
accordance with this invention comprise compounds formed from the
elements of Group III-A of the periodic system and particularly
those having atomic weights of from 10 to 119 and elements selected
from Group V-B having atomic weights of from 12 to 133. Included in
this group of compounds are the nitrides, phosphides, arsenides and
antimonides of boron, aluminum, gallium and indium. The bismuthides
and thallium compounds, while operable, are less suitable. In
addition to the use of the above compounds by themselves, mixtures
of these compounds are also contemplated as epitaxial films, e.g.,
aluminum nitride and indium antimonide mixed in varying proportions
when produced by the instant process produce suitable semiconductor
compositions.
Other combinations of elements within the above group which are
contemplated herein include ternary and quaternary compositions, or
mixed binary crystals, such as combinations having the formulas
GaAs.sub.x P.sub.1.sub.-x, InAs.sub.x P.sub.1.sub.-x, GaP.sub.x
N.sub.1.sub.-x, AlP.sub.x As.sub.1.sub.-x, Ga.sub.x In.sub.1.sub.-x
As, Ga.sub.x In.sub.1.sub.-x P, In.sub.x Ga.sub.1.sub.-x Sb,
Ga.sub.x Al.sub.1.sub.-x P, Ga.sub.y In.sub..sub.-y As.sub.x
P.sub.1.sub.-x and GaAs.sub.x (PyN.sub.1.sub.-y).sub.1.sub.-x,
where x and y have a numerical value greater than zero and less
than one.
Materials useful as substrates herein include the same materials
used in the epitaxial films as just described and, in addition,
compounds of elements of Groups II and VI (II-VI compounds) and
compounds of Groups I and VII elements (I-VII compounds), and the
elements silicon and germanium are suitable substrates. Suitable
dimensions of the seed crystal are 1 mm thick, 10 mm wide and 15-20
mm long, although larger or smaller crystals may be used.
It should be appreciated that by following the teaching of this
invention it is possible to form semiconductor bodies having a
plurality of layers of differing conductivities, wherein the width
of each layer may be precisely controlled. This allows the
transition region or junction, if different type conductivity
layers are involved, to be accurately positioned in the
semiconductor body. It is also possible to provide in any layer
formed, any variation in conductivity desired in any plane parallel
to the transition region by varying the concentration of vapor
source of active impurity atoms in the flow to the reaction chamber
during formation of the layer. The benefits from flexibility of
such controls, compared to prior art techniques for forming
transition regions, are immediately apparent.
As illustrated by the devices shown, any desired type of
semiconductor device may be made by utilizing the method of the
present invention. In each case, the semiconductor device will
include at least two layers of semiconductor material having
different conductivities and separated by a transition region. In
some instances, the transition region will be a P-N junction, while
in other instances it may be a P-I or an N-I junction and in still
other instances it may be a sharp transition region between layers
of high and low resistivity material of the same conductivity type.
It will be appreciated that where references is made herein to
different conductivities in layers in any assembly thereof, that
the difference may be either in kind or in degree. In the case of a
P-N junction, the layers separated thereby may have the same degree
of conductivity (or resistivity) but the type of conductivity will,
of course, be different. Alternatively, in the case of, for example
an N+-N transition region the conductivity type will be the same
for the layers but the degree of conductivity will, of course, be
different. In any case, however, the width of the layers of
material and the location and type of the junction or transition
region may be very accurately defined and controlled by the method
of the present invention.
It should also be recognized that each of the discs 6, 7 can be
replaced by glass frit discs (not shown) and which are sufficiently
porous to permit the gas flow therethrough.
It is possible to provide a modified form of epitaxial deposition
reactor B substantially as illustrated in FIGS. 4 - 6 and which is
substantially similar to the previously described deposition
reactor A. The reactor B, however, while substantially identical in
almost all respects to the reactor A is horizontally disposed in
the same manner as the reactor described in my copending
application Ser. No. 521,240, filed Jan. 3, 1966. However, a
substantially different type of deposition chamber is employed when
compared to the deposition chamber described and illustrated in the
aforementioned copending application.
In the epitaxial deposition reactor B a substrate holder or
so-called "fork" 50 is secured to the inner end of the main drive
shaft 34. Again, the substrate holder 50 may be integrally formed
with the quartz shaft 34, or it may be secured to the upper end of
a metal shaft in any conventional manner. The substrate holder 50
generally comprises a support shaft 51 which is integrally formed
with a pair of spaced opposed outwardly extending fingers 52 in the
manner as illustrated in FIG. 5. The fingers 42 are each provided
with longitudinal slots 53 on their interior surface for
accommodating wafers w. The slots may be sized to accommodate one
wafer or they may be sized to accommodate a pair of wafers which
are disposed in back-to-back relationship so that the bottom
surface of each wafer is not exposed to the gas streams, that is,
where the undersurface of each of the wafers is facewise disposed
upon each other.
It is also possible to provide a modified form of substrate holder
54, substantially as illustrated in FIG. 6 and which is
substantially similar to the previously described substrate holder
50. The substrate holder 54 includes a shaft 55 which integrally
merges into four outwardly extending fingers 56. Each of the
fingers 56 lies at the corners of and in effect, form a perfect
rectangle. Furthermore, each of the fingers is spaced from the next
adjacent finger by a distance substantially equal to the diametral
size of a wafer w. Each of the fingers 56 is provided with pairs of
slots 57,58 which are located at 90.degree. angles with respect to
each other. Thus, one finger has a slot 57, which is aligned with
respect to a similar slot 57 on an opposed finger 56. The first
finger also has a slot 58 which is located at 90.degree. with
respect to the slot 57 and the latter slot 58 being opposed to a
similar slot 58 formed in another finger being located at
90.degree.. In this manner, it is possible to retain four wafers
between each of the four fingers 56. It also should be recognized
that the slots 57 may be made sufficiently large for accommodating
a pair of wafers where the underside of each of the wafers is
facewise disposed against each other in back-to-back relationship.
It can be seen that this type of substrate holder permits gas flow
along all surfaces of each of the eight wafers which are retained
thereon and furthermore does not interfere with the gas flow in the
reactor. It is within the scope of the present invention to provide
substrate holders which employ more than four fingers so that a
number of substrates greater than four can be retained at any one
time.
It should be recognized in connection with the present invention
that the epitxial deposition reaction system B is as versatile as
the previously described reaction system A and furthermore, the
various films which can be manufactured in the reaction system A
can also be manufactured in the reaction system B.
EXAMPLES
The invention is further illustrated by but not limited to the
following examples. These examples exemplify the difference
existing between the epitaxial deposition reactor of the prior art
and the procedures employed therein and the epitaxial deposition
reactors of the present invention and the associated procedures.
The first of the examples employs a so-called "open tube" of the
prior art type and using prior art methods. The open tube reactor
was employed in Example 1 to make an accurate comparison of the
modified form of open tube reactor of the present invention, which
is employed in the subsequent examples. A second example indicates
the results achieved with a vertically disposed reactor, but where
the substrate holder is rotated. Example 3 discloses the results
achieved when the vertically disposed reactor of Example 2 was
employed and when the substrate holder was rotated. Example 4
indicates the superior results achieved when a horizontally
disposed reactor of the type disclosed herein is employed.
Example 1
An epitaxial deposition open tube reactor of the prior art type
made of quartz is used in this example. A radiant heater is
disposed about the reactor and effectively subdivides the reactor
into two temperature zones. Connected to one end of the reactor is
a source of hydrogen chloride which is passed through a
purification train. Also connected to the same end of the reactor
is a source of hydrogen which is passed through a palladium
purifier. Tellurium doped solid gallium arsenide is disposed in
zone 1.
Hydrogen chloride and hydrogen gases are passed through these zones
at a flow rate of approximately 100 cubic centimeters per minute.
The reactor has an inner diameter of 20 millimeters and an overall
length of 36 inches. However, the effective length is only 28
inches.
The substrates are gallium arsenide wafers which are oriented in
the 1.sup.. 0.sup.. 0 plane (Miller Indices). The gases are passed
through the reactor for approximately 20 minutes. The substrates
are held at approximately 800.degree. C and the gallium arsenide
source region is maintained at approximately 900.degree. C. The
deposition portion of the reactor is held to a 10.degree. C
temperature decreasing gradient per inch. The net carrier level
n.sub.d type is found to be between 5.2 .times. 10.sup.16 /cm.sup.3
.ltoreq. n.sub.d .ltoreq. 2.85 .times. 10.sup.17 /cm.sup.3.
Two wafers are employed in each run for this example and a series
of 11 runs are conducted under the same conditions. The wafer on
the proximate end is designated as the first wafer in Table 1 set
forth below and the wafer on the distal end is designated as the
second wafer. The thicknesses in microns of these layers are
measured and tabulated in Table 1. The difference of the
thicknesses, the averages and the deviation from the average are
also calculated and set forth in Table 1. The percentage deviation
from the average is plotted for each run in FIG. 8 and accordingly
two curves showing plus and minus values as deviations from the
average are plotted in solid lines. These curves show the wide
deviation from a zero error value for each of the runs and the
difficulty in achieving uniform thickness.
The dopant levels are also measured in each wafer and these data
are set forth in Table 2. The difference between the dopant levels
of each wafer in a run is calculated and tabulated in Table 2 and
similarly the averages and deviations from the normal are also set
forth in Table 2. These deviations are plotted in FIG. 9 and show
the wide deviation of dopant levels from the normal.
---------------------------------------------------------------------------
TABLE 1
LAYER THICKNESS DATA
Run No. 1st. 2nd. Diff. Avg. Dev.
__________________________________________________________________________
6.0 - 7.5 1.5 6.75 .+-.11.6% 6.0 - 9.2 3.2 7.6 .+-.21.0% 5.5 - 6.5
1.0 6.0 .+-. 8.35% 3.0 - 3.8 0.8 3.4 .+-.11.75% 5.0 - 5.9 0.9 5.45
.+-. 8.25% 4.6 - 5.4 0.8 5.0 .+-. 8.0% 3.6 - 5.1 1.5 4.35
.+-.17.25% 4.5 - 5.7 1.2 5.10 .+-.11.75% 3.8 - 5.6 1.8 4.7
.+-.19.2% 10 6.0 - 8.0 2.0 7.0 .+-.14.3% 4.4 - 5.7 1.3 5.05
.+-.12.9%
__________________________________________________________________________
TABLE 2
DOPING LEVEL DATA
Doping Levels Run No. (.times. 10.sup.17) Diff. Avg. Dev.
__________________________________________________________________________
1.72 - 1.15 0.57 1.435 .+-.19.8% 0.79 - 1.29 0.50 1.04 .+-.24% 1.9
- 2.4 0.50 2.15 .+-.11.6% 1.65 - 2.3 0.65 1.975 .+-.16.4% 1.9 - 2.0
0.10 1.95 .+-. 2.6% 2.85 - 2.78 0.07 2.82 .+-. 2.5% 1.4 - 2.0 0.6
1.7 .+-.17.6% 2.1 - 2.6 0.6 2.3 .+-.13.1% 0.93 - 1.3 0.37 1.11
.+-.16.7% 10 1.08 - 1.8 0.72 1.44 .+-.25% 11 0.52 - 0.92 0.40 0.72
.+-.27.8%
__________________________________________________________________________
Example 2
This example employs a vertically disposed epitaxial deposition
reactor constructed in accordance with the present invention. The
reactor vessel is divided into three chambers, namely a reacting
chamber, a mixing chamber and a deposition chamber. The actual
reactor tube was constructed of quartz and the left hand section of
the tube was constructed of a 25 mm by 22 millimeter tubing and had
a 29/42Ts joint at the open end. The length of the tube from the
open end to the beginning of the mixing chamber was approximately
30 inches. A No. 1 porosity quartz frit was positioned at a
distance 27 inches from the open end of the tube and served to
inhibit back diffusion of Group V constituents and dopants into the
source region. The gallium source material was situated upstream
from the frit at a point corresponding to the proper temperature
required for the type of source used, namely gallium metal. The
next section or mixing chamber was approximately 3 inches long and
the dimensions of the tube increased from 25 .times. 22 millimeters
to 70 .times. 74 millimeters. The latter dimension continued for
approximately 19 inches. A 7 .times. 9 millimeter addition tube
extended along the 25 .times. 22 millimeter tube and entered the
mixing chamber where the chamber diameter began to increase. The
mixing chamber ended in a flat bulk head containing a quartz frit
which served to uniformly distribute the reaction gas mixture in
the deposition chamber.
A removable stainless steel drive mechanism such as the type
illustrated in FIG. 4 completes the reactor assembly. The substrate
holder at the end of the drive rod was formed of quartz. The
substrate holder was designed to hold 8 substrates with a maximum
diameter of 20 mm. The angle of inclination of the wafers was
30.degree. with respect to the vertical. The substrate holder was
in the form of an octagonal pyramid of approximately 2.5 inches
height with a diameter at the base of approximately 2.5 inches.
However, in this example, the substrate holder was not rotated and
the substrates were retained in a relatively motionless
position.
The substrates are prepared according to the following procedure:
Slices -- 15 mils thick are cut from an x-ray oriented ingot. They
are mounted on three-1/2 inch diameter No. 316 stainless steel
polishing blocks using standard techniques with beeswax as the
adhesive. Each block will hold approximately 10 slices. They are
next lapped on a John Crane Lapmaster-12 lapping machine using 3
.mu. Microgrit obtained from the Geoscience Instrument Corp.
Approximately 2.5 mils are removed in this operation. They are next
polished on a Robinson-Houchin Twin-Bowl Polisher with Linde C
abrasive and a Linde B abrasive for one hour each using Buehler
Texmet No. 40-7666AB polishing pads. Approximately 0.5 mils are
removed in this operation and the polished wafers have a
mirror-like scratch-free surface to the naked eye. They are next
chemically polished in a 16:1 solution of concentrated sulfuric
acid and 30 percent hydrogen peroxide against a flat Teflon block
using the rotating beaker technique. After the chemical polish
during which another 2 mils are removed the wafers are demounted
from the polishing block, thoroughly cleaned with trichloroethylene
and warm isopropanol and stored in a petri dish for subsequent use.
Immediately prior to use the substrates are etched in a 5:1:1
solution of concentrated sulfuric acid, 30 percent hydrogen
peroxide, and water. They are rinsed with pure water, warm
isopropanol, and blown dry with a stream of pure nitrogen.
A solid gallium arsenide source material in the form of 1/8 inch
cubes is located in the reactor chamber on the upstream side of a
small diameter frit at a point corresponding to a temperature of
approximately 900.degree. C. A mixture of hydrogen chloride in
hydrogen was passed over the source material at a linear velocity
of approximately 1 centimeter per second to allow sufficient
contact time and thereby obtain complete reaction between the
hydrogen chloride and gallium arsenide. Additional purified
hydrogen was fed through the Group V addition tube to bring the
total gas flow to the required volume to produce the desired nozzle
injection velocity. A number of runs were made using this reactor
system and the results thereof are set forth in the following
table, Table 3. The temperature of the gallium arsenide source was
890.degree.-900.degree. C and the temperature of the deposition
zone was approximately 795.degree. +/- 3.degree. C. ##SPC1##
Example 3
This example employs an epitaxial deposition reactor constructed in
accordance with the present invention and which is of the
vertically disposed type. The reactor was substantially identical
in all respects to the reactor employed in Example 2, with the
exception that the substrate holder was rotated at approximately 12
rpm. The substrate holder was similarly identical to that employed
in Example 2.
Eight wafers were disposed on the eight sides of the substrate
holders and reactions were conducted for a period of 60 minutes
during each of the runs.
In this example, a slightly different reaction system was employed.
A gallium reservoir was disposed in the reaction chamber and
hydrogen chloride and pure hydrogen were admitted to the reaction
chamber and passed through the gallium reservoir. The reactant
gases were next passed into the mixing chamber and mixed with
AsH.sub.3 which was added to the mixing chamber.
The gas flow rate was maintained at 1000 milliliters per minute
with a HCL concentration of 0.86 percent by volume and a AsH.sub.3
concentration of 2.0 percent by volume. The velocity of the gas
passing over the substrate was 22.6 centimeters per minute and the
substrate temperature was 800.degree. C.
After the epitaxial deposition reaction, infrared thicknesses were
measured on each of the epitaxial layers of each of the wafers. The
epitaxial layers were measured in five positions, namely, the top,
the bottom, the left and right side margins and the center thereof.
These data are set forth in Table 4. Also set forth in Table 4 is
the average thickness and the deviation from the average within
each wafer and from wafer to wafer
The second run using eight additional wafers under the same
reaction conditions was employed and the data for this run is set
forth in Table 5 herein below. ##SPC2## ##SPC3##
Example 4
This example employs an expitaxial deposition reactor constructed
in accordance with and embodying the present invention and which is
of the horizontally disposed type. The procedure for preparing the
substrates to be used in this example is similar to the procedure
employed in Example 2. The reaction conditions employed in this
example are also similar to the reaction conditions employed in
Example 3. The reactor employed is substantially identical to the
reactor employed in Example 3 with the exception of the substrate
holder. The substrate holder used in this example contains a quartz
rod with four radially offset axially extending forks for retaining
a total of eight substrates.
After the epitaxial deposition reaction, infrared thicknesses are
measured on each of the layers of each of the wafers. The epitaxial
layers are measured in five positions, namely, the top, the bottom,
the left and right side margins and the center thereof. These data
are set forth in Table 6. Also set forth in Table 6 is the average
thickness and the deviation from the average within each wafer and
from wafer to wafer. ##SPC4##
It should be understood that changes and modifications in the form,
construction, arrangement and combination of parts presently
described and pointed out may be made and substituted for those
herein shown without departing from the nature and principle of my
invention.
* * * * *