U.S. patent application number 10/685251 was filed with the patent office on 2004-05-13 for process for producing low defect density silicon.
This patent application is currently assigned to MEMC Electronic Materials, Inc.. Invention is credited to Falster, Robert J., Holzer, Joseph C., Johnson, Bayard K., Markgraf, Steve A., McQuaid, Seamus A., Mutti, Paolo.
Application Number | 20040089224 10/685251 |
Document ID | / |
Family ID | 21918645 |
Filed Date | 2004-05-13 |
United States Patent
Application |
20040089224 |
Kind Code |
A1 |
Falster, Robert J. ; et
al. |
May 13, 2004 |
Process for producing low defect density silicon
Abstract
The present invention relates to single crystal silicon, in
ingot or wafer form, which contains an axially symmetric region
which is free of agglomerated intrinsic point defects, and a
process for the preparation thereof.
Inventors: |
Falster, Robert J.; (London,
GB) ; Holzer, Joseph C.; (St. Charles, MO) ;
Markgraf, Steve A.; (Plymouth, MN) ; Mutti,
Paolo; (Milan, IT) ; McQuaid, Seamus A.;
(Victoria, ES) ; Johnson, Bayard K.; (Jefferson
Hills, PA) |
Correspondence
Address: |
SENNIGER POWERS LEAVITT AND ROEDEL
ONE METROPOLITAN SQUARE
16TH FLOOR
ST LOUIS
MO
63102
US
|
Assignee: |
MEMC Electronic Materials,
Inc.
|
Family ID: |
21918645 |
Appl. No.: |
10/685251 |
Filed: |
October 14, 2003 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10685251 |
Oct 14, 2003 |
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10135597 |
Apr 30, 2002 |
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6632278 |
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10135597 |
Apr 30, 2002 |
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09816015 |
Mar 23, 2001 |
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6409826 |
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09816015 |
Mar 23, 2001 |
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09057801 |
Apr 9, 1998 |
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6254672 |
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60041845 |
Apr 9, 1997 |
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Current U.S.
Class: |
117/13 ;
257/E21.321 |
Current CPC
Class: |
Y10T 117/1004 20150115;
C30B 29/06 20130101; C30B 15/203 20130101; H01L 21/3225 20130101;
C30B 15/00 20130101; C30B 15/14 20130101; C30B 33/00 20130101; Y10T
428/21 20150115; C30B 15/206 20130101 |
Class at
Publication: |
117/013 |
International
Class: |
C30B 015/00; C30B
021/06; C30B 027/02; C30B 028/10; C30B 030/04 |
Claims
What is claimed is:
1. A process for growing a single crystal silicon ingot in which
the ingot comprises a central axis, a seed-cone, an end-cone and a
constant diameter portion between the seed-cone and the end-cone
having a circumferential edge and a radius extending from the
central axis to the circumferential edge, the ingot being grown
from a silicon melt and then cooled from the solidification
temperature in accordance with the Czochralski method, the process
comprising controlling (i) a growth velocity, v, (ii) an average
axial temperature gradient, G.sub.0, during the growth of the
constant diameter portion of the crystal over the temperature range
from solidification to a temperature of no less than about
1325.degree. C., and (iii) the cooling rate of the crystal from the
solidification temperature to about 1,050.degree. C. to cause the
formation of an axially symmetrical segment which is substantially
free of agglomerated intrinsic point defects wherein the axially
symmetric region extends inwardly from the circumferential edge of
the ingot, has a width as measured from the circumferential edge
radially toward the central axis of the ingot which is at least
about three-tenths the length of the radius of the ingot, and has a
length as measured along the central axis of at least about
two-tenths the length of the constant diameter portion of the
ingot.
2. The process of claim 1 wherein the crystal has a nominal
diameter of about 150 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 10 hours.
3. The process of claim 1 wherein the crystal has a nominal
diameter of about 150 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 15 hours.
4. The process of claim 1 wherein the crystal has a nominal
diameter of about 200 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 10 hours.
5. The process of claim 1 wherein the crystal has a nominal
diameter of about 200 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 20 hours.
6. The process of claim 1 wherein the crystal has a nominal
diameter of greater than 200 mm and is cooled from the
solidification temperature to a temperature of at least about
1,050.degree. C. over a period of at least about 40 hours.
7. The process of claim 1 wherein the crystal has a nominal
diameter of greater than 200 mm and is cooled from the
solidification temperature to a temperature of at least about
1,050.degree. C. over a period of at least about 60 hours.
8. The process of claim 1 wherein the length of the axially
symmetric region is at least about three-tenths the length of the
constant diameter portion of the ingot.
9. The process of claim 8 wherein the crystal has a nominal
diameter of about 150 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 10 hours.
10. The process of claim 8 wherein the crystal has a nominal
diameter of about 150 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 15 hours.
11. The process of claim 8 wherein the crystal has a nominal
diameter of about 200 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 10 hours.
12. The process of claim 8 wherein the crystal has a nominal
diameter of about 200 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 20 hours.
13. The process of claim 8 wherein the crystal has a nominal
diameter of greater than 200 mm and is cooled from the
solidification temperature to a temperature of at least about
1,050.degree. C. over a period of at least about 40 hours.
14. The process of claim 8 wherein the crystal has a nominal
diameter of greater than 200 mm and is cooled from the
solidification temperature to a temperature of at least about
1,050.degree. C. over a period of at least about 60 hours.
15. The process of claim 1 wherein the growth velocity, v, and the
instantaneous axial temperature gradient, G.sub.0, are controlled
such that the ratio, v/G.sub.0, ranges in value from about 0.6 to
about 1.5 times the critical value of v/G.sub.0.
16. The process of claim 1 wherein the growth velocity, v, and the
instantaneous axial temperature gradient, G.sub.0, are controlled
such that the ratio v/G.sub.0 ranges in value from about 0.75 to
about 1 times the critical value of v/G.sub.0.
17. The process of claim 1 wherein the average axial temperature
gradient, G.sub.0, is controlled over the temperature range from
solidification to a temperature of no less than about 1350.degree.
C.
18. The process of claim 17 the crystal has a nominal diameter of
about 150 mm and is cooled from the solidification temperature to a
temperature of at least about 1,050.degree. C. over a period of at
least about 15 hours.
19. The process of claim 17 the crystal has a nominal diameter of
about 200 mm and is cooled from the solidification temperature to a
temperature of at least about 1,050.degree. C. over a period of at
least about 15 hours.
20. The process of claim 17 the crystal has a nominal diameter of
greater than 200 mm and is cooled from the solidification
temperature to a temperature of at least about 1,050.degree. C.
over a period of at least about 40 hours.
Description
REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation application based on U.S.
patent application Ser. No. 10/135,597, filed Apr. 30, 2002, which
is a continuation of U.S. patent application Ser. No. 09/816,015,
filed Mar. 3, 2001, now U.S. Pat. No. 6,409,826, which is a
continuation of U.S. patent application Ser. No. 09/057,801, filed
Apr. 9, 1998, now U.S. Pat. No. 6,254,672, which claims priority
from U.S. provisional application, U.S. Ser. No. 60/041,845, filed
on Apr. 9, 1997.
BACKGROUND OF THE INVENTION
[0002] The present invention generally relates to the preparation
of semiconductor grade single crystal silicon which is used in the
manufacture of electronic components. More particularly, the
present invention relates to single crystal silicon ingots and
wafers having an axially symmetric region which is devoid of
agglomerated intrinsic point defects, and a process for the
preparation thereof.
[0003] Single crystal silicon, which is the starting material for
most processes for the fabrication of semiconductor electronic
components, is commonly prepared by the so-called Czochralski
("Cz")method. In this method, polycrystalline silicon
("polysilicon") is charged to a crucible and melted, a seed crystal
is brought into contact with the molten silicon and a single
crystal is grown by slow extraction. After formation of a neck is
complete, the diameter of the crystal is enlarged by decreasing the
pulling rate and/or the melt temperature until the desired or
target diameter is reached. The cylindrical main body of the
crystal which has an approximately constant diameter is then grown
by controlling the pull rate and the melt temperature while
compensating for the decreasing melt level. Near the end of the
growth process but before the crucible is emptied of molten
silicon, the crystal diameter must be reduced gradually to form an
end-cone. Typically, the end-cone is formed by increasing the
crystal pull rate and heat supplied to the crucible. When the
diameter becomes small enough, the crystal is then separated from
the melt.
[0004] In recent years, it has been recognized that a number of
defects in single crystal silicon form in the crystal growth
chamber as the crystal cools after solidification. Such defects
arise, in part, due to the presence of an excess (i.e. a
concentration above the solubility limit) of intrinsic point
defects, which are known as vacancies and self-interstitials.
Silicon crystals grown from a melt are typically grown with an
excess of one or the other type of intrinsic point defect, either
crystal lattice vacancies ("V") or silicon self-interstitials
("I"). It has been suggested that the type and initial
concentration of these point defects in the silicon are determined
at the time of solidification and, if these concentrations reach a
level of critical supersaturation in the system and the mobility of
the point defects is sufficiently high, a reaction, or an
agglomeration event, will likely occur. Agglomerated intrinsic
point defects in silicon can severely impact the yield potential of
the material in the production of complex and highly integrated
circuits.
[0005] Vacancy-type defects are recognized to be the origin of such
observable crystal defects as D-defects, Flow Pattern Defects
(FPDs), Gate Oxide Integrity (GOI) Defects, Crystal Originated
Particle (COP) Defects, crystal originated Light Point Defects
(LPDs), as well as certain classes of bulk defects observed by
infrared light scattering techniques such as Scanning Infrared
Microscopy and Laser Scanning Tomography. Also present in regions
of excess vacancies are defects which act as the nuclei for ring
oxidation induced stacking faults (OISF). It is speculated that
this particular defect is a high temperature nucleated oxygen
agglomerate catalyzed by the presence of excess vacancies.
[0006] Defects relating to self-interstitials are less well
studied. They are generally regarded as being low densities of
interstitial-type dislocation loops or networks. Such defects are
not responsible for gate oxide integrity failures, an important
wafer performance criterion, but they are widely recognized to be
the cause of other types of device failures usually associated with
current leakage problems.
[0007] The density of such vacancy and self-interstitial
agglomerated defects in Czochralski silicon is
conventionally-within the range of about 1*10.sup.3/cm.sup.3 to
about 1*10.sup.7/cm.sup.3. While these values are relatively low,
agglomerated intrinsic point defects are of rapidly increasing
importance to device manufacturers and, in fact, are now seen as
yield-limiting factors in device fabrication processes.
[0008] To date, there generally exists three main approaches to
dealing with the problem of agglomerated intrinsic point defects.
The first approach includes methods which focus on crystal pulling
techniques in order to reduce the number density of agglomerated
intrinsic point defects in the ingot. This approach can be further
subdivided into those methods having crystal pulling conditions
which result in the formation of vacancy dominated material, and
those methods having crystal pulling conditions which result in the
formation of self-interstitial dominated material. For example, it
has been suggested that the number density of agglomerated defects
can be reduced by (i) controlling v/G.sub.0 to grow a crystal in
which crystal lattice vacancies are the dominant intrinsic point
defect, and (ii) influencing the nucleation rate of the
agglomerated defects by altering (generally, by slowing down) the
cooling rate of the silicon ingot from about 1100.degree. C. to
about 1050.degree. C. during the crystal pulling process. While
this approach reduces the number density of agglomerated defects,
it does not prevent their formation. As the requirements imposed by
device manufacturers become more and more stringent, the presence
of these defects will continue to become more of a problem.
[0009] Others have suggested reducing the pull rate, during the
growth of the body of the crystal, to a value less than about 0.4
mm/minute. This suggestion, however, is also not satisfactory
because such a slow pull rate leads to reduced throughput for each
crystal puller. More importantly, such pull rates lead to the
formation of single crystal silicon having a high concentration of
self-interstitials. This high concentration, in turn, leads to the
formation of agglomerated self-interstitial defects and all the
resulting problems associated with such defects.
[0010] A second approach to dealing with the problem of
agglomerated intrinsic point defects includes methods which focus
on the dissolution or annihilation of agglomerated intrinsic point
defects subsequent to their formation. Generally, this is achieved
by using high temperature heat treatments of the silicon in wafer
form. For example, Fusegawa et al. propose, in European Patent
Application 503,816 A1, growing the silicon ingot at a growth rate
in excess of 0.8 mm/minute, and heat treating the wafers which are
sliced from the ingot at a temperature in the range of 1150.degree.
C. to 1280.degree. C. to reduce the defect density in a thin region
near the wafer surface. The specific treatment needed will vary
depending upon the concentration and location of agglomerated
intrinsic point defects in the wafer. Different wafers cut from a
crystal which does not have a uniform axial concentration of such
defects may require different post-growth processing conditions.
Furthermore, such wafer heat treatments are relatively costly, have
the potential for introducing metallic impurities into the silicon
wafers, and are not universally effective for all types of
crystal-related defects.
[0011] A third approach to dealing with the problem of agglomerated
intrinsic point defects is the epitaxial deposition of a thin
crystalline layer of silicon on the surface of a single crystal
silicon wafer. This process provides a single crystal silicon wafer
having a surface which is substantially free of agglomerated
intrinsic point defects. Epitaxial deposition, however,
substantially increases the cost of the wafer.
[0012] In view of these developments, a need continues to exist for
a method of single crystal silicon preparation which acts to
prevent the formation of agglomerated intrinsic point defects by
suppressing the agglomeration reactions which produce them. Rather
than simply limiting the rate at which such defects form, or
attempting to annihilate some of the defects after they have
formed, a method which acts to suppress agglomeration reactions
would yield a silicon substrate that is substantially free of
agglomerated intrinsic point defects. Such a method would also
afford single crystal silicon wafers having epi-like yield
potential, in terms of the number of integrated circuits obtained
per wafer, without having the high costs associated with an
epitaxial process.
SUMMARY OF THE INVENTION
[0013] Among the objects of the present invention, therefore, is
the provision of single crystal silicon in ingot or wafer form
having an axially symmetric region of substantial radial width
which is substantially free of defects resulting from an
agglomeration of crystal lattice vacancies or silicon
self-interstitials; and the provision of a process for preparing a
single crystal silicon ingot in which the concentration of
vacancies and self-interstitials is controlled in order to prevent
an agglomeration of intrinsic point defects in an axially symmetric
segment of a constant diameter portion of the ingot, as the ingot
cools from the solidification temperature.
[0014] Briefly, therefore, the present invention is directed to a
process for growing a single crystal silicon ingot in which the
ingot comprises a central axis, a seed-cone, an end-cone and a
constant diameter portion between the seed-cone and the end-cone
having a circumferential edge and a radius extending from the
central axis to the circumferential edge. In the process, the ingot
is grown from a silicon melt and then cooled from the
solidification temperature in accordance with the Czochralski
method. In particular, the process comprises controlling (i) a
growth velocity, v, (ii) an average axial temperature gradient,
G.sub.0, during the growth of the constant diameter portion of the
crystal over the temperature range from solidification to a
temperature of no less than about 1325.degree. C., and (iii) the
cooling rate of the crystal from the solidification temperature to
about 1,050.degree. C. to cause the formation of an axially
symmetrical segment which is substantially free of agglomerated
intrinsic point defects wherein the axially symmetric region
extends inwardly from the circumferential edge of the ingot, has a
width as measured from the circumferential edge radially toward the
central axis of the ingot which is at least about three-tenths the
length of the radius of the ingot, and has a length as measured
along the central axis of at least about two-tenths the length of
the constant diameter portion of the ingot.
[0015] Other objects and features of this invention will be in part
apparent and in part pointed out hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a graph which shows an example of how the initial
concentration of self-interstitials, [I], and vacancies, [V],
changes with an increase in the value of the ratio v/G.sub.0, where
v is the growth rate and G.sub.0 is the average axial temperature
gradient.
[0017] FIG. 2 is a graph which shows an example of how
.DELTA.G.sub.I, the change in free energy required for the
formation of agglomerated interstitial defects, increases as the
temperature, T, decreases, for a given initial concentration of
self-interstitials, [I].
[0018] FIG. 3 is a graph which shows an example of how
.DELTA.G.sub.I, the change in free energy required for the
formation of agglomerated interstitial defects, decreases (as the
temperature, T, decreases) as a result of the suppression of the
concentration of self-interstitials, [I], through the means of
radial diffusion. The solid line depicts the case for no radial
diffusion whereas the dotted line includes the effect of
diffusion.
[0019] FIG. 4 is a graph which shows an example of how
.DELTA.G.sub.I, the change in free energy required for the
formation of agglomerated interstitial defects, is sufficiently
decreased (as the temperature, T, decreases), as a result of the
suppression of the concentration of self-interstitials, [I],
through the means of radial diffusion, such that an agglomeration
reaction is prevented. The solid line depicts the case for no
radial diffusion whereas the dotted line includes the effect of
diffusion.
[0020] FIG. 5 is a graph which shows an example of how the initial
concentration of self-interstitials, [I], and vacancies, [V], can
change along the radius of an ingot or wafer, as the value of the
ratio v/G.sub.0 decreases, due to an increase in the value of
G.sub.0. Note that at the V/I boundary a transition occurs from
vacancy dominated material to self-interstitial dominated
material.
[0021] FIG. 6 is a top plan view of a single crystal silicon ingot
or wafer showing regions of vacancy, V, and self-interstitial, I,
dominated materials respectively, as well as the V/I boundary that
exists between them.
[0022] FIG. 7a is a graph which shows an example of how the initial
concentration of vacancies or self-interstitials changes as a
function of radial position due to radial diffusion of
self-interstitials. Also shown is how such diffusion causes the
location of the V/I boundary to move closer to the center of the
ingot (as a result of the recombination of vacancies and
self-interstitials), as well as the concentration of
self-interstitials, [I], to be suppressed.
[0023] FIG. 7b is a graph of .DELTA.G.sub.I, as a function of
radial position which shows an example of how the suppression of
self-interstitial concentration, [I], (as depicted in FIG. 7a) is
sufficient to maintain .DELTA.G.sub.I, everywhere to a value which
is less than the critical value at which the silicon
self-interstitial reaction occurs.
[0024] FIG. 7c is a graph which shows another example of how the
initial concentration of vacancies or self-interstitials changes as
a function of radial position due to radial diffusion of
self-interstitials. Note that, in comparison to FIG. 7a, such
diffusion caused the location of the V/I boundary to be closer to
the center of the ingot (as a result of the recombination of
vacancies and self-interstitials), resulting in an increase in the
concentration of interstitials in the region outside of the V/I
boundary.
[0025] FIG. 7d is a graph of .DELTA.G.sub.I as a function of radial
position which shows an example of how the suppression of
self-interstitial concentration, [I], (as depicted in FIG. 7c) is
not sufficient to maintain .DELTA.G.sub.I everywhere to a value
which is less than the critical value at which the silicon
self-interstitial reaction occurs.
[0026] FIG. 7e is a graph which shows another example of how the
initial concentration of vacancies or self-interstitials changes as
a function of radial position due to radial diffusion of
self-interstitials. Note that, in comparison to FIG. 7a, increased
diffusion resulted in greater suppression the self-interstitial
concentration.
[0027] FIG. 7f is a graph of .DELTA.G.sub.I as a function of radial
position which shows an example of how greater suppression of the
self-interstitial concentration, [I], (as depicted in FIG. 7e)
results in a greater degree of suppression in .DELTA.G.sub.I, as
compared to FIG. 7b.
[0028] FIG. 7g is a graph which shows another example of how the
initial concentration of vacancies or self-interstitials changes as
a function of radial position due to radial diffusion of
self-interstitials. Note that, in comparison to FIG. 7c, increased
diffusion resulted in greater suppression the self-interstitial
concentration.
[0029] FIG. 7h is a graph of .DELTA.G.sub.I as a function of radial
position which shows an example of how greater suppression of the
self-interstitial concentration, [I], (as depicted in FIG. 7g)
results in a greater degree of suppression in .DELTA.G.sub.I, as
compared to FIG. 7d.
[0030] FIG. 7i is a graph which shows another example of how the
initial concentration of vacancies or self-interstitials changes as
a function of radial position due to radial diffusion of
self-interstitials. Note that in this example a sufficient quantity
of self-interstitials recombine with vacancies, such that there is
no longer a vacancy-dominated region.
[0031] FIG. 7j is a graph of .DELTA.G.sub.I as a function of radial
position which shows an example of how radial diffusion of
self-interstitials (as depicted in FIG. 7i) is sufficient to
maintain a suppression of agglomerated interstitial defects
everywhere along the crystal radius.
[0032] FIG. 8 is a longitudinal, cross-sectional view of a single
crystal silicon ingot showing, in detail, an axially symmetric
region of a constant diameter portion of the ingot.
[0033] FIG. 9 is a longitudinal, cross-sectional view of a segment
of a constant diameter portion of a single crystal silicon ingot,
showing in detail axial variations in the width of an axially
symmetric region.
[0034] FIG. 10 is a longitudinal, cross-sectional view of a segment
of a constant diameter portion of a single crystal silicon ingot
having axially symmetric region of a width which is less than the
radius of the ingot, showing in detail that this region further
contains a generally cylindrical region of vacancy dominated
material.
[0035] FIG. 11 is a latitudinal, cross-sectional view of the
axially symmetric region depicted in FIG. 10.
[0036] FIG. 12 is a longitudinal, cross-sectional view of a segment
of a constant diameter portion of a single crystal silicon ingot
having an axially symmetric region of a width which is equal to the
radius of the ingot, showing in detail that this region is a
generally cylindrical region of self-interstitial dominated
material which is substantially free of agglomerated intrinsic
point defects.
[0037] FIG. 13 is an image produced by a scan of the minority
carrier lifetime of an axial cut of the ingot following a series of
oxygen precipitation heat treatments, showing in detail a generally
cylindrical region of vacancy dominated material, a generally
annular shaped axially symmetric region of self-interstitial
dominated material, the V/I boundary present between them, and a
region of agglomerated interstitial defects.
[0038] FIG. 14 is a graph of pull rate (i.e. seed lift) as a
function of crystal length, showing how the pull rate is decreased
linearly over a portion of the length of the crystal.
[0039] FIG. 15 is an image produced by a scan of the minority
carrier lifetime of an axial cut of the ingot following a series of
oxygen precipitation heat treatments, as described in Example
1.
[0040] FIG. 16 is a graph of pull rate as a function of crystal
length for each of four single crystal silicon ingots, labeled 1-4
respectively, which are used to yield a curve, labeled v*(Z), as
described in Example 1.
[0041] FIG. 17 is a graph of the average axial temperature gradient
at the melt/solid interface, G.sub.0, as a function of radial
position, for two different cases as described in Example 2.
[0042] FIG. 18 is a graph of the initial concentration of
vacancies, [V], or self-interstitials, [I], as a function of radial
position, for two different cases as described Example 2.
[0043] FIG. 19 is a graph of temperature as a function of axial
position, showing the axial temperature profile in ingots for two
different cases as described in Example 3.
[0044] FIG. 20 is a graph of the self-interstitial concentrations
resulting from the two cooling conditions illustrated in FIG. 19
and as more fully described in Example 3.
[0045] FIG. 21 is an image produced by a scan of the minority
carrier lifetime of an axial cut of an entire ingot following a
series of oxygen precipitation heat treatments, as described in
Example 4.
[0046] FIG. 22 is a graph illustrating the position of the V/I
boundary as a function of the length of the single crystal silicon
ingot, as described in Example 5.
[0047] FIG. 23a is an image produced by a scan of the minority
carrier lifetime of an axial cut of a segment of an ingot, ranging
from about 100 mm to about 250 mm from the shoulder of the ingot,
following a series of oxygen precipitation heat treatments, as
described in Example 6.
[0048] FIG. 23b is an image produced by a scan of the minority
carrier lifetime of an axial cut of a segment of an ingot, ranging
from about 250 mm to about 400 mm from the shoulder of the ingot,
following a series of oxygen precipitation heat treatments, as
described in Example 6.
[0049] FIG. 24 is a graph illustrating the axial temperature
profile for an ingot in four different hot zone configurations.
[0050] FIG. 25 is a graph of the axial temperature gradient,
G.sub.0, at various axial positions for an ingot, as described in
Example 7.
[0051] FIG. 26 is a graph of the radial variations in the average
axial temperature gradient, G.sub.0, at various for an ingot, as
described in Example 7.
[0052] FIG. 27 is a graph illustrating the relationship between the
width of the axially symmetric region and the cooling rate, as
described in Example 7.
[0053] FIG. 28 is a photograph of an axial cut of a segment of an
ingot, ranging from about 235 mm to about 350 mm from the shoulder
of the ingot, following copper decoration and a defect-delineating
etch, described in Example 7.
[0054] FIG. 29 is a photograph of an axial cut of a segment of an
ingot, ranging from about 305 mm to about 460 mm from the shoulder
of the ingot, following copper decoration and a defect-delineating
etch, described in Example 7.
[0055] FIG. 30 is a photograph of an axial cut of a segment of an
ingot, ranging from about 140 mm to about 275 mm from the shoulder
of the ingot, following copper decoration and a defect-delineating
etch, described in Example 7.
[0056] FIG. 31 is a photograph of an axial cut of a segment of an
ingot, ranging from about 600 mm to about 730 mm from the shoulder
of the ingot, following copper decoration and a defect-delineating
etch, described in Example 7.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0057] Based upon experimental evidence to date, it appears that
the type and initial concentration of intrinsic point defects is
initially determined as the ingot cools from the temperature of
solidification (i.e., about 1410.degree. C.) to a temperature
greater than 1300.degree. C. (i.e., at least about 1325.degree. C.,
at least about 1350.degree. C. or even at least about 1375.degree.
C.). That is, the type and initial concentration of these defects
are controlled by the ratio v/G.sub.0, where v is the growth
velocity and G.sub.0 is the average axial temperature gradient over
this temperature range.
[0058] Referring to FIG. 1, for increasing values of v/G.sub.0, a
transition from decreasingly self-interstitial dominated growth to
increasingly vacancy dominated growth occurs near a critical value
of v/G.sub.0 which, based upon currently available information,
appears to be about 2.1.times.10.sup.-5 cm.sup.2/sK, where G.sub.0
is determined under conditions in which the axial temperature
gradient is constant within the temperature range defined above. At
this critical value, the concentrations of these intrinsic point
defects are at equilibrium.
[0059] As the value of v/G.sub.0 exceeds the critical value, the
concentration of vacancies increases. Likewise, as the value of
v/G.sub.0 falls below the critical value, the concentration of
self-interstitials increases. If these concentrations reach a level
of critical supersaturation in the system, and if the mobility of
the point defects is sufficiently high, a reaction, or an
agglomeration event, will likely occur. Agglomerated intrinsic
point defects in silicon can severely impact the yield potential of
the material in the production of complex and highly integrated
circuits.
[0060] In accordance with the present invention, it has been
discovered that the reaction in which silicon self-interstitial
atoms react to produce agglomerated interstitial defects can be
suppressed. Without being bound to any particular theory, it is
believed that the concentration of self-interstitials is controlled
during the growth and cooling of the crystal ingot in the process
of the present invention, such that the change in free energy of
the system never exceeds a critical value at which the
agglomeration reaction spontaneously occurs to produce agglomerated
interstitial defects.
[0061] In general, the change in system free energy available to
drive the reaction in which agglomerated interstitial defects are
formed from silicon self-interstitials in single crystal silicon is
governed by Equation (I): 1 G I = kT ln ( [ I ] [ I ] eq ) ( I
)
[0062] wherein
[0063] .DELTA.G.sub.I is the change in free energy,
[0064] k is the Boltzmann constant,
[0065] T is the temperature in K,
[0066] [I] is the concentration of self-interstitials at a point in
space and time in the single crystal silicon, and
[0067] [I].sup.eq is the equilibrium concentration of
self-interstitials at the same point in space and time at which [I]
occurs and at the temperature, T.
[0068] According to this equation, for a given concentration of
self-interstitials, [I], a decrease in the temperature, T,
generally results in an increase in .DELTA.G.sub.I due to a sharp
decrease in [I].sup.eq with temperature.
[0069] FIG. 2 schematically illustrates the change in
.DELTA.G.sub.I and the concentration of silicon self-interstitials
for an ingot which is cooled from the temperature of solidification
without simultaneously employing some means for suppression of the
concentration of silicon self-interstitials. As the ingot cools,
.DELTA.G.sub.I increases according to Equation (I), due to the
increasing supersaturation of [I], and the energy barrier for the
formation of agglomerated interstitial defects is approached. As
cooling continues, this energy barrier is eventually exceeded, at
which point a reaction occurs. This reaction results in the
formation of agglomerated interstitial defects and the concomitant
decrease in .DELTA.G.sub.I as the supersaturated system is relaxed,
i.e., as the concentration of [I] decreases.
[0070] The agglomeration of self-interstitials can be avoided as
the ingot cools from the temperature of solidification by
maintaining the free energy of the silicon self-interstitial system
at a value which is less than that at which an agglomeration
reaction will occur. In other words, the system can be controlled
so as to never become critically supersaturated. This can be
achieved by establishing an initial concentration of
self-interstitials (controlled by v/G.sub.0(r) as hereinafter
defined) which is sufficiently low such that critical
supersaturation is never achieved. However, in practice such
concentrations are difficult to achieve across an entire crystal
radius and, in general, therefore, critical supersaturation may be
avoided by suppressing the initial silicon self-interstitial
concentration subsequent to crystal solidification, i.e.,
subsequent to establishing the initial concentration determined by
v/G.sub.0(r).
[0071] FIGS. 3 and 4 schematically illustrate two possible effects
of suppressing [I] upon the increase in .DELTA.G.sub.I as the ingot
of FIG. 2 is cooled from the temperature of solidification. In FIG.
3, the suppression of [I] results in a decrease in the rate of
increase of .DELTA.G.sub.I but, in this case, the suppression is
insufficient to maintain .DELTA.G.sub.I everywhere at a value which
is less than the critical value at which the reaction occurs; as a
result, the suppression merely serves to reduce the temperature at
which the reaction occurs. In FIG. 4, an increased suppression of
[I] is sufficient to maintain .DELTA.G.sub.I everywhere to a value
which is less than the critical value at which the reaction occurs;
the suppression, therefore, inhibits the formation of defects.
[0072] Surprisingly, it has been found that due to the relatively
large mobility of self-interstitials, which is generally about
10.sup.-4 cm.sup.2/second, it is possible to effect the suppression
over relatively large distances, i.e. distances of about 5 cm to
about 10 cm or more, by the radial diffusion of self-interstitials
to sinks located at the crystal surface or to vacancy dominated
regions located within the crystal. Radial diffusion can be
effectively used to suppress the concentration of
self-interstitials, provided sufficient time is allowed for the
radial diffusion of the initial concentration of intrinsic point
defects. In general, the diffusion time will depend upon the radial
variation in the initial concentration of self-interstitials, with
lesser radial variations requiring shorter diffusion times.
[0073] Typically, the average axial temperature gradient, G.sub.0,
increases as a function of increasing radius for single crystal
silicon, which is grown according to the Czochralski method. This
means that the value of v/G.sub.0 is typically not singular across
the radius of an ingot. As a result of this variation, the type and
initial concentration of intrinsic point defects is not constant.
If the critical value of v/G.sub.0, denoted in FIGS. 5 and 6 as the
V/I boundary 2, is reached at some point along the radius 4 of the
ingot, the material will switch from being vacancy dominated to
self-interstitial dominated. In addition, the ingot will contain an
axially symmetric region of self-interstitial dominated material 6
(in which the initial concentration of silicon self-interstitial
atoms increases as a function of increasing radius), surrounding a
generally cylindrical region of vacancy dominated material 8 (in
which the initial concentration of vacancies decreases as a
function of increasing radius).
[0074] FIGS. 7a and 7b schematically illustrate the effect of
suppressing [I] upon the increase in .DELTA.G.sub.I as an ingot is
cooled from the temperature of solidification in accordance with
one embodiment of the present invention. When the ingot is pulled
in accordance with the Czochralski method, the ingot contains an
axially symmetric region of interstitial dominated material
extending from the edge of the ingot to the position along the
radius at which the V/I boundary occurs and a generally cylindrical
region of vacancy dominated material extending from the center of
the ingot to the position along the radius at which the V/I
boundary occurs. As the ingot is cooled from the temperature of
solidification, radial diffusion of interstitial atoms causes a
radially inward shift in the V/I boundary due to a recombination of
self-interstitials with vacancies and a significant suppression of
the self-interstitial concentration outside the V/I boundary. In
addition, radial diffusion of self-interstitials to the surface of
the crystal will occur as the crystal cools. The surface of the
crystal is capable of maintaining near equilibrium point defect
concentrations as the crystal cools. As a result, the suppression
of [I] is sufficient to maintain .DELTA.G.sub.I everywhere to a
value which is less than the critical value at which the silicon
self-interstitial reaction occurs.
[0075] Referring now to FIGS. 8 and 9, in the process of the
present invention a single crystal silicon ingot 10 is grown in
accordance with the Czochralski method. The silicon ingot comprises
a central axis 12, a seed-cone 14, an end-cone 16 and a constant
diameter portion 18 between the seed-cone and the end-cone. The
constant diameter portion has a circumferential edge 20 and a
radius 4 extending from the central axis to the circumferential
edge. The process comprises controlling the growth conditions,
including growth velocity, v, the average axial temperature
gradient, G.sub.0, and the cooling rate, to cause the formation of
an axially symmetric region 6 which, upon cooling of the ingot from
the solidification temperature, is substantially free of
agglomerated intrinsic point defects.
[0076] In one embodiment, the growth conditions are controlled to
maintain the V/I boundary 2 at a position which maximizes the
volume of the axially symmetric region 6 relative to the volume of
the constant diameter portion 18 of the ingot 10. In general,
therefore, in this embodiment it is preferred that the axially
symmetric region have a width 22 (as measured from the
circumferential edge radially toward the central axis of the ingot)
and a length 24 (as measured along the central axis of the ingot)
which equals the radius 4 and length 26, respectively, of the
constant diameter portion of the ingot. As a practical matter,
however, operating conditions and crystal puller hardware
constraints may dictate that the axially symmetric region occupy a
lesser proportion of the constant diameter portion of the ingot. In
general, therefore, the axially symmetric region in this embodiment
preferably has a width of at least about 30%, more preferably at
least about 40%, still more preferably at least about 60%, and most
preferably at least about 80% of the radius of the constant
diameter portion of the ingot. In addition, the axially symmetric
region extends over a length of at least about 20%, preferably at
least about 40%, more preferably at least about 60%, and still more
preferably at least about 80% of the length of the constant
diameter portion of the ingot.
[0077] Referring to FIG. 9, the width 22 of the axially symmetric
region 6 may have some variation along the length of the central
axis 12. For an axially symmetric region of a given length,
therefore, the width is determined by measuring the distance from
the circumferential edge 20 of the ingot 10 radially toward a point
which is farthest from the central axis. In other words, the width
22 is measured such that the minimum distance within the given
length 24 of the axially symmetric region 6 is determined.
[0078] Referring now to FIGS. 10 and 11, when the axially symmetric
region 6 of the constant diameter portion 18 of the ingot 10 has a
width 22 which is less than the radius 4 of the constant diameter
portion, the region is generally annular in shape. A generally
cylindrical region of vacancy dominated material 8, which is
centered about the central axis 12, is located radially inward of
the generally annular shaped segment. Referring to FIG. 12, it is
to be understood that when the width 22 of the axially symmetric
region 6 is equal to the radius 4 of the constant diameter portion
18, the region does not contain this vacancy dominated region;
rather, the axially symmetric region itself is generally
cylindrical and contains self-interstitial dominated material which
is substantially free of agglomerated intrinsic point defects.
[0079] While it is generally preferred that the crystal growth
conditions be controlled to maximize the width of the interstitial
dominated region, there may be limits for a given crystal puller
hot zone design. As the V/I boundary is moved closer to the central
crystal axis, provided the cooling conditions and G.sub.0(r) do not
change, where G.sub.0(r) is the radial variation of G.sub.0, the
minimum amount of radial diffusion required increases. In these
circumstances, there may be a minimum radius of the vacancy
dominated region which is required to suppress the formation of
agglomerated interstitial defects by radial diffusion.
[0080] FIGS. 7c and 7d schematically illustrate an example in which
the minimum radius of the vacancy dominated region is exceeded. In
this example, the cooling conditions and G.sub.0(r) are the same as
those employed for the crystal of FIGS. 7a and 7b in which there
was sufficient outdiffusion to avoid agglomerated interstitial
defects for the position of the V/I boundary illustrated. In FIGS.
7c and 7d, the position of the V/I boundary is moved closer to the
central axis (relative to FIGS. 7a and 7b) resulting in an increase
in the concentration of interstitials in the region outside of the
V/I boundary. As a result, more radial diffusion is required to
sufficiently suppress the interstitial concentration. If sufficient
outdiffusion is not achieved, the system .DELTA.G.sub.I will
increase beyond the critical value and the reaction which produces
agglomerated interstitial defects will occur, producing a region of
these defects in an annular region between the V/I boundary and the
edge of the crystal. The radius of the V/I boundary at which this
occurs is the minimum radius for the given hot zone. This minimum
radius is decreased if more radial diffusion of interstitials is
allowed.
[0081] FIGS. 7e, 7f, 7g and 7h illustrate the effect of an
increased radial outdiffusion on interstitial concentration
profiles and the rise of system .DELTA.G.sub.I for a crystal grown
with the same initial vacancy and interstitial concentration
profiles as the crystal exemplified in FIGS. 7a, 7b, 7c and 7d.
Increased radial diffusion of interstitials results in a greater
suppression of interstitial concentration, thus suppressing the
rise in the system .DELTA.G.sub.I to a greater degree than in FIGS.
7a, 7b, 7c and 7d. In this case the system .DELTA.G.sub.I is not
exceeded for the smaller radius of the V/I boundary.
[0082] FIGS. 7i and 7j illustrate an example in which sufficient
radial diffusion is allowed such that the minimum radius is reduced
to zero by insuring sufficient radial diffusion to achieve a
suppression of agglomerated interstitial defects everywhere along
the crystal radius.
[0083] In one embodiment of the process of the present invention,
the initial concentration of silicon self-interstitial atoms is
controlled in the axially symmetric, self-interstitial dominated
region of the ingot. Referring again to FIG. 1, in general, the
initial concentration of silicon self-interstitial atoms is
controlled by controlling the crystal growth velocity, v, and the
average axial temperature gradient, G.sub.0, such that the value of
the ratio v/G.sub.0 is relatively near the critical value of this
ratio, at which the V/I boundary occurs. In addition, the average
axial temperature gradient, G.sub.0, can be established such that
the variation of G.sub.0, i.e. G.sub.0(r), (and thus, v/G.sub.0(r))
as a function of the ingot radius is also controlled.
[0084] The growth velocity, v, and the average axial temperature
gradient, G.sub.0, (as previously defined) are typically controlled
such that the ratio v/G.sub.0 ranges in value from about 0.5 to
about 2.5 times the critical value of v/G.sub.0 (i.e., about
1.times.10.sup.-5 cm.sup.2/sK to about 5.times.10.sup.-5
cm.sup.2/sK based upon currently available information for the
critical value of v/G.sub.0). Preferably, the ratio v/G.sub.0 will
range in value from about 0.6 to about 1.5 times the critical value
of v/G.sub.0 (i.e., about 1.3.times.10.sup.-5 cm.sup.2/sK to about
3.times.10.sup.-5 cm.sup.2/sK based upon currently available
information for the critical value of v/G.sub.0). Most preferably,
the ratio v/G.sub.0 will range in value from about 0.75 to about 1
times the critical value of v/G.sub.0 (i.e., about
1.6.times.10.sup.-5 cm.sup.2/sK to about 2.1.times.10.sup.-5
cm.sup.2/sK based upon currently available information for the
critical value of v/G.sub.0). These ratios are achieved by
independent control of the growth velocity, v, and the average
axial temperature gradient, G.sub.0.
[0085] In general, control of the average axial temperature
gradient, G.sub.0, may be achieved primarily through the design of
the "hot zone" of the crystal puller, i.e. the graphite (or other
materials) that makes up the heater, insulation, heat and radiation
shields, among other things. Although the design particulars may
vary depending upon the make and model of the crystal puller, in
general, G.sub.0 may be controlled using any of the means currently
known in the art for controlling heat transfer at the melt/solid
interface, including reflectors, radiation shields, purge tubes,
light pipes, and heaters. In general, radial variations in G.sub.0
are minimized by positioning such an apparatus within about one
crystal diameter above the melt/solid interface. G.sub.0 can be
controlled further by adjusting the position of the apparatus
relative to the melt and crystal. This is accomplished either by
adjusting the position of the apparatus in the hot zone, or by
adjusting the position of the melt surface in the hot zone. In
addition, when a heater is employed, G.sub.0 may be further
controlled by adjusting the power supplied to the heater. Any, or
all, of these methods can be used during a batch Czochralski
process in which melt volume is depleted during the process.
[0086] It is generally preferred for some embodiments of the
present invention that the average axial temperature gradient,
G.sub.0, be relatively constant as a function of diameter of the
ingot. However, it should be noted that as improvements in hot zone
design allow for variations in G.sub.0 to be minimized, mechanical
issues associated with maintaining a constant growth rate become an
increasingly important factor. This is because the growth process
becomes much more sensitive to any variation in the pull rate,
which in turn directly effects the growth rate, v. In terms of
process control, this means that it is favorable to have values for
G.sub.0 which differ over the radius of the ingot. Significant
differences in the value of G.sub.0, however, can result in a large
concentration of self-interstitials generally increasing toward the
wafer edge and, thereby, increase the difficultly in avoiding the
formation of agglomerated intrinsic point defects.
[0087] In view of the foregoing, the control of G.sub.0 involves a
balance between minimizing radial variations in G.sub.0 and
maintaining favorable process control conditions. Typically,
therefore, the pull rate after about one diameter of the crystal
length will range from about 0.2 mm/minute to about 0.8 mm/minute.
Preferably, the pull rate will range from about 0.25 mm/minute to
about 0.6 mm/minute and, more preferably, from about 0.3 mm/minute
to about 0.5 mm/minute. It is to be noted that the pull rate is
dependent upon both the crystal diameter and crystal puller design.
The stated ranges are typical for 200 mm diameter crystals. In
general, the pull rate will decrease as the crystal diameter
increases. However, the crystal puller may be designed to allow
pull rates in excess of those stated here. As a result, most
preferably the crystal puller will be designed to enable the pull
rate to be as fast as possible while still allowing for the
formation of an axially symmetric region in accordance with the
present invention.
[0088] In a second and preferred embodiment, the amount of
self-interstitial diffusion is controlled by controlling the
cooling rate as the ingot is cooled from the solidification
temperature (about 1410.degree. C.) to the temperature at which
silicon self-interstitials become immobile, for commercially
practical purposes. Silicon self-interstitials appear to be
extremely mobile at temperatures near the solidification
temperature of silicon, i.e. about 1410.degree. C. This mobility,
however, decreases as the temperature of the single crystal silicon
ingot decreases. Generally, the diffusion rate of
self-interstitials slows such a considerable degree that they are
essentially immobile for commercially practical time periods at
temperatures less than about 700.degree. C., and perhaps at
temperatures as great as 800.degree. C., 900.degree. C.,
1000.degree. C., or even 1050.degree. C.
[0089] It is to be noted in this regard that, although the
temperature at which a self-interstitial agglomeration reaction
occurs may in theory vary over a wide range of temperatures, as a
practical matter this range appears to be relatively narrow for
conventional, Czochralski grown silicon. This is a consequence of
the relatively narrow range of initial self-interstitial
concentrations which are typically obtained in silicon grown
according to the Czochralski method. In general, therefore, a
self-interstitial agglomeration reaction may occur, if at all, at
temperatures within the range of about 1100.degree. C. to about
800.degree. C., and typically at a temperature of about
1050.degree. C.
[0090] Within the range of temperatures at which self-interstitials
appear to be mobile, and depending upon the temperature in the hot
zone, the cooling rate will typically range from about 0.1.degree.
C./minute to about 3.degree. C./minute. Preferably, the cooling
rate will range from about 0.1.degree. C./minute to about
1.5.degree. C./minute, more preferably from about 0.1.degree.
C./minute to about 1.degree. C./minute, and still more preferably
from about 0.1.degree. C./minute to about 0.5.degree. C./minute.
Stated another way, to maximize the width of the axially symmetric
region it is generally preferred that the silicon reside at a
temperature in excess of about 1050.degree. C. for a period of (i)
at least about 5 hours, preferably at least about 10 hours, and
more preferably at least about 15 hours for 150 mm nominal diameter
silicon crystals, (ii) at least about 5 hours, preferably at least
about 10 hours, more preferably at least about 20 hours, still more
preferably at least about 25 hours, and most preferably at least
about 30 hours for 200 mm nominal diameter silicon crystals, and
(iii) at least about 20 hours, preferably at least about 40 hours,
more preferably at least about 60 hours, and most preferably at
least about 75 hours for silicon crystals having a nominal diameter
greater than 200 mm. Referring to FIG. 24, as can be seen from
these axial temperature profiles for different hot zone
configurations, control of the cooling rate can be achieved by
using any means currently known in the art for minimizing heat
transfer in the hot zone, including the use of insulators, heaters,
radiation shields, and magnetic fields.
[0091] By controlling the cooling rate of the ingot within a range
of temperatures in which self-interstitials appear to be mobile,
the self-interstitials may be given more time to diffuse to sinks
located at the crystal surface, or to vacancy dominated regions,
where they may be annihilated. The concentration of such
interstitials may therefore be suppressed, which act to prevent an
agglomeration event from occurring. Utilizing the diffusivity of
interstitials by controlling the cooling rate acts to relax the
otherwise stringent v/G.sub.0 requirements that may be required in
order to obtain an axially symmetric region free of agglomerated
defects. Stated another way, as a result of the fact that the
cooling rate may be controlled in order to allow interstitials more
time to diffuse, a large range of v/G.sub.0 values, relative to the
critical value, are acceptable for purposes of obtaining an axially
symmetric region free of agglomerated defects.
[0092] To achieve such cooling rates over appreciable lengths of
the constant diameter portion of the crystal, consideration must
also be given to the growth process of the end-cone of the ingot,
as well as the treatment of the ingot once end-cone growth is
complete. Typically, upon completion of the growth of the constant
diameter portion of the ingot, the pull rate will be increased in
order to begin the tapering necessary to form the end-cone.
However, such an increase in pull rate will result in the lower
segment of the constant diameter portion cooling more quickly
within the temperature range in which interstitials are
sufficiently mobile, as discussed above. As a result, these
interstitials may not have sufficient time to diffuse to sinks to
be annihilated; that is, the concentration in this lower segment
may not be suppressed to a sufficient degree and agglomeration of
interstitial defects may result.
[0093] In order to prevent the formation of such defects from
occurring in this lower segment of the ingot, it is therefore
preferred that constant diameter portion of the ingot have a
uniform thermal history in accordance with the Czochralski method.
A uniform thermal history may be achieved by pulling the ingot from
the silicon melt at a relatively constant rate during the growth of
not only the constant diameter portion, but also during the growth
of the end-cone of the crystal and possibly subsequent to growth of
the end-cone. The relatively constant rate may be achieved, for
example, by (i) reducing the rates of rotation of the crucible and
crystal during the growth of the end-cone relative to the crucible
and crystal rotation rates during the growth of the constant
diameter portion of the crystal, and/or (ii) increasing the power
supplied to the heater used to heat the silicon melt during the
growth of the end-cone relative to the power conventionally
supplied during end-cone growth. These additional adjustments of
the process variables may occur either individually or in
combination.
[0094] When the growth of the end-cone is initiated, a pull rate
for the end-cone is established such that, any segment of the
constant diameter portion of the ingot which remains at a
temperature in excess of about 1050.degree. C. experiences the same
thermal history as other segment(s) of the constant diameter
portion of the ingot which contain an axially symmetric region free
of agglomerated intrinsic point defects which have already cooled
to a temperature of less than about 1050.degree. C.
[0095] As previously noted, a minimum radius of the vacancy
dominated region exists for which the suppression of agglomerated
interstitial defects may be achieved. The value of the minimum
radius depends on v/G.sub.0(r) and the cooling rate. As crystal
puller and hot zone designs will vary, the ranges presented above
for v/G.sub.0(r), pull rate, and cooling rate will also vary.
Likewise these conditions may vary along the length of a growing
crystal. Also as noted above, the width of the interstitial
dominated region free of agglomerated interstitial defects is
preferably maximized. Thus, it is desirable to maintain the width
of this region to a value which is as close as possible to, without
exceeding, the difference between the crystal radius and the
minimum radius of the vacancy dominated region along the length of
the growing crystal in a given crystal puller.
[0096] The optimum width of the axially symmetric region and the
required optimal crystal pulling rate profile for a given crystal
puller hot zone design may be determined empirically. Generally
speaking, this empirical approach involves first obtaining readily
available data on the axial temperature profile for an ingot grown
in a particular crystal puller, as well as the radial variations in
the average axial temperature gradient for an ingot grown in the
same puller. Collectively, this data is used to pull one or more
single crystal silicon-ingots, which are then analyzed for the
presence of agglomerated interstitial defects. In this way, an
optimum pull rate profile can be determined.
[0097] FIG. 13 is an image produced by a scan of the minority
carrier lifetime of an axial cut of a section of a 200 mm diameter
ingot following a series of oxygen precipitation heat-treatments
which reveal defect distribution patterns. It depicts an example in
which a near-optimum pull rate profile is employed for a given
crystal puller hot zone design. In this example, a transition
occurs from a v/G.sub.0(r) at which the maximum width of the
interstitial dominated region is exceeded (resulting in the
generation of regions of agglomerated interstitial defects 28) to
an optimum v/G.sub.0(r) at which the axially symmetric region has
the maximum width.
[0098] In addition to the radial variations in v/G.sub.0 resulting
from an increase in G.sub.0 over the radius of the ingot, v/G.sub.0
may also vary axially as a result of a change in v, or as a result
of natural variations in G.sub.0 due to the Czochralski process.
For a standard Czochralski process, v is altered as the pull rate
is adjusted throughout the growth cycle, in order to maintain the
ingot at a constant diameter. These adjustments, or changes, in the
pull rate in turn cause v/G.sub.0 to vary over the length of the
constant diameter portion of the ingot. In accordance with the
process of the present invention, the pull rate is therefore
controlled in order to maximize the width of the axially symmetric
region of the ingot. As a result, however, variations in the radius
of the ingot may occur. In order to ensure that the resulting ingot
has a constant diameter, the ingot is therefore preferably grown to
a diameter larger than that which is desired. The ingot is then
subjected to processes standard in the art to remove excess
material from the surface, thus ensuring that an ingot having a
constant diameter portion is obtained.
[0099] For an ingot prepared in accordance with the process of the
present invention and having a V/I boundary, i.e. an ingot
containing material which is vacancy dominated, experience has
shown that low oxygen content material, i.e., less than about 13
PPMA (parts per million atomic, ASTM standard F-121-83), is
preferred. More preferably, the single crystal silicon contains
less than about 12 PPMA oxygen, still more preferably less than
about 11 PPMA oxygen, and most preferably less than about 10 PPMA
oxygen. This is because, in medium to high oxygen contents wafers,
i.e., 14 PPMA to 18 PPMA, the formation of oxygen-induced stacking
faults and bands of enhanced oxygen clustering just inside the V/I
boundary becomes more pronounced. Each of these are a potential
source for problems in a given integrated circuit fabrication
process. However, it is to be noted that, when the axially
symmetric region has a width about equal to the radius of the
ingot, the oxygen content restriction is removed; this is because,
given that no vacancy type material is present, the formation of
such faults and clusters will not to occur.
[0100] The effects of enhanced oxygen clustering may be further
reduced by a number of methods, used singularly or in combination.
For example, oxygen precipitate nucleation centers typically form
in silicon which is annealed at a temperature in the range of about
350.degree. C. to about 750.degree. C. For some applications,
therefore, it may be preferred that the crystal be a "short"
crystal, that is, a crystal which has been grown in a Czochralski
process until the seed end has cooled from the melting point of
silicon (about 1410.degree. C.) to about 750.degree. C. after which
the ingot is rapidly cooled. In this way, the time spent in the
temperature range critical for nucleation center formation is kept
to a minimum and the oxygen precipitate nucleation centers have
inadequate time to form in the crystal puller.
[0101] Preferably, however, oxygen precipitate nucleation centers
formed during the growth of the single crystal are dissolved by
annealing the single crystal silicon. Provided they have not been
subjected to a stabilizing heat-treatment, oxygen precipitate
nucleation centers can be annealed out of silicon by rapidly
heating the silicon to a temperature of at least about 875.degree.
C., and preferably continuing to increase the temperature to at
least 1000.degree. C., at least 1100.degree. C., or more. By the
time the silicon reaches 1000.degree. C., substantially all (e.g.,
>99%) of such defects have annealed out. It is important that
the wafers be rapidly heated to these temperatures, i.e., that the
rate of temperature increase be at least about 10.degree. C. per
minute and more preferably at least about 50.degree. C. per minute.
Otherwise, some or all of the oxygen precipitate nucleation centers
may be stabilized by the heat-treatment. Equilibrium appears to be
reached in relatively short periods of time, i.e., on the order of
about 60 seconds or less. Accordingly, oxygen precipitate
nucleation centers in the single crystal silicon may be dissolved
by annealing it at a temperature of at least about 875.degree. C.,
preferably at least about 950.degree. C., and more preferably at
least about 1100.degree. C., for a period of at least about 5
seconds, and preferably at least about 10 minutes.
[0102] The dissolution may be carried out in a conventional furnace
or in a rapid thermal annealing (RTA) system. The rapid thermal
anneal of silicon may be carried out in any of a number of
commercially available rapid thermal annealing ("RTA") furnaces in
which wafers are individually heated by banks of high power lamps.
RTA furnaces are capable of rapidly heating a silicon wafer, e.g.,
they are capable of heating a wafer from room temperature to
1200.degree. C. in a few seconds. One such commercially available
RTA furnace is the model 610 furnace available from AG Associates
(Mountain View, Calif.). In addition, the dissolution may be
carried out on silicon ingots or on silicon wafers, preferably
wafers.
[0103] It is to be noted that wafers prepared in accordance with
the present invention are suitable for use as substrates upon which
an epitaxial layer may be deposited. Epitaxial deposition may be
performed by means common in the art.
[0104] Furthermore, it is also to be noted that wafers prepared in
accordance with the present invention are suitable for use in
combination with hydrogen or argon annealing treatments, such as
the treatments described in European Patent Application No. 503,816
A1.
[0105] Detection of Agglomerated Defects
[0106] Agglomerated defects may be detected by a number of
different techniques. For example, flow pattern defects, or
D-defects, are typically detected by preferentially etching the
single crystal silicon sample in a Secco etch solution for about 30
minutes, and then subjecting the sample to microscopic inspection.
(see, e.g., H. Yamagishi et al., Semicond. Sci. Technol. 7, A135
(1992)). Although standard for the detection of agglomerated
vacancy defects, this process may also be used to detect
agglomerated interstitial defects. When this technique is used,
such defects appear as large pits on the surface of the sample when
present.
[0107] Agglomerated defects may also be detected using laser
scattering techniques, such as laser scattering tomography, which
typically have a lower defect density detection limit that other
etching techniques.
[0108] Additionally, agglomerated intrinsic point defects may be
visually detect by decorating these defects with a metal capable of
diffusing into the single crystal silicon matrix upon the
application of heat. Specifically, single crystal silicon samples,
such as wafers, slugs or slabs, may be visually inspected for the
presence of such defects by first coating a surface of the sample
with a composition containing a metal capable of decorating these
defects, such as a concentrated solution of copper nitrate. The
coated sample is then heated to a temperature between about
900.degree. C. and about 1000.degree. C. for about 5 minutes to
about 15 minutes in order to diffuse the metal into the sample. The
heat treated sample is then cooled to room temperature, thus
causing the metal to become critically supersaturated and
precipitate at sites within the sample matrix at which defects are
present.
[0109] After cooling, the sample is first subjected to a non-defect
delineating etch, in order to remove surface residue and
precipitants, by treating the-sample with a bright etch solution
for about 8 to about 12 minutes. A typical bright etch solution
comprises about 55 percent nitric acid (70% solution by weight),
about 20 percent hydrofluoric acid (49% solution by weight), and
about 25 percent hydrochloric acid (concentrated solution).
[0110] The sample is then rinsed with deionized water and subjected
to a second etching step by immersing the sample in, or treating it
with, a Secco or Wright etch solution for about 35 to about 55
minutes. Typically, the sample will be etched using a Secco etch
solution comprising about a 1:2 ratio of 0.15 M potassium
dichromate and hydrofluoric acid (49% solution by weight). This
etching step acts to reveal, or delineate, agglomerated defects
which may be present.
[0111] Definitions
[0112] As used herein, the following phrases or terms shall have
the given meanings: "agglomerated intrinsic point defects" mean
defects caused (i) by the reaction in which vacancies agglomerate
to produce D-defects, flow pattern defects, gate oxide integrity
defects, crystal originated particle defects, crystal originated
light point defects, and other such vacancy related defects, or
(ii) by the reaction in which self-interstitials agglomerate to
produce dislocation loops and networks, and other such
self-interstitial related defects; "agglomerated interstitial
defects" shall mean agglomerated intrinsic point defects caused by
the reaction in which silicon self-interstitial atoms agglomerate;
"agglomerated vacancy defects" shall mean agglomerated vacancy
point defects caused by the reaction in which crystal lattice
vacancies agglomerate; "radius" means the distance measured from a
central axis to a circumferential edge of a wafer or ingot;
"substantially free of agglomerated intrinsic point defects" shall
mean a concentration of agglomerated defects which is less than the
detection limit of these defects, which is currently about 10.sup.3
defects/cm.sup.3; "V/I boundary" means the position along the
radius of an ingot or wafer at which the material changes from
vacancy dominated to self-interstitial dominated; and "vacancy
dominated" and "self-interstitial dominated" mean material in which
the intrinsic point defects are predominantly vacancies or
self-interstitials, respectively.
EXAMPLES
[0113] As the following examples illustrate, the present invention
affords a process for preparing a single crystal silicon ingot in
which, as the ingot cools from the solidification temperature in
accordance with the Czochralski method, the agglomeration of
intrinsic point defects is prevented within an axially symmetric
region of the constant. diameter portion of the ingot, from which
wafers may be sliced.
[0114] The following examples set forth one set of conditions that
may be used to achieve the desired result. Alternative approaches
exist for determining an optimum pull rate profile for a given
crystal puller. For example, rather than growing a series of ingots
at various pull rates, a single crystal could be grown at pull
rates which increase and decrease along the length of the crystal;
in this approach, agglomerated self-interstitial defects would be
caused to appear and disappear multiple times during growth of a
single crystal. Optimal pull rates could then be determined for a
number of different crystal positions. Accordingly, the following
examples should not be interpreted in a limiting sense.
Example 1
Optimization Procedure For a Crystal Puller Having a Pre-existing
Hot Zone Design
[0115] A first 200 mm single crystal silicon ingot was grown under
conditions in which the pull rate was ramped linearly from about
0.75 mm/min. to about 0.35 mm/min. over the length of the crystal.
FIG. 14 shows the pull rate as a function of crystal length. Taking
into account the pre-established axial temperature profile of a
growing 200 mm ingot in the crystal puller and the pre-established
radial variations in the average axial temperature gradient,
G.sub.0, i.e., the axial temperature gradient at the melt/solid
interface, these pull rates were selected to insure that ingot
would be vacancy dominated material from the center to the edge at
one end of the ingot and interstitial dominated material from the
center to the edge of the other end of the ingot. The grown ingot
was sliced longitudinally and analyzed to determine where the
formation of agglomerated interstitial defects begins.
[0116] FIG. 15 is an image produced by a scan of the minority
carrier lifetime of an axial cut of the ingot over a section
ranging from about 635 mm to about 760 mm from the shoulder of the
ingot following a series of oxygen precipitation heat-treatments
which reveal defect distribution patterns. At a crystal position of
about 680 mm, a band of agglomerated interstitial defects 28 can be
seen. This position corresponds to a critical pull rate of v*(680
mm)=0.33 mm/min. At this point, the width of the axially symmetric
region 6 (a region which is interstitial dominated material but
which lacks agglomerated interstitial defects) is at its maximum;
the width of the vacancy dominated region 8, R.sub.v*(680) is about
35 mm and the width of the axially symmetric region, R.sub.I*(680)
is about 65 mm.
[0117] A series of four single crystal silicon ingots were then
grown at steady state pull rates which were somewhat greater than
and somewhat less than the pull rate at which the maximum width of
the axially symmetric region of the first 200 mm ingot was
obtained. FIG. 16 shows the pull rate as a function of crystal
length for each of the four crystals, labeled, respectively, as
1-4. These four crystals were then analyzed to determine the axial
position (and corresponding pull rate) at which agglomerated
interstitial defects first appear or disappear. These four
empirically determined points (marked "*") are shown in FIG. 16.
Interpolation between and extrapolation from these points yielded a
curve, labeled v*(Z) in FIG. 16. This curve represents, to a first
approximation, the pull rate for 200 mm crystals as a function of
length in the crystal puller at which the axially symmetric region
is at its maximum width.
[0118] Growth of additional crystals at other pull rates and
further analysis of these crystals would further refine the
empirical definition of v*(Z).
Example 2
Reduction of Radial Variation in G.sub.0(r)
[0119] FIGS. 17 and 18 illustrate the improvement in quality that
can be achieved by reduction of the radial variation in the axial
temperature gradient at the melt/solid interface, G.sub.0(r). The
initial concentration (about 1 cm from the melt/solid interface) of
vacancies and interstitials are calculated for two cases with
different G.sub.0(r):(1) G.sub.0(r)=2.65+5.times.10.sup.-4r.sup.2
(K/mm) and (2) G.sub.0(r)=2.65+5.times.10.sup.-5r.sup.2 (K/mm). For
each case the pull rate was adjusted such that the boundary between
vacancy-rich silicon and interstitial-rich silicon is at a radius
of 3 cm. The pull rate used for case 1 and 2 were 0.4 and 0.35
mm/min, respectively. From FIG. 18 it is clear that the initial
concentration of interstitials in the interstitial-rich portion of
the crystal is dramatically reduced as the radial variation in the
initial axial temperature gradient is reduced. This leads to an
improvement in the quality of the material since it becomes easier
to avoid the formation of interstitial defect clusters due to
supersaturation of interstitials.
Example 3
Increased Out-diffusion Time For Interstitials
[0120] FIGS. 19 and 20 illustrate the improvement in quality that
can be achieved by increasing the time for out-diffusion of
interstitials. The concentration of interstitials is calculated for
two cases with differing axial temperature profiles in the crystal,
dT/dz. The axial temperature gradient at the melt/solid interface
is the same for both cases, so that the initial concentration
(about 1 cm from the melt/solid interface) of interstitials is the
same for both cases. In this example, the pull rate was adjusted
such that the entire crystal is interstitial-rich. The pull rate
was the same for both cases, 0.32 mm/min. The longer time for
interstitial out-diffusion in case 2 results in an overall
reduction of the interstitial concentration. This leads to an
improvement in the quality of the material since it becomes easier
to avoid the formation of interstitial defect clusters due to
supersaturation of interstitials.
Example 4
[0121] A 700 mm long, 150 mm diameter crystal was grown with a
varying pull rate. The pull rate varied nearly linearly from about
1.2 mm/min at the shoulder to about 0.4 mm/min at 430 mm from the
shoulder, and then nearly linearly back to about 0.65 mm/min at 700
mm from the shoulder. Under these conditions in this particular
crystal puller, the entire radius is grown under interstitial-rich
conditions over the length of crystal ranging from about 320 mm to
about 525 mm from the shoulder of the crystal. Referring now to
FIG. 21, at an axial position of about 525 mm and a pull rate of
about 0.47 mm/min, the crystal is free of agglomerated intrinsic
point defects clusters across the entire diameter. Stated another
way, there is one small section of the crystal in which the width
of the axially symmetric region, i.e., the region which is
substantially free of agglomerated defects, is equal to the radius
of the ingot.
Example 5
[0122] As described in Example 1, a series of single crystal
silicon ingots were grown at varying pull rates and then analyzed
to determine the axial position (and corresponding pull rate) at
which agglomerated interstitial defects first appeared or
disappeared. Interpolation between and extrapolation from these
points, plotted on a graph of pull rate v. axial position, yielded
a curve which represents, to a first approximation, the pull rate
for a 200 mm crystal as a function of length in the crystal puller
at which the axially symmetric region is at its maximum width.
Additional crystals were then grown at other pull rates and further
analysis of these crystals was used to refine this empirically
determined optimum pull rate profile.
[0123] Using this data and following this optimum pull rate
profile, a crystal of about 1000 mm in length and about 200 mm in
diameter was grown. Slices of the grown crystal, obtained from
various axial position, were then analyzed using oxygen
precipitation methods standard in the art in order to (i) determine
if agglomerated interstitial defects were formed, and (ii)
determine, as a function of the radius of the slice, the position
of the V/I boundary. In this way the presence of an axially
symmetric region was determined, as well as the width of this
region a function of crystal length or position.
[0124] The results obtained for axial positions ranging from about
200 mm to about 950 mm from the shoulder of the ingot are present
in the graph of FIG. 22. These results show that a pull rate
profile may be determined for the growth of a single crystal
silicon ingot such that the constant diameter portion of the ingot
may contain an axially symmetric region having a width, as measured
from the circumferential edge radially toward the central axis of
the ingot, which is at least about 40% the length of the radius of
the constant diameter portion. In addition, these results show that
this axially symmetric region may have a length, as measured along
the central axis of the ingot, which is about 75% of the length of
the constant diameter portion of the ingot.
Example 6
[0125] A single crystal silicon ingot have a length of about 1100
mm and a diameter of about 150 mm was grown with a decreasing pull
rate. The pull rate at the shoulder of the constant diameter
portion of the ingot was about 1 mm/min. The pull rate decreased
exponentially to about 0.4 mm/min., which corresponded to an axial
position of about 200 mm from the shoulder. The pull rate then
decreased linearly until a rate of about 0.3 mm/min. was reached
near the end of the constant diameter portion of the ingot.
[0126] Under these process conditions in this particular hot zone
configuration, the resulting ingot contains a region wherein the
axially symmetric region has a width which about equal to the
radius of the ingot. Referring now to FIGS. 23a and 23b, which are
images produced by a scan of the minority carrier lifetime of an
axial cut of a portion of the ingot following a series of oxygen
precipitation heat treatments, consecutive segments of the ingot,
ranging in axial position from about 100 mm to about 250 mm and
about 250 mm to about 400 mm are present. It can be seen from these
figures that a region exists within the ingot, ranging in axial
position from about 170 mm to about 290 mm from the shoulder, which
is free of agglomerated intrinsic point defects across the entire
diameter. Stated another way, a region is present within the ingot
wherein the width of the axially symmetric region, i.e., the region
which is substantially free of agglomerated interstitial defects,
is about equal to the radius of the ingot.
[0127] In addition, in a region ranging from an axially position
from about 125 mm to about 170 mm and from about 290 mm to greater
than 400 mm there are axially symmetric regions of interstitial
dominated material free of agglomerated intrinsic point defects
surrounding a generally cylindrical core of vacancy dominated
material which is also free of agglomerated intrinsic point
defects.
[0128] Finally, in a region ranging from an axially position from
about 100 mm to about 125 mm there is an axially symmetric region
of interstitial dominated material free of agglomerated defects
surrounding a generally cylindrical core of vacancy dominated
material. Within the vacancy dominated material, there is an
axially symmetric region which is free of agglomerated defects
surrounding a core containing agglomerated vacancy defects.
Example 7
Cooling Rate and Position of V/I Boundary
[0129] A series of single crystal silicon ingots (150 mm and 200 mm
nominal diameter), were grown in accordance with the Czochralski
method using different hot zone configurations, designed by means
common in the art, which affected the residence time of the silicon
at temperatures in excess of about 1050.degree. C. The pull rate
profile for each ingot was varied along the length of the ingot in
an attempt to create a transition from a region of agglomerated
vacancy point defects to a region of agglomerated interstitial
point defects.
[0130] Once grown, the ingots were cut longitudinally along the
central axis running parallel to the direction of growth, and then
further divided into sections which were each about 2 mm in
thickness. Using the copper decoration technique previously
described, one set of such longitudinal sections was then heated
and intentionally contaminated with copper, the heating conditions
being appropriate for the dissolution of a high concentration of
copper interstitials. Following this heat treatment, the samples
were then rapidly cooled, during which time the copper impurities
either outdiffused or precipitated at sites where oxide clusters or
agglomerated interstitial defects where present. After a standard
defect delineating etch, the samples were visually inspected for
the presence of precipitated impurities; those regions which were
free of such precipitated impurities corresponded to regions which
were free of agglomerated interstitial defects.
[0131] Another set of the longitudinal sections was subjected to a
series of oxygen precipitation heat treatments in order to cause
the nucleation and growth of new oxide clusters prior to carrier
lifetime mapping. Contrast bands in lifetime mapping were utilized
in order to determine and measure the shape of the instantaneous
melt/solid interface at various axial positions in each ingot.
Information on the shape of the melt/solid interface was then used,
as discussed further below, to estimate the absolute value of, and
the radial variation in, the average axial temperature gradient,
G.sub.0. This information was also used, in conjunction with the
pull rate, to estimate the radial variation in v/G.sub.0.
[0132] To more closely examine the effect growth conditions have on
the resulting quality of a single crystal silicon ingot, several
assumptions were made which, based on experimental evidence
available to date, are believed to be justified. First, in order to
simplify the treatment of thermal history in terms of the time
taken to cool to a temperature at which the agglomeration of
interstitial defects occurs, it was assumed that about 1050.degree.
C. is a reasonable approximation for the temperature at which the
agglomeration of silicon self-interstitials occurs. This
temperature appears to coincide with changes in agglomerated
interstitial defect density observed during experiments in which
different cooling rates were employed. Although, as noted above,
whether agglomeration occurs is also a factor of the concentration
of interstitials, it is believed that agglomeration will not occur
at temperatures above about 1050.degree. C. because, given the
range of interstitial concentrations typical for Czochralski-type
growth processes, it is reasonable to assume that the system will
not become critically supersaturated with interstitials above this
temperature. Stated another way, for concentrations of
interstitials which are typical for Czochralski-type growth
processes, it is reasonable to assume that the system will not
become critically supersaturated, and therefore an agglomeration
event will not occur, above a temperature of about 1050.degree.
C.
[0133] The second assumption that was made to parameterize the
effect of growth conditions on the quality of single crystal
silicon is that the temperature dependence of silicon
self-interstitial diffusivity is negligible. Stated another way, it
is assumed that self-interstitials diffuse at the same rate at all
temperatures between about 1400.degree. C. and about 1050.degree.
C. Understanding that about 1050.degree. C. is considered a
reasonable approximation for the temperature of agglomeration, the
essential point of this assumption is that the details of the
cooling curve from the melting point does not matter. The diffusion
distance depends only on the total time spent cooling from the
melting point to about 1050.degree. C.
[0134] Using the axial temperature profile data for each hot zone
design and the actual pull rate profile for a particular ingot, the
total cooling time from about 1400.degree. C. to about 1050.degree.
C. may be calculated. It should be noted that the rate at which the
temperature changes for each of the hot zones was reasonably
uniform. This uniformity means that any error in the selection of a
temperature of nucleation for agglomerated interstitial defects,
i.e. about 1050.degree. C., will arguably lead only to scaled
errors in the calculated cooling time.
[0135] In order to determine the radial extent of the vacancy
dominated region of the ingot (R.sub.vacancy) or alternatively the
width of the axially symmetric region, it was further assumed that
the radius of the vacancy dominated core, as determined by the
lifetime map, is equivalent to the point at solidification where
v/G.sub.0=v/G.sub.0 critical. Stated another way, the width of the
axially symmetric region was generally assumed to be based on the
position of the V/I boundary after cooling to room temperature.
This is pointed out because, as mentioned above, as the ingot cools
recombination of vacancies and silicon self-interstitials may
occur. When recombination does occur, the actual position of the
V/I boundary shifts inwardly toward the central axis of the ingot.
It is this final position which is being referred to here.
[0136] To simplify the calculation of G.sub.0, the average axial
temperature gradient in the crystal at the time of solidification,
the melt/solid interface shape was assumed to be the melting point
isotherm. The crystal surface temperatures were calculated using
finite element modeling (FEA) techniques and the details of the hot
zone design. The entire temperature field within the crystal, and
therefore G.sub.0, was deduced by solving Laplace's equation with
the proper boundary conditions, namely, the melting point along the
melt/solid interface and the FEA results for the surface
temperature along the axis of the crystal. The results obtained at
various axial positions from one of the ingots prepared and
evaluated are presented in FIG. 25.
[0137] To estimate the effect that radial variations in G.sub.0
have on the initial interstitial concentration, a radial position
R', that is, a position halfway between the V/I boundary and the
crystal surface, was assumed to be the furthest point a silicon
self-interstitial can be from a sink in the ingot, whether that
sink be in the vacancy dominated region or on the crystal surface.
By using the growth rate and the G.sub.0 data for the above ingot,
the difference between the calculated v/G.sub.0 at the position R'
and v/G.sub.0 at the V/I boundary (i.e., the critical v/G.sub.0
value) provides an indication of the radial variation in the
initial interstitial concentration, as well as the effect this has
on the ability for excess interstitials to reach a sink on the
crystal surface or in the vacancy dominated region.
[0138] For this particular data set, it appears there is no
systematic dependence of the quality of the crystal on the radial
variation in v/G.sub.0. As can be seen in FIG. 26, the axial
dependence in the ingot is minimal in this sample. The growth
conditions involved in this series of experiments represent a
fairly narrow range in the radial variation of G.sub.0. As a
result, this data set is too narrow to resolve a discernable
dependence of the quality (i.e., the presence of absence of a band
of agglomerated intrinsic point defects) on the radial variation of
G.sub.0.
[0139] As noted, samples of each ingot prepared were evaluated at
various axial positions for the present or absence of agglomerated
interstitial defects. For each axial position examined, a
correlation may be made between the quality of the sample and the
width of the axially symmetric region. Referring now to FIG. 27, a
graph may be prepared which compares the quality of the given
sample to the time the sample, at that particular axial position,
was allowed to cool from solidification to about 1050.degree. C. As
expected, this graph shows the width of the axially symmetric
region (i.e., R.sub.crystal-R.sub.vacancy) has a strong dependence
on the cooling history of the sample within this particular
temperature range. In order of the width of the axially symmetric
region to increase, the trend suggests that longer diffusion times,
or slower cooling rates, are needed.
[0140] Based on the data present in this graph, a best fit line may
be calculated which generally represents a transition in the
quality of the silicon from "good" (i.e., defect-free) to "bad"
(i.e., containing defects), as a function of the cooling time
allowed for a given ingot diameter within this particular
temperature range. This general relationship between the width of
the axially symmetric region and the cooling rate may be expressed
in terms of the following equation:
(R.sub.crystal-R.sub.transition).sup.2=D.sub.eff*t.sub.1050.degree.
C.
[0141] wherein
[0142] R.sub.crystal is the radius of the ingot,
[0143] R.sub.transition is the radius of the axially symmetric
region at an axial position in the sample were a transition occurs
in the interstitial dominated material from being defect-free to
containing defects, or vice versa,
[0144] D.sub.eff is a constant, about 9.3*10.sup.-4
cm.sup.2sec.sup.-1, which represents the average time and
temperature of interstitial diffusivity, and
[0145] t.sub.1050.degree. C. is the time required for the given
axial position of the sample to cool from solidification to about
1050.degree. C.
[0146] Referring again to FIG. 27, it can be seen that, for a given
ingot diameter, a cooling time may be estimated in order to obtain
an axially symmetric region of a desired diameter. For example, for
an ingot having a diameter of about 150 mm, an axially symmetric
region having a width about equal to the radius of the ingot may be
obtained if, between the temperature range of about 1410.degree. C.
and about 1050.degree. C., this particular portion of the ingot is
allowed to cool for about 10 to about 15 hours. Similarly, for an
ingot having a diameter of about 200 mm, an axially symmetric
region having a width about equal to the radius of the ingot may be
obtained if between this temperature range this particular portion
of the ingot is allowed to cool for about 25 to about 35 hours. If
this line is further extrapolated, cooling times of about 65 to
about 75 hours may be needed in order to obtain an axially
symmetric region having a width about equal to the radius of an
ingot having a diameter of about 300 mm. It is to be noted in this
regard that, as the diameter of the ingot increases, additional
cooling time is required due to the increase in distance that
interstitials must diffuse in order to reach sinks at the ingot
surface or the vacancy core.
[0147] Referring now to FIGS. 28, 29, 30 and 31, the effects of
increased cooling time for various ingots may be observed. Each of
these figures depicts a portion of a ingot having a nominal
diameter of 200 mm, with the cooling time from the temperature of
solidification to 1050 .degree. C. progressively increasing from
FIG. 28 to FIG. 31.
[0148] Referring to FIG. 28, a portion of an ingot, ranging in
axial position from about 235 mm to about 350 mm from the shoulder,
is shown. At an axial position of about 255 mm, the width of the
axially symmetric region free of agglomerated interstitial defects
is at a maximum, which is about 45% of the radius of the ingot.
Beyond this position, a transition occurs from a region which is
free of such defects, to a region in which such defects are
present.
[0149] Referring now to FIG. 29, a portion of an ingot, ranging in
axial position from about 305 mm to about 460 mm from the shoulder,
is shown. At an axial position of about 360 mm, the width of the
axially symmetric region free of agglomerated interstitial defects
is at a maximum, which is about 65% of the radius of the ingot.
Beyond this position, defect formation begins.
[0150] Referring now to FIG. 30, a portion of an ingot, ranging in
axial position from about 140 mm to about 275 mm from the shoulder,
is shown. At an axial position of about 210 mm, the width of the
axially symmetric region is about equal to the radius of the ingot;
that is, a small portion of the ingot within this range is free of
agglomerated intrinsic point defects.
[0151] Referring now to FIG. 31, a portion of an ingot, ranging in
axial position from about 600 mm to about 730 mm from the shoulder,
is shown. Over an axial position ranging from about 640 mm to about
665 mm, the width of the axially symmetric region is about equal to
the radius of the ingot. In addition, the length of the ingot
segment in which the width of the axially symmetric region is about
equal to the radius of the ingot is greater than what is observed
in connection with the ingot of FIG. 30.
[0152] When viewed in combination, therefore, FIGS. 28, 29, 30, and
31 demonstrate the effect of cooling time to 1050.degree. C. upon
the width and the length of the defect-free, axially symmetric
region. In general, the regions containing agglomerated
interstitial defects occurred as a result of a continued decrease
of the crystal pull rate leading to an initial interstitial
concentration which was too large to reduce for the cooling time of
that portion of the crystal. A greater length of the axially
symmetric region means a larger range of pull rates (i.e., initial
interstitial concentration) are available for the growth of such
defect-free material. Increasing the cooling time allows for
initially higher concentration of interstitials, as sufficient time
for radial diffusion may be achieved to suppress the concentration
below the critical concentration required for agglomeration of
interstitial defects. Stated in other words, for longer cooling
times, somewhat lower pull rates (and, therefore, higher initial
interstitial concentrations) will still lead to maximum axially
symmetric region 6. Therefore, longer cooling times lead to an
increase in the allowable pull rate variation about the condition
required for maximum axially symmetric region diameter and ease the
restrictions on process control. As a result, the process for an
axially symmetric region over large lengths of the ingot becomes
easier.
[0153] Referring again to FIG. 31, over an axial position ranging
from about 665 mm to greater than 730 mm from the shoulder of
crystal, a region of vacancy dominated material free of
agglomerated defects is present in which the width of the region is
equal to the radius of the ingot.
[0154] As can be seen from the above data, by means of controlling
the cooling rate, the concentration of self-interstitials may be
suppressed by allowing more time for interstitials to diffuse to
regions where they may be annihilated. As a result, the formation
of agglomerated interstitial defects is prevented within
significant portion of the single crystal silicon ingot.
[0155] In view of the above, it will be seen that the several
objects of the invention are achieved.
[0156] As various changes could be made in the above compositions
and processes without departing from the scope of the invention, it
is intended that all matter contained in the above description be
interpreted as illustrative and not in a limiting sense.
* * * * *