Title of Invention

METHOD AND APPARATUS FOR CRYSTAL GROWTH .

Abstract The invention generally relates to robust and efficient methods for producing sheets of crystalline material from a molten substance. In particular, the invention relates to a method for producing ribbons of crystalline silicon for use in solar cells. There is a need to produce these sheets of silicon having improved flatness, at a lower cost. A melt (302) is retained by capillary attachment to edge features (304) of a crucible (300). The boundary profile (808) of the resulting melt surface results in an effect which induces a ribbon (800) grown from the surface of the melt (302) to grow as a flat body. Further, the size of the melt (302) is substantially reduced by bringing these edges (304) close to the ribbon (80), thereby reducing the materials cost and electric power cost associated with the process.
Full Text METHOD AND APPARATUS FOR CRYSTAL GROWTH
Cross-reference to Related Applications
This application claims the benefits of and priority to U.S. provisional patent
application serial no. 60/419,769 filed on October 18,2002, the entire disclosures of which
are herein incorporated by reference.
Technical Field
The invention generally relates to growing crystalline or polycrystalline materials.
More particularly, the invention relates to methods and apparatus for growing crystalline or
polycrystalline silicon sheet material for use in making low dost solar cells.
Background of the Invention
Silicon sheet material or ribbon is particularly important in making low cost solar
cells. Continuous growth of silicon ribbon obviates the need for slicing of bulk produced
silicon. Methods for doing this are described in U.S. Patent Nos. 4,594,229; 4,627,887;
4,661,200; 4,689,109; 6,217,649, and IP No 199943 and IP A no. IN/PCT/2001/01144, the disclosures of which are
herein incorporated by reference in their entireties. In these patents, continuous silicon ribbon
growth is carried out by introducing two high temperature material strings up through a
crucible that includes a shallow layer of molten silicon. The strings serve to stabilize the
edges of the growing ribbon and the molten silicon freezes into a solid ribbon just above tfi6'
molten layer. The molten layer that forms between the strings and the growing ribbon is
defined by the meniscus of the molten silicon. U.S. Patent No.*^2t^-, 649 'and FP3B& 19394 2>
describe a method and apparatus for continuous replenishment of the feedstock material m a
continuous silicon ribbon.
In order to produce lower cost solar cells and hence expand large-scale electrical
applications of solar electricity, it is important to have lower cost and higher quality substrate
materials for making the solar cell. The current invention provides new and improved
methods and apparatus for growing silicon ribbons.
Summary of the Invention
The invention, in one embodiment, relates to a method and apparatus of growing or
pulling a crystalline or poly-crystalline sheet material or ribbon from a melt, wherein the melt
is retained by capillary attachment to edge features of a mesa crucible. In a preferred
embodiment, the invention is practiced with string ribbon or edge-stabilized ribbon wherein
stringS or fibers are used to stabilize the edges of the ribbon by capillary attachment This
method allows for the growth of ribbons, including continuous ribbons, directly from the
surface of the melt. The melt may be of infinite extent in directions perpendicular to the.,
growth direction of the ribbon, which is the location of the ribbon defined by the location of
the strings.
In one aspect, the invention provides a method of forming a crystalline ribbon. The
method includes providing a mesa crucible having a top surface and edges defining a
boundary of the top surface of the mesa crucible and forming a melt of a source material on
the top surface of the mesa crucible. The edges of the melt are retained by capillary
attachment to the edges of the mesa crucible. A crystalline ribbon is pulled from the melt. In
various embodiments, the pulling step includes placing a seed in the melt and pulling the seed
from the melt between a pair of strings positioned along the edges of the crystalline ribbon.
The melt is solidified between the pair of strings to form the crystalline ribbon, and the
crystalline ribbon is continuously pulled from the melt.
In one embodiment, at least a portion of a boundary profile of the melt is concave
downward prior to the pulling step. At least a portion of the boundary profile of the melt may
be concave downward outside the region of the crystalline ribbon as well. In one
embodiment, pulling the crystalline ribbon from the melt forms an inflection point in a cross-
sectional boundary profile of the melt. In some embodiments, the method includes forming a
substantial portion of the melt above the edges of the mesa crucible. The inflection point in at
least a portion of the cross-sectional boundary profile of the melt predisposes the crystalline
ribbon to grow substantially flat.
In various embodiments, more than one crystalline ribbon may be formed. The
method may include replenishing the source material on the top surface of the mesa crucible
for continuous crystalline ribbon growth. In some embodiments, the temperature of the mesa
crucible is controlled while forming the crystalline ribbon.
In another aspect, the invention provides an apparatus for forming a crystalline ribbon.
The apparatus includes a mesa crucible having edges defining a boundary of a top surface of
the mesa crucible. The mesa crucible retains edges of a melt by capillary attachment to the
edges of the mesa crucible. In some embodiments, a pair of strings is positioned along the
edges of the crystalline ribbon. The pair of strings define a region within which a crystalline
ribbon is formed. The mesa crucible may be graphite. In some embodiments, the edges of
the mesa crucible define a recessed top surface of the mesa crucible. The width of the mesa
crucible may be between about 15 mm and about 30 mm.
In yet another aspect, the invention provides a method of forming a crystalline ribbon.
The method includes providing a crucible having a top surface and edges defining a boundary
of the top surface of the crucible. A melt of a source material is formed on the top surface of
the crucible, and a crystalline ribbon is pulled from the melt. The crucible may be a mesa
crucible. In various embodiments, the melt has a boundary profile at least a portion of which
is concave downward. In some embodiments, pulling a crystalline ribbon from the melt
forms an inflection point in at least a portion of a cross-sectional boundary profile of the melt.
A substantial portion of the melt may be above the edges of the crucible.
In another aspect, the invention provides a method of controlling temperature of a
mesa crucible while forming a crystalline ribbon. The method includes positioning an
insulator comprising movable elements along a mesa crucible and disposing the mesa
crucible in a furnace. Controlled heat leaks are created by moving the moveable elements of
the insulator relative to the mesa crucible.
In still another aspect, the invention provides an apparatus for controlling temperature
of a mesa crucible while forming a crystalline ribbon. The apparatus includes a mesa crucible
disposed within a furnace, and an insulator comprising movable elements disposed along the
mesa crucible. The apparatus also includes means for moving the moveable elements of the
insulator relative to the mesa crucible to create controlled heats leaks.
In another aspect, the invention provides a method of replenishing a melt of a source
material on a mesa crucible. The method includes distributing a source material onto a mesa
crucible, thereby reducing the heat load required to melt the source material.
In one embodiment, the distributing step includes positioning a feeder at a distance from
a mesa crucible and moving a feeder in a first direction and a second direction along a mesa
crucible. The feeder is vibrated during motion in at least one of the first direction and the
second direction, such that a source material disposed within the feeder enters a melt on the
mesa crucible during such motion. The method may include melting the source material prior
to source material from a subsequent motion in the first direction reaching the melt. In
various embodiments, the distance from the mesa crucible is less than the width of the mesa
crucible.
In yet another aspect, the invention provides an apparatus for replenishing a melt of a
source material on a mesa crucible. The apparatus includes means for distributing a source
material onto a mesa crucible, thereby reducing the heat load required to melt the source
material.
Other aspects and advantages of the invention will become apparant from the
following drawings, detailed description, and claims, all of which illustrate the principles of
the invention, by way of example only.
Brief Descriptions of the accompanying Drawings
The advantages of the invention described above, together with farther advantages,
may be better understood by referring to the following description taken in conjunction with
the accompanying drawings. In the drawings, like reference characters generally refer to the
same parts throughout the different views. The drawings are not necessarily to scale,
emphasis instead generally being placed upon illustrating the principles of the invention.
FIG. 1 shows a flat ribbon growing perpendicularly from a free melt surface.
FIG. 2 shows the constant curvature approximation for the meniscus height.
FIG. 3 A-3E show how pulling at an angle to the melt results in changes to the height
of the interface.
FIG. 4 shows a 3-D view of a ribbon growing in a trough shape from the surface of a
melt.
FIG. 5 shows the relationship between the width of a ribbon, the radius of its trough
and the depth of the trough.
FIG. 6A shows a ribbon growing from the center of a narrow crucible.
FIG. 6B shows a ribbon growing displaced from the center of a narrow crucible.
FIG. 7 A-7C show exemplary embodiments of a melt pool on top of a mesa crucible.
FIG. 8 shows a ribbon growing from a mesa crucible.
FIG. 9A - 9D show four examples of the shape of the meniscus from growth of ribbon
from a mesa crucible.
FIG. 10 shows the growth of ribbon from a mesa crucible at a slight angle to the
vertical.
FIG. 11 shows a mesa crucible in isometric view.
FIG. 12 shows an isometric view of a graphite mesa crucible suitable for growth of
multiple ribbons.
FIG. 13 depicts an apparatus mat minimizes mechanical and thermal disturbance to a
system while replenishing a melt on a mesa crucible.
FIG. 14 depicts an apparatus for controlling the temperature of a mesa crucible.
Detailed Description of the Invention
The invention, in one embodiment, relates to a method of growing crystalline or poly-
crystalline sheet material. As used herein, the term crystalline refers to single crystal,
polycrystalline and semi-crystalline materials. In a preferred embodiment, the invention is
practiced with string ribbon or edge-stabilized ribbon wherein strings or fibers are used to
stabilize the edges of the ribbon by capillary attachment. This method allows for the growth
of ribbons, including continuous ribbons, directly from the surface of the melt. The melt may
be of infinite extent in directions perpendicular to the growth direction of the ribbon, which is
the location of the ribbon defined by the location of the strings. The invention is described in
reference to silicon, although other materials may be used. Other materials include
germanium, alloys of silicon, and alloys of germanium, and generally those materials that can
be produced by crystal growth from the liquid.
In an existing technique for crystal growth, a crucible with walls is used to contain the
molten material. When a large crucible is used, the walls of the crucible are far from the
growing ribbon, and thus the ribbon behaves as though it were growing from an inrmitely
large pool of melt. However, as the size of the crucible is reduced in order to reduce the cost
of the process, the walls of the crucible come closer to the growing ribbon, resulting in an
effect which causes the ribbon to grow in a non-flat or trough-like configuration. Such non-
flat growth can also result from other factors such as a direction of pulling or withdrawal of
the ribbon which is not precisely perpendicular to the surface of the melt.
The present invention, in one embodiment, provides a means alternative to a
conventional crucible for confining and defining the location of the melt from which the
string ribbon is grown. This means is comprised of defining the edges of the pool of melt by
capillary attachment to edge features of a wetted, or partially wetted material, with a
substantial portion of the volume of the melt positioned above these edges. The shape of the
surface of the melt on top of this "mesa" crucible without ribbon present is characteristically
concave downward, in contrast to the characteristically concave upward shape of the melt
surface in a conventional crucible with walls without ribbon present. Regions outside the
ribbon may also be coneave-downward as well. In addition, ai will be described in more
detail below, an inflection point is formed in a cross-section of the boundary profile of the
melt. This inflection point creates an effect that pro-disposes the ribbon to grow flat.
This effect is essentially the opposite of the effect that takes place because of the walls
of a conventional crucible, wherein the ribbon is predisposed to grow in a non-flat shape.
The predisposition of the ribbon to grow flat due to the concave down shape can also mitigate
factors such as off-axis pulling which tends to create a non-flat ribbon. As used herein, the
term "mesa" refers to a crucible which has the general form of a mesa - a generally flat top
surface and steep side walls. In the case of the mesa crucible, a surface is defined by the
edges of the mesa. In the preferred embodiment this surface is planar. In some embodiments,
the edges of the mesa are curved or undulating. Such curvature shapes the meniscus across
the width of the ribbon, may influence the nature of and propagation of grain, structure, and
stress in the ribbon. Note that the surface of the crucible itself can have a slight depression,
e.g., on the order of about 1 mm, as shown in FIG. 11. However, there is still a plane defined
by the top edges of the mesa. In the case of a slight depression, or raised edges, the raised
edges may have a land.
When growing crystal ribbons from a mesa crucible, the meniscus shape is self-
stabilizing, in that the growing ribbon moves back to the center in response to any
perturbation. Another advantage is that the base edge of the meniscus is reasonably far from
the interface between liquid and solid. This is helpful because particles can grow at the base
of the meniscus where it attaches to a crucible. During the growth of a crystalline ribbon in a
crucible made of graphite (the preferred practice), silicon carbide particles can grow, and if
any oxygen is present, silicon oxide particles can grow. These particles can disturb the
flatness and structure of the growing crystals and can even interrupt the growth. As the base
edge of the meniscus is reasonably from the growth interface when using a mesa, crucible, the
impact of such particles is minimized.
As a consequence of this concave down melt surface shape and its effect of leading to
the growth of flat ribbon, the edges of the melt pool may be brought into close proximity with
the ribbon and the size of the melt pool minimized. The small size of the melt pool, in
combination with the lack of need for walls of the crucible, leads to a dramatic reduction in
the amount of crucible material needed and in the expense associated with machining it into
shape. In addition, less power is needed to keep the melt pool and mesa crucible at the proper
temperature. These factors result in a reduction in manufacturing cost for the ribbon
produced. At the same time, the "flattening" effect induced by the shape of the melt surface,
results in flatter, higher quality ribbon. This improved ribbon flatness results in higher yields
in the subsequent handling of the ribbon. Another advantage of the mesa crucible approach is
that it can be scaled to the growth of multiple ribbons from a single crucible by further
elongating the crucible
With the conventional practice of string ribbon, the ribbon is grown from a pool of
melt that is large enough in horizontal extent that it appears to be infinite in extent to the
growing ribbon. In such a case, the meniscus that forms between the melt and the growth
interface has a shape which is determined by capillary and the height of this interface above
the free melt surface. The curvature is calculated using the Laplace Equation:

Where AP is the pressure difference across the interface between liquid and gas (the meniscus
surface), y is the surface tension of the liquid, and R1 aad R2 are the principal radii of
curvature of the meniscus.
The pressure difference across the interface between liquid and gas at a given point on
this interface can be found from the height of this point above the "free melt surface." At the
free melt surface, the curvature of the liquid/gas interface is zero, and there is ho pressure
drop across the liquid/gas interface. As the meniscus is above the free melt surface, the
pressure within it is lower than in the gas surrounding it. The pressure difference across the
interface between liquid and gas at a height y above the free melt surface is given by:

Where g is the acceleration of gravity, and p is the density of molten silicon.
FIG. 1 shows a flat ribbon 1 growing perpendicularly from a free melt surface 3. The
drawing is roughly to scale and the ribbon is 500 microns. This is thicker than a typical
ribbon, which might range from about 200-300 microns thick, but the higher value is used to
aid in illustration. Further, the concept can be used over a wide range, including the growth
of thin ribbon of 30-100 micron thickness as might be useful for lower cost, higher efficiency
and/or flexible solar cells. For the case of a flat ribbon, one of the principal radii of curvature
of equation (1) is infinite (for example, R2 is taken to be infinite). A numerical calculation
may be done using a technique such as the Finite Difference method, to calculate the
eurvature of the monisous at each point along its surface, and integrate the resulting shaps.
This calculation can be conveniently started at the interface 5 between solid and liquid silicon
using as an initial position the known equilibrium angle 7 between the solid and liquid silicon
at the growth interface of 11°. A guess is made as to where the interface is and the numerical
calculation produces the shape of the meniscus. The guess is refined until the proper
boundary condition Is met at the surface of the malt—that la that the menisoua reaches the
height of the pre-melt surface with a slope of 0 (horizontal). By using such a technique, it can
be found that at the center of a wide silicon ribbon, the height of the interface above the melt
surface is approximately 7.10 mm. FIG. 1 is a scale drawing of the shape of the meniscus
calculated by such a finite difference method.
Alternatively, an approximate method can be employed wherein the curvature of the
meniscus is assumed to be constant and have a value of R' (and not be a function of the
height above the free melt surface). A further approximation is made that the equilibrium
angle between solid and liquid silicon is 0°. Thus, the height of the meniscus will be equal to
the magnitude of the radius of curvature of the meniscus, R', as illustrated in FIG. 2 (again for
the case of a ribbon of thickness 500 microns). A final approximation takes the pressure drop
across the liquid/gas interface to be equal to that present at half the height of the meniscus.
Substituting a value of R'/2 for y in equation 2, we find that ?P=pgR'/2 (the pressure within
the meniscus is lower than outside the meniscus). Substituting this value of ?P and a value
of R'/2 for R1 in equation 1 we obtain:

Re-arranging equation 3 and using s to represent the meniscus height, we obtain:

Where a is defined as y/pg, for convenience.
Substituting values of y=0.7 N/m, p- 2300 kg/m3, and 9.8 m/sec2 for the acceleration
of gravity, g for molten silicon, we find that this approximate analysis produces a meniscus
height of 7.88 mm. Thus, the approximate analysis produces a result fairly close to that of the
numerical analysis. These two methods will be used with modification to describe the current
invention below.
During growth, string ribbon can be subject to some influences that lead to growth
conditions, which are less than ideal. For example, if the device pulling the ribbon (the
fuller") is located at a position slightly displaced from directly above the region where the
ibbon grows, the ribbon will be pulled at a slight angle with respect to the melt.
FIG. 3 shows a series of drawings depicting a close-up of the upper region of the
meniscus, the lower region of the growing ribbon and the interface between liquid and solid.
The drawings are approximately to scale for silicon ribbon growing from a melt surface. The
scale of the drawings is approximately 10:1 (the drawings are shown approximately 10x
larger than actual size) with a ribbon thickness of 0.5 mm. The position of the free melt
surface is shown in FIG. 3, although the scale of the drawing does not allow for the menisci to
be drawn all the way down to this level without many lines crossing over each other and
rendering the drawing difficult to interpret.
In FIG. 3a the ribbon 1 is shown growing vertically from the melt 3, much as: in FIG.
1. FIG. 3b shows the ribbon as it grows when pulled at an angle of 10 degrees from the
vertical, with consideration of only the physics governing the shape of the meniscus and its
interface to the growing ribbon. Note that 10 degrees is an extreme angle - much larger than
an angle that might be encountered due to a misaligned puller and is chosen for purposes of
illustration. Not considered in FIG. 3b are the heat transfer considerations discussed below.
These heat transfer considerations will force the ribbon to grow differently than shown in
FIG. 3b. Note that in FIG. 3b, the meniscus height 100 on the "underside" is higher than the
meniscus height 102 on the "topside." The origin of this difference in height is that on the
"underside" the meniscus must be allowed to reach a greater height in order to curve over and
meet the ribbon at the thermodynamically determined angle at the interface. The result is that
the interface between liquid and solid 104 is inclined at a steep angle with respect to the
ribbon. This situation can be modeled by the integration of the Laplace equation, as
discussed above, but this time the initial angle conditions have changed. Thus, if the ribbon
is being pulled at an angle of 10° from the vertical, the angle of the meniscus surface on the
"underside" meniscus is an angle of 1° from the vertical where the meniscus meets the ribbon
(the equilibrium solid-liquid angle of 11 degrees - the pulling angle of 10 degrees). The
angle of meniscus surface for the "topside" meniscus is an angle of 21° from the vertical
where the meniscus meets the ribbon (the equilibrium solid-liquid angle of 11 degrees + the
pulling angle of 10 degrees). The change in meniscus height due to pulling at an angle from
the vertical may be related to the pulling angle as follows:

Where As is the change in meniscus height from the value when pulling vertical ribbon, r is
the radius of curvature at the top of the meniscus and ? is the angle of pulling, measured from
the vertical. The radius of curvature of the meniscus at the top of the meniscus is found from
the Laplace equation at a height s above the free melt surface (r = y/pgs). In this approximate
result, the equilibrium angle of 11° between solid and liquid silicon is ignored. For the case
of pulling at 10 degrees from the vertical, equation 5 gives As = 0.78 mm. Thus, the
meniscus on the "underside" is higher by 0.78 mm than the meniscus for vertical ribbon,
while the meniscus on the "topside" is 0.78 mm lower than the meniscus for vertical ribbon.
A very similar result may be obtained using the finite difference numerical approach
described above, starting with different boundary conditions for the angle of meniscus at the
top of the meniscus.
However, as noted above, heat transfer considerations will not allow the situation of
FIG. 3b to persist. Note that FIG. 3c shows the direction and approximate magnitudes of the
heat fluxes up the ribbon and out its surfaces. Note that there is a significant flux from the
interface to the "topside" 106 of the ribbon (there must be, as the interface is, by definition, at
the melting point of silicon and the surface of the ribbon is cooler). However, since the two
sides of the ribbon lose approximately the same amount of heat to the environment (the
inclination of the ribbon may allow the topside to loose a bit more heat, but not much), there
is no way that the higher heat fluxes moving from the interface to the top surface of the
ribbon can be supported. As a consequence, the extra heat arriving at the top surface will
tend to melt the ribbon back, leading to an increase of the meniscus height at the topside of
the ribbon. An analogous argument leads to the conclusion that the ribbon on the underside
108 will be caused to temporarily grow faster than in the case of vertically pulled ribbon,
leading to a decrease in the height of the meniscus on the underside of the ribbon, as follows.
The inclination of the interface of FIG. 3b leads to heat being conducted toward the topside of
the ribbon. Less heat is directed toward the underside of the ribbon than for vertical growth
of ribbons. The ribbon will therefore solidify faster on this side and the meniscus height will
decrease. An this manner, thermal considerations force the meniscus to look more like that
shown in FIG. 3d where the meniscus heights are closer to equal on top and bottom sides, as
compared with the situation of FIG. 3c. However, the situation of FIG. 3d cannot persist as
the equilibrium requirements of the angle of the melt with respect to the growing solid is not
satisfied.
The meniscus of FIG. 3d forces the ribbon to grow at an angle different from that of
the pulling direction for a transient period. The direction of growth is determined by a chain
of effects. Laplace's equation determines the shape of the meniscus. Thermal conditions
influence the height of the meniscus. The height in combination with the shape determines
the angle of the meniscus at its top (where it meets the solid silicon). The liquid and solid
silicon must maintain the equilibrium angle of 11 degrees at the interface. The angle of the
ribbon surface is thus determined. FIG. 3e shows the pulling direction as a dotted line and
shows the ribbon 110 growing at less of an angle with respect to the vertical (less than the
angle of the pulling direction). As a consequence, the ribbon advances over the surface of the
melt in the direction of the arrow shown in FIG. 3e. This growth is toward the side of the
ribbon that has the higher meniscus. This is a general result applicable to situations other
than pulling a ribbon at an angle to the melt. The Tesult is that any situation that tends to
cause the meniscus on one side of the ribbon to be higher than the meniscus on the other side,
will result in the ribbon growing in a direction determined by the higher meniscus height.
In the case of the ribbon which is pulled at an angle to the melt, the center portion of
the ribbon is now caused to grow in the direction of the ribbon that has the higher meniscus,
however, the edges of the ribbon axe fixed in place by the location of the strings. As a
consequence, the ribbon 120 tends to grow in the shape of a trough from the melt 122 as
illustrated in FIG. 4. For small angles of pulling from the vertical, an equilibrium trough
shape will be reached and maintained. The equilibrium trough shape arises from the fact that
the troughing itself changes the meniscus height on the two sides of the ribbon. The
curvatures of the surface of the meniscus must at all points obey Laplace's equation, equation
1. As noted previously, in the case of a flat ribbon, one of the principal radii of curvature, R2,
is infinite in extent, and therefore drops out of Equation 1. However, when the ribbon grows
as a trough, the concave side of the ribbon (the topside in FIG. 4) now has a finite value of R2,
and it is of the same sign as R1. As a consequence, R1 must increase (in magnitude) from the
value it has for a flat ribbon. On the convex side of the ribbon, i.e., the underside in FIG. 4,
the troughing results in a finite value of R2, but one that is of sign opposite to R1, As a
consequence, R1 must assume a value smaller in magnitude than that for a flat ribbon. The
result is that the troughing results in a shorter meniscus on the convex side (corresponding to
the underside of a ribbon pulled at an angle to the melt), and a higher meniscus on the
concave side (corresponding to the topside of a ribbon pulled at an angle to the melt). The
changes in meniscus height due to troughing result in changes in menisoua height, which
counteract the effect of pulling at an angle.
The constant curvature approximate method used to arrive at the approximation of
Equations 3 and 4 can be extended to the case of troughing. In this derivation, the ribbon will
be examined in a snapshot where it is growing vertically from the surface of the melt, but
with a trough. While such a situation will not persist, the relationship between troughing and
meniscus height will be easiest to analyze for this case. As in the derivation of equation 3, R'
is the radius of curvature of the meniscus in the vertical plane. For convenience, R', which is
concave, is taken to be positive in value. In this case, R* is the radius of curvature of the
trough (which can assume both positive and negative values). Again, the pressure drop across
the meniscus is taken to be that at half the meniscus height. Further, under the approximation
that the liquid meets the solid with no discontinuity in angle, the meniscus height is equal to
R'. Thus,

The first term in equation 7 is the meniscus height for the case of vertical ribbon
growth. The second term is the change in meniscus height due to troughing. As noted above,
the concave side of the trough (positive value of R*) experiences an increase in meniscus
height, while the convex side experiences a decrease in meniscus height. This problem may
also be treated by the numerical method, and these predictions match the approximate results
of Equation 7 with good accuracy.
The growth of the ribbon in the shape of a trough is a response to pulling off-angle
and can lead to a stable growth situation for small angles of pulling. The chain of events
begins by pulling at an angle to the vertical. This alters the shape of meniscus. However,
thermal effects enter and cause the ribbon to grow in the direction of the higher meniscus.
The center of the ribbon can move, but the edges cannot, and a trough results. The troughing
in turn, alters the shape of the meniscus so as to lower the meniscus height on the underside
of the ribbon and raise it on the topside - the exact opposite of the effect of pulling an angle
from the vertical. If the angle of pulling is small (close to the vertical), the trough may be
sufficient to completely counteract the effect of pulling off-angle and result in meniscus
heights that are approximately equal on the two sides of the ribbon.
For a ribbon 124 of width w, we can relate the troughing radius, R*, to the depth of the
trough, 5, as illustrated in FIG. 5 (which shows a vertical view of a cross-section through the
ribbon) as follows:

As an example, if we pull a ribbon at an angle of 1° from the vertical, we can use
equation 5 to calculate that meniscus height on the topside of the ribbon will decrease by
approximately 78 microns, while that on the bottom of the ribbon will increase by
approximately 78 microns. The center of the ribbon will move in the direction of the higher
meniscus and the ribbon will grow in the shape of a trough. The trough will deepen until the
change in meniscus height predicted by equation 7 counteracts the change predicted by
equation 5. The result will be a trough of radius R* = 0.4 m. If the width of the ribbon is 60
mm, for example, the depth of the trough maybe calculated from equation 8 as 1.1 mm, a
significant deviation from flatness. The trough deepens as the ribbon width increases
according to equation 8.
In any real system, there will always be some errors or noises in the system resulting,
for example, in the ribbon being pulled at a slight angle with respect to the vertical. As can
be seen from this discussion, in order to compensate for such disturbances, the ribbon
responds by deviating from the desired condition of a flat ribbon. The tendency of the
troughing to cause a restoration of flatness may be thought of as something analogous to a
restoring force from a spring which is pulled from an equilibrium position. This "restoring"
tendency may be quantitatively expressed as the change in meniscus height for one side of the
ribbon that is induced by a displacement of the ribbon center from its flat position. Thus, for
the case of a trough-shaped growth of the ribbon, this restoring force may be expressed as:
Using equation 7 in the numerator and equation 8 in the denominator:

For Silicon ribbon of width w = 56 mm, the Restoring tendency from equation 9A has
a value of 0.08. Thus for a case where a 56 mm wide ribbon grows in a trough shape with a
depth of the trough of 1 mm, the meniscus height on the concave side will rise by 0.08 mm
and on the convex side will fall by 0.08 mm. Silicon ribbons with a width of 81.2mm may
also be grown with the result of a lower "Restoring Tendency."
When the ribbon begins to grow in a non-flat configuration, new disturbances may be
introduced. For example, when a trough-shaped ribbon enters the pulling device, may exert
bending moments on the ribbon resulting in further disturbances to the growth. The analysis
presented here is intended to provide understanding about the basic aspects of the process.
It should be understood that prior to the current invention, observations were made
relating the axis of the pulling of the ribbon to its tendency to grow in a trough-shaped curve.
However, neither the physical mechanisms, nor a quantitative understanding of this
phenomenon is known.
In a practical system, it is important to rmnimize the size of the crucible and the melt
pool. Minimizing this size reduces the consumable material used, such as the graphite used
for the crucible. Further, the time required to machine the crucible is reduced. Further, the
energy required to operate the furnace will be minimized.
The desirable case then is to make the crucible 130 narrower - that is to bring the
crucible walls 132 close to the plane of the ribbon 134 being pulled from the melt 136, as
illustrated in FIG. 6a. However, this arrangement leads to a situation where the ribbon is less
likely to stay flat, or, in the limit, cannot stay flat. FIG. 6b illustrates what happens as the
ribbon 134 moves off-center and therefore closer to one wall 138 than to the other wall 140.
The boundary condition that is maintained at the wall is that the wetting angle of the
meniscus to the wall of the crucible stays constant. In essence, the capillary attachment to the
walls of the crucible causes an upward force on the meniscus. As the ribbon gets closer to one
wall, this upward force has more effect on this side of the ribbon, resulting in a meniscus
height which is higher on that side. The numerical approach described above can be extended
to this case. For example, with a crucible that has a separation between walls of 60 mm, if
the ribbon moves off center by 1 mm, the difference in the height of the meniscus from one
side of the ribbon to the other will be approximately 15 microns. This effect may be
expressed with the same sort of ratio used to describe the stabilizing effect of the troughing
above. In this case (for reasons discussed below), it is a destabilizing effect which is
expressed as the ratio of the change of meniscus height for one side of the ribbon, to the
change in the distance of the ribbon to the crucible wall. Table I tabulates this destabilizing
effect for different crucible widths. The relevant dimension is the dimension between the
ribbon and the inside wall of the crucible.

The effect is a destabilizing effect because, as the ribbon moves toward a wall, the
meniscus height on the side of the ribbon closer to that wall increases, while the meniscus
height on the side of the ribbon further from the wall decreases. The heat transfer internal to
the ribbon causes the ribbon to grow in the direction of the higher meniscus, as described
above. This results in the continued growth of the ribbon towards the closer wall. This
growth will continue in this direction until reaching the wall. Thus we see that the growth in
the configuration of a trough-shaped ribbon is a stabilizing effect, while bringing a. crucible
wall closer to the plane of the ribbon is a destabilizing effect. Both effects are proportional to
the distance that the center of the ribbon moves from the original growth plane, at least for
small distances.
If these two effects are equal in magnitude, they will cancel each other, resulting in no
predisposition of the ribbon to grow either toward the wall of the crucible or flat. As noted
earlier, the Restoring Tendency for a 56mm wide ribbon is 0.08. Thus, for this ribbon width,
the effects will oanoel each other at a ribbon-crucible wall value of somewhere between 15
and 20 mm. If the destabilizing effect from a nearby crucible wall is larger, the ribbon will
tend to grow into a trough and continue to worsen in flatness. If the stabilizing effect from
troughing is larger (corresponding to crueible wall that is far away), the ribbon will, in
principle, grow flat. The destabilizing influence of the crucible walls may reduce the ability
of the ribbon to reject disturbances such as pulling off the vertical. A 81.2 mm ribbon is
grown from a wider crucible for stability.
In summary, bringing crucible walls in towards the plane of the ribbon, while having
the potential of improving the economics of the process, has the deleterious effect of leading
to ribbon which is less flat.
If the free melt surface (surface of the molten silicon with no ribbon present) is shaped
convex-up, it can be shown that a flatness stabilizing effect is produced on the growing
ribbon.
In one embodiment, this convex-up or concave-down shape is produced by using a
crucible with walls that are non-wetted by the molten silicon. A non-wetting wall is defined
as one which has a contact angle greater than 90°. By analogy, a pool of mercury contained in
a glass vessel will have a free liquid surface that is convex-up due to the fact that molten
mercury does not wet glass. The entire crucible may be made of such non-wetted material, or
small pieces of non-wetted material may be inserted into the wall of the crucible where the
melt wets the wall. For example in the case of molten silicon, Pyrolitic Boron Nitride can be
used as a non-wetted material.
In a preferred embodiment of this invention, the concave-down shape is created by
disposing all of or a portion of the melt above the wetted edges and allowing gravity in
combination with capillarity to determine the shape of the free melt surface. FIG. 7 shows a
cross-section through a flat sheet of wetted material 300 with a pool of molten silicon 302 on
top. The wetted sheet is an example of a "mesa" crucible that contains melt on its surface
without walls. Rather, the melt is contained by capillarity and is substantially above the
wetted edges of the mesa 304. This silicon wets the edges of the sheet while the shape of the
melt is determined by capillary action in the presence of the gravity field. The outside walls
of the mesa crucible can be vertical as shown in FIG. 7a or can be disposed at a different
angle as shown in FIG. 7b. A re-entrant angle such as that shown in FIG. 7b provides for
greater resistance to the melt spilling over the side of the crucible, but may be less convenient
for fabrication and somewhat less durable. A shallower angle is also possible, but is less
resistant to melt spilling than even the vertical side walls. The edge of the meniscus is stable
over a wide range of melt heights and melt volumes in part due to the ability of the meniscus
to assume a wide range of angles at the edge of the mesa, as is also shown in FIG. 9, which is
described below. FIG. 7c. shows a detail of one edge of the mesa crucible of FIG 7a. Note
that the edge need not be a perfectly abrupt angle, but rather can have a radius as in FIG. 7c.
In fact, in general the crucible will have such a radius, even if machined as a "hard" angle -
albeit at a small scale. Further, if it is found to be advantageous for manufacturing cost or
durability, a radius can be deliberately machined into the crucible. The spot or location of the
meniscus on the radius is determined by satisfying the wetting angle condition between the
liquid and the material of the crucible. In the case of FIG. 7c, this angle is approximately 30
degrees - a typical angle for a wetting system.
The Finite Difference numerical method of calculating the meniscus shape, els
described above, may be extended to calculate the shape of the free melt surface on this mesa
crucible in the absence of a ribbon. For a given width of mesa, a height of melt at the center
of the mesa is assumed. This height is measured from the plane defined by the edges of the
mesa. Next, a guess is made as to radius of curvature of the melt at the top center of the
mesa. The shape of the melt is then calculated. Iteration is performed until the melt passes
through the edge of the mesa. For example, if the radius at the top center is assumed too
large, the first iteration will produce a result where the melt surface passes over the edge. A
second iteration can then be done with a smaller radius of curvature. There is no need to
match a particular angle at the point where the meniscus intercepts the edge of the mesa as the
liquid can assume a wide range of angles at this point. Indeed, this is part of what makes the
mesa crucible stable over a wide range of conditions. This type of analysis can be repeated
with different widths of mesa and different heights of melt. The pool of melt atop the mesa
may be stable for a wide range of melt height. The limits to stability stem from the angle of
wetting of the liquid at the edge of the mesa. If the melt pool is too shallow, the angle of
wetting may be smaller than the equilibrium wetting angle on the mesa material, and the pool
may shrink in away from the edge. In FIGS. 11 and 12, both described below in more detail,
a recess is created in the crucible, which substantially reduces this danger. If the pool is too
deep, the wall of the pool will exceed the vertical at the edge, and be prone to instability.
Although in principal the wall of the pool may somewhat exceed the vertical at the edge (for
example, in FIG. 7b), this is not the preferred embodiment. For example, for a mesa with a
total width of 60 mm (30 mm from each face of the ribbon), the mesa will hold silicon until
the silicon reaches a height of approximately 8 mm above the plane defined by the edges of
the mesa. For a mesa with a total width of 20 mm, the mesa will hold silicon until the silicon
reaches a height of approximately 6mm above the plane defined by the edges of the mesa.
PIG. 7 shows the shape of the pool of molten silicon on a mesa of total width 20mm in a case
where the height of the melt at the center is 5 mm.
Table II shows tabulations for two mesa widths and two heights of melt. For each of
the four combinations, four calculations are tabulated. "Angle" refers to the angle of the
meniscus where it meets the edge of the mesa, measured from the horizontal. "Radius of
Curvature" refers to the radius of curvature of the melt at the top of the meniscus, which over
the center of the mesa. "Pressure" refers to the pressure difference across the meniscus at the
top of the meniscus and it is calculated from the Laplace equation using the radius; of
curvature of the meniscus at the top of the mesa. "Height, ambient Press" is explained below.
Table II. Four characteristics of a Melt on a Mesa with no Ribbon in Place For
Four Combinations of Melt Height and Mesa Width

FIG. 8 shows a growing ribbon 800 in place, growing from the pool on top of a mesa
crucible 802. Note that string introduction tubes 804, as described in U.S. Patent No.
4,627,887, have been inserted on the bottom of the mesa crucible to allow for the strings 806
defining the edges to come up through the bottom of the crucible. The Finite Difference
numerical method described above can be used to calculate the shape of the liquid meniscus
808 on top of the mesa. In this calculation, the width of the mesa is taken as a given. The
Finite Difference calculation starts from growth interface and propagates toward the edge of
the mesa. At the growth interface, the equilibrium angle between liquid and solid silicon of
11° is from the vertical is assumed. An initial guess is made as to the height of the interface
above the edge of the mesa.
A final piece of information is needed for this calculation - the pressure inside the
meniscus at some identified height. This is contrasted with the case of the infinite melt pool
where the surface far from the ribbon has no curvature and that the liquid immediately under
it is therefore at the same pressure as the ambient gas. A convenient approach is to take the
height in the liquid silicon at which the pressure is equal to the ambient pressure. As noted
above in the discussion of the mesa crucible with no ribbon growing, the curvature at the top
of the free melt surface results in an internal pressure in the liquid at the top of the melt pool.
Thus, the elevation in the melt pool at which the pressure is equal to the ambient may be
calculated by taking the height of the free melt surface outside the region in which the ribbon
is growing, and adding to it the height of silicon required to drop the pressure to ambient.
This height is tabulated in Table II and identified as "Height, Ambient Press." For example,
for the case of the mesa width of 20 mm and the melt height of 5 mm, the pressure difference
caused by the curvature at the top of the melt is 38.8 Pascal. This is equivalent to 1.7 mm of
silicon. Therefore, a column of liquid silicon 5+1.7 = 6.7 mm tall is required at ambient
pressure.
The numerical solution may now be iterated by choosing starting values of meniscus
height until the meniscus passes through the edge of the mesa. FIGs. 9A through 9D show
four different meniscus geometries corresponding to two widths of mesa and two different
melt heights. These plots show the meniscus height as a function of horizontal position from
the surface of the ribbon. Note that in each case, the surface of the meniscus has a point of
inflection, that is a point at which the curvature changes from concave down (near the mesa
edge) to concave down (near the growth interface). The inflection point is formed in the
cross-sectional boundary profile of the melt as the crystalline ribbon is pulled. In the plots of
Figure 9, the vertical axis represents a face of the ribbon (these plots assume that the ribbon is
very thin with respect to the width of the mesa). Accordingly, the intercept of the meniscus
profile with the vertical axis always has the equilibrium value of 11 degrees required by a
growing silicon crystal. The intercept of the profile with the horizontal axes occurs at the
edge of the mesa. Note that this angle is different for each of the four plots of Figure 9. The
attachment at the edge allows for a wide range of angles and this is what makes the liquid
pool atop the mesa stable over a range of wide melt heights.
Growth from the mesa results in flatess stabilizing affect. Any motion of the
ribbon away from the center of the mesa will result in a tendency to grow back toward the
center. As the ribbon is perturbed from the center of the mesa, one face of the ribbon will be
closer to one edge of the mesa while the other face will be further from its corresponding
edge. The face that is closer will have a lower equilibrium meniscus height while the face
that is further will have a higher equilibrium meniscus height. As before, thermal effects
coupled with the shape of the meniscus will cause the ribbon to grow in the direction defined
by the higher meniscus. Thus, growth from a mesa results in a restoring force causing ribbon
to grow flat and centered on the mesa.
We can attain a qualitative understanding for reduction of the equilibrium meniscus
height on a face that comes closer to an edge of the mesa by examining two factors. First, the
free surface of the melt on the top of the mesa drops as the edge is approached. Second the
angle of the free surface changes as the edge is approached. This angle can be considered as a
boundary condition where the meniscus joins the free melt surface and the effect of this
change in boundary condition is also to lower the equilibrium meniscus height.
The flatness stabilizing effect of the mesa may be calculated from the numerical
solution by calculating the equilibrium meniscus height for a ribbon centered on the mesa and
for a ribbon displaced slightly off center. Table HI tabulates the restoring force Circulated by
these means. The restoring force is defined in the same manner as above, the change in
meniscus height As for one side of the ribbon as the ribbon moves off-center, divided by the
distance that the ribbon has moved off-center.

Table III shows this restoring tendency for the same four cases as are tabulated in
Table II. The melt height is that height in a region of the melt on the mesa well away from
the growing ribbon. Two values are given in each cell; the "restoring tendency" as described
above and the height above the mesa at which the pressure in the melt is the same as the
ambient (this is the same as that in Table II).
Table HI. The Restoring tendency for four combinations of Mesa width and Height of
Melt

As may be seen from Table ID, the restoring tendency is a strong function of the width
of the mesa and increases as the width of the mesa decreases. In fact, the restoring tendency
due to the mesa can easily exceed the restoring force that the ribbon can induce by growing in
a trough. For example, the restoring tendency due to troughing of a 56 mm wide ribbon is
0.08. However, the restoring tendency for a 20 mm wide mesa is 0.159, for the case of the
Height of Melt above Mesa far from Ribbon = 5mm - as may be seen by reference to Table
III. Thus, the mesa induced restoring tendency is a very substantial effect leading to the
growth of a flatter ribbon. Further, the restoring tendency due to the mesa does not change
with the width of the ribbon. In contrast, the restoring tendency due to troughing decreases as
the ribbon width increases. Thus, the mesa may be used to grow flat, wide ribbon. Note,
that the restoring tendencies of the mesa and the troughing effect add, further promoting the
growth of flat ribbon.
As can be seen by reference to Table III, the "restoring tendency" varies with both the
width of the mesa and the "Height of Melt above Mesa far from ribbon." For convenience
the "Height of Melt above Mesa far from ribbon" will be referred to simply as the Melt
Height in this discussion. The restoring tendency increases as the width of the mesa is
decreased and as the malt height t increase. The choice of the width of the mesa is made as
a compromise. A narrower mesa will lead to a greater restoring tendency and better ribbon
flatness. A wider mesa will place the edges and any particles that accumulate at the edges
further from the growth interface. A suitable compromise is a mesa width of 20mm. The
choice of Melt Height is also made at a compromise. A higher value of Melt Height leads to
a higher restoring tendency. However, a lower value of Melt Height provides a greater
margin of safety against melt spilling over the edge of the mesa - especially in the went of
ribbon or ribbons detaching from the melt with the liquid content of their menisci
redistributing itself along the mesa. A suitable height above the melt is l-3mm. Note that
ribbon growth from a mesa is even stable with a melt height of zero (for example in the case
of a 20mm mesa, the restoring tendency for this condition is approximately 0.055). In fact,
for a 20mm mesa, the melt height can go slightly negative (a bit over 1mm) before the ribbon
becomes unstable from a flatness point of view. This provides a margin of safety during
manufacturing if temporary interruptions of melt replenishment are encountered during
growth (resulting in drawdown of the melt height). However, this is not the preferred mode
of operation as the flatness stabilization is much compromised. Even when the mesa is
practiced with a slightly negative melt height (below the plane defined by the edges of the
mesa), during growth, any detachment of ribbon will result in redistribution of the liquid in
the meniscus of the growing ribbon and in an increase in the melt height, typically to a
positive value.
Another concern centers on the volume of liquid contained in the meniscus and the
effect of a detachment of the meniscus. Periodically, the meniscus may detach from the
growing ribbon, and drop down. This might occur for example if the puller momentarily
pulls at a higher rate than desired. There is a significant volume of molten silicon in the
meniscus, which will fall into the melt pool on the top of the mesa. The mesa crucible must
be able to tolerate such a detachment and accommodate the additional molten silicon that
previously was contained within the meniscus. A necessary but not sufficient condition is
that the mesa be able to accommodate the volume of silicon after it has reached a quiescent
stage. This condition may be calculated by calculating the volume of the liquid under the
growing ribbon, and calculating the volume of the free melt surface after it redistributes itself.
For example, the volume of silicon contained in the meniscus of a ribbon growing from a 20
mm wide mesa in the case where the height of the melt far from the ribbon is 2 mm (the case
of FIG. 9a) is 0.76 cubic centimeters per centimeter of ribbon width. However, a 20 mm
wide mesa can hold molten silicon at a height of up to approximately 6mm, at which point the
volume of melt is approximately 0.95 cubic centimeters per centimeter of mesa length. Thus,
if the meniscus of the ribbon collapses, the mesa can accommodate the additional melt. This
calculation is for the extreme case where the ribbon extends for the full length of the mesa.
Ordinarily there will be additional mesa area outside of the growing ribbon that will be able to
further accommodate the melt from a collapsed meniscus. Note, that if the melt height during
growth is too close to the maximum height that a mesa can hold, the melt from a collapsed
meniscus will result in spillage over the side of the mesa.
A more stringent condition results from the fact that when the meniscus collapses as
the detached meniscus falls, the fluid within it, acquires some velocity. The momentum of
this fluid then initiates a small wave and this wave propagates to the edge of the mesa. The
mesa must be able to absorb the shock of this wave without spilling over the edge.
Experimentally it has been found that the mesa is quite resistant to this wave shock. This
may be due to the fact that the meniscus does not detach across the full width of the ribbon
simultaneously, but rather the detachment begins at one point and propagates across the
ribbon width. The impact of this detachment is thus minimized.
Another use of the flatness stabilization aspect of the mesa is to mitigate or
completely compensate for the destabilizing effect of inadvertently pulling the ribbon at an
angle from the vertical. As noted earlier, pulling at an angle from the vertical from an large
melt pool will result in an increase in the meniscus height on the underside of the ribbon,
which will in turn result in the center of the ribbon growing toward the direction of the pull
and a trough shaped ribbon, as shown in FIG. 4. On a large melt pool, this trough will only
stabilize once it has reached a significant depth and the difference in curvatures of the two
sides of the ribbon is enough to equalize the meniscus heights on the two sides of the ribbon.
However, the mesa brings a strong stabilizing factor into play as the motion of the center of
the ribbon away from the center of the mesa will raise the meniscus on the side of the ribbon
closer to the center and lower it on the side further from the center. This effect quickly leads
to the equalization of the meniscus heights on the two sides of the ribbon with only a small
deviation of the center of the ribbon from the flat condition.
However, it is possible to achieve an even higher degree of flatness in the presence of
unintentional pulling at an angle from the melt. If, the ribbon is pulled at an angle to the melt
and the position of the strings is defined by passage through an orifice, the position of growth
of the ribbon will be displaced from the center of the mesa. As noted above, such
displacement from the center of the mesa will cause the meniscus on the side of the ribbon
closer to the center of the mesa to be higher than the meniscus on the side of the ribbon facing
away from the center. However, the angle of pulling will cause the meniscus on the side
closer to the center to be lower than the meniscus on the side of the ribbon facing away from
the center. If the proper geometry i» selected, these two effects can cancel each other
resulting in the growth of flat ribbon at an angle to the melt.
FIG. 10 shows a ribbon 810 being pulled from a mesa 802 at a slight angle to the
vertical and defines three relevant geometric parameters. The angle of the ribbon with respect
to the vertical is denoted as ft The vertical height between the growth interface and the point
of confinement of the strings 1000 is denoted as H. The third parameter is the horizontal
distance between the center of the mesa and the center of the ribbon, denoted as Distance off
Center. These are related as follows:

We may relate the angle of pulling to the difference in meniscus height, As in a
manner analogous to that used in Equation 5

where r is the radius of curvature at the top of the meniscus and where b is vertical distance
between the growth interface and the height at which the pressure inside the melt is the same
as that in the ambient outside the liquid.
Pulling at an angle from the vertical produces a destabilizing tendency - a tendency to
grow into a trough. For the case where the angle of pulling can be related to the Distance off
Center by equation 11, this destabilizing tendency can be defined by analogy to equation 10
as:

However, the mesa itself has a Restoring Tendency as summarized in Table HI. In a
case where the Destabilizing Tendency of equation 14 is equal in magnitude to the Restoring
Tendency of the mesa, the net result will be that the ribbon can grow at an angle to the melt
and remain flat. Thus, an unintentional pulling at an angle to the melt will not create a trough
shaped ribbon.
FIG. 11 shows an isometric view of a graphite mesa crucible. The width of the mesa
crucible shown in FIG. 11 is 20 mm. In operation, silicon overfills this crucible to a typical
height of approximately 1 -2 mm above the plane defined by edges 1200. The small
depression in the top 1202 allow for the silicon to stay wetted to the edge even when the
silicon level drops to the level of the edges 1200. While a flat top mesa might de-wet as the
melt height drops, this crucible will not de-wet. The strings come up through string
introduction holes 1204 and the ribbon is puled between these. The 1/4-circle cutouts in the
bottom of the crucible 1208 accept heaters, one on each side of the crucible. Support ears
1210 support the crucible.
As described above, the mesa crucible has a top surface and edges defining a
boundary of the top surface of the mesa crucible. The melt is formed on the top surface of the
mesa crucible, and the edges of the melt are retained by capillary attachment to the edges of
the mesa crucible. The crystalline ribbon is then pulled from the melt. In various
embodiments, a seed is placed in the melt, and the seed is pulled from the melt between a pair
of strings positioned along the edges of the crystalline ribbon. The melt solidifies between
the pair of strings to form the crystalline ribbon. The crystalline ribbon may be continuously
pulled from the melt continuously.
The mesa crucible and all concepts described herein can be applied to the concurrent
growth of multiple ribbons from a single furnace. In this case, the length of the crucible is
increased, while maintaining the approximate width and height. FIG. 12 shows an isometric
view of a graphite mesa crucible suitable for the growth of multiple ribbons, e.g., four
ribbons, each of width 81.3 mm with 38.1 mm between adjacent ribbons. The mesa is
defined by edges 1304 and is 20 mm wide and 650 mm long. The corners of the mesa 1314
are rounded to increase the durability of the crucible and to reduce the possibility of a leak
occurring at a sharp corner. There are eight string introduction holes 1302, two for each
ribbon. The left-most two are annotated in the isometric drawing - corresponding to the left-
most ribbon. The crucible is supported in the furnace by tangs 1300. Section 1 shows a cross
section through the region between strings. This same cross section applies to the majority of
the crucible. Section 2 shows a cross section through one of the eight holes used to introduce
string. Recess 1306, running the full length of the mesa is approximately 1mm deep and
helps to guarantee that the silicon does not de-wet from the edge. This recess also provides a
bit extra depth of liquid silicon to receive the granular silicon feedstock during replenishment.
Note from section 1 and section 2 that the edge of the mesa need not be a "knife-edge" but
rather can have a small flat 1318 (or land) to improve its durability, as evident in "Detail A"
which is an enlargement of the top-left corner of Section 1. Typically foia fiat might be
0.25mm wide. Melt replenishment is accomplished by dropping granular material, in the
general area marked as 1316 and generally the material will be distributed over a length of
crucible of approximately 100mm in the manner previously described. The melt
replenishment can be performed at one end of the crucible - as is contemplated in FIG. 12.
Alternatively, the melt replenishment can be performed in the center of the crucible with two
or more ribbons grown to either side. Further, the mesa need not be of a uniform width along
its entire length, although uniform width does present economy of manufacture, m particular,
the region in which melt replenishment is performed may be a different width, especially
wider than the region where ribbon is grown. In this manner, the melt-in of feedstock will be
facilitated without decreasing the "Restoring Tendency" of the mesa crucible. Cutouts 1310
are to accommodate heaters. Suitable grades of graphite for use in the growth of silicon
ribbon include grade G530 available from Tokai and grade R6650 available from. SGL
Carbon. It will be appreciated that with a long crucible it is particularly important to have the
crucible be level so that the melt will be uniformly distributed along the length and not
accumulate substantially at one end. Typically the crucible is leveled to at least within 0.2
mm along the length.
The new charge of silicon is continually dropped in the region 1205. Typically,
silicon "BB's" made by fluidized bed using the thermal decomposition of silane and provided
by MEMC Corp. are used to replenish the melt continuously as ribbon is grown, although
other granular forms of silicon feedstock can be used as known in the art. For "BB's", the
size ranges from approximately 1 mm diameter to 4 mm diameter. FIG. 13 shows a technique
to accomplish melt replenishment of a mesa crucible which minimizing the mechanical (e.g.
splashing) and thermal disturbance to the system. A mesa crucible 1404 is held inside a metal
furnace shell 1402 (the crucible is held by the end tangs, one of which is evident in FIG. 13,
however, the supports which mate to these tangs are not shown). Insulation 1400 helps to
maintain the crucible at temperature. The granular silicon feedstock will be transported into
the furnace through a horizontally, or substantially horizontal tube 1406. The tube may be
made of any refractory material, however, quartz tubing is a good choice for silicon crystal
growth as it is chemically compatible, economical and has good resistance to thermal shock.
Further, the elastic modulus of quartz is reasonably high and this is helpful as explained
below. Tube 1406 is clamped into trough 1414 by clamp 1426. The frough/tube assembly is
support atop a vibratory feeder 1416, such as those know in the art. The vibratory feeder can
move left and right (it sits on a track, not shown, and is moved by a motor as is well know in
the art). FIG. 13a shows the tube/trough/vibrator assembly in its right-most position -
furthest out of the furnace. FIG. 13b shows the tube/trough/vibrator assembly in its left-most
position - furthest into the furnace. Hopper 1410 is used to hold the granular feedstock,
which is metered out by device 1412. Suitable methods of metering are described in U.S.
Patent Nos. 6,090,199 and 6,217,649. Enclosure 1418 serves to isolate the contents from air
and the enclosed volume is in communication with the interior of the furnace through the hole
in 1402 through which tube 1406 penetrates. FIGS. 13a and 13b show the hardware without
silicon present, for clarity.
FIGS. 13c and 13d illustrate the cycle used in feeding. As the tube is withdrawn from
the furnace, the vibrator is turned on and the silicon feedstock is transported down the tube
and falls on the melt 1420, which is atop the mesa crucible. The tube and trough move
together as a single unit and the tube must be stiff enough and light enough to enforce motion
as a rigid body so that the vibration will be well defined (hence the advantage of high elastic
modulus). The stiffness to weight ratio of the tube can also be increase by increasing its
outside diameter, while keeping the wall thickness the same. However, the tube cannot be
made so large that the heat loss down the tube and out the furnace is too large or that the
location of the BB's when they drop is too ill-defined to guarantee that they land on the mesa.
For a 20mm wide mesa a quartz tube of 14mm OD and 1mm wall has been found suitable.
The amplitude of vibration is adjusted so that the traverse time for a BB down the tube is on
the same order as the time required to complete one in/out cycle, or not too much greater that
this time. As long as this time is kept fairly short, the tube acts to rapidly transport the
metered feedstock in and back-ups and tube plugging are prevented. At the same time, too
high a vibrational amplitude will result in BB's "spraying" out the end and therefore not
necessarily dropping where intended. The drop from tube to melt is small, typically 10 mm.
This helps to avoid splashing and waves on the liquid silicon. It also minimizes the chance
that a BB will bounce off another BB present in the melt and fall outside the mesa. The
possibility of BB's falling on top of one another is further reduced by withdrawing the tube
during feeding so that, for the most part, BB'a fall on clear melt Distributing the BB's along
a length of the mesa also has the advantage of distributing the cooling effect of the BB's and
thereby reducing the overheat needed in the crucible to melt the BB's. Note that the silicon
BB's float on the surface of the melt due to the lower density of solid silicon (as compared to
liquid silicon) and due to surface tension effects. The BB's may tend to stay in the center of
the mesa or go to the edges, depending on factors including the ourvature of the melt and the
direction of the temperature gradient across the mesa.
In FIG. 13d, the tube/trough/vibrator is moving back, into the furnace with the vibrator
turned off and no silicon feeding in order to minimize the number of collisions of BB's. A
few BB's which remain on the melt are almost fully melted at this stage and will be fully
melted by the time the tube returns to the right-most position on the next withdrawal stroke.
Typically, the feeding/withdrawal stroke takes approximately 5 seconds, the return stroke
approximately 1 second and the traverse time of BB's in the tube approximately 10 sec. The
metering device and hopper may be fixed and need not move with the tube/trough/'vibrator.
In this case, the trough needs to be long enough to capture the BB's over the fall travel.
It will be appreciated that temperature control must be adequately maintained along
the length of the crucible so as to grow ribbon of predictable and consistent thickness. This
may be accomplished by positioning small, 'dimming" heater elements along the length of
the crucible, beneath the crucible. Such methods are well known in the art of high
temperature furnace design. Another method of mamtaining the temperature along the length
of the crucible is to provide for movable portions of the insulation pack, which surrounds the
crucible, as shown in FIG. 14. Mesa crucible 1500 is disposed within furnace shell 1504 and
held in place by supports not shown. Lower insulation pack 1506 is shown, however, all
insulation above the crucible has been omitted for clarity. Replenishment feed tube 1502 is
shown for reference. The lower insulation pack 1506 has openings 1520. Three movable
insulation elements are shown an these elements are actuated from outside the furnace by rods
1508,1510, and 1512. Examining the rightmost movable element, we see a piece of
insulation 1514 on top of a plate 1516 attached to actuation rod 1512. Plate 1516 acts to
support the fragile insulation. The rightmost movable element is in the fully-up position,
resulting in minimum heat loss. The center element is fully down, resulting in maximum heat
loss. The left-most element is in the middle, resulting in an intermediate heat loss condition.
The rods may be positioned by hand or by an electro-mechanical positioning mechanism as is
known in the art, the latter allowing for automated control of position.
The invention, as described herein, has been described in the context of String
Ribbon. However, the mesa crucible can be applied to other methods of growing ribbons and
sheets including, but not limited to, the Edge-defined Film-fed Growth (EFG) of crystalline
ribbons. For example, a mesa crucible shaped in a closed polygon may be used to grow such
a hollow, polygonal crystalline ribbon.
While the invention has been particularly shown and described with reference to
specific illustrative embodiments, various changes in form and detail may be made without
departing from the spirit and scope of the invention as defined by the appended claims.
We claim:
1. A method of forming a crystalline ribbon, the method comprising:
providing a crucible (300) having a top surface and edges (304) defining a boundary of
the top surface of the crucible (300);
forming a melt of a source material (302) on the top surface of the crucible (300);
supporting substantially all of the melt (302) both laterally and vertically by
capillary attachment to the top surface and edges (304) of the crucible (300); and
pulling a crystalline ribbon (800) from the melt (302).
2. The method as claimed in claim 1, wherein the pulling step comprises:
placing a seed in the melt (302);
pulling the seed from the melt (302) between a pair of strings (806) positioned along
the edges (304) of the crystalline ribbon (800) thereby solidifying the melt (302)
between the pair of strings (806) to form the crystalline ribbon (800); and
continuously pulling the crystalline ribbon (800) from the melt (302).
3. The method as claimed in claim 1, wherein at least a portion of a boundary profile (808) of
the melt (302) is concave downward prior to the pulling step.
4. The method as claimed in claim 1, wherein at least a portion of a boundary profile (808) of
the melt (302) is concave downward outside the region of the crystalline ribbon (800).
5. The method as claimed in claim 1, wherein pulling the crystalline ribbon (800) from the
melt (302) forms an inflection point in a cross-sectional boundary profile (808) of the melt
(302).
6. The method as claimed in claim 1 further comprising forming a substantial portion of the
melt (302) above the edges (304) of the crucible (300).
7. The method as claimed in claim 1 further comprising forming more than one crystalline
ribbon (800).
8. The method as claimed in claim 5, wherein the inflection point in at least a portion of the
cross-sectional boundary profile (808) of the melt (302) predisposes the crystalline ribbon
(800) to grow substantially flat.
9. The method as claimed in claim 1 further comprising replenishing the source material
(302) on the top surface of the crucible (300) for continuous crystalline ribbon (800)
growth.
10. The method as claimed in claim 1 further comprising controlling the temperature of the
crucible (300) while forming the crystalline ribbon (800).
11. An apparatus for forming a crystalline ribbon, comprising:
a crucible including:
a crucible body (300) having a top surface and edges (304) defining a boundary of
the top surface of the crucible (300), wherein the top surface is capable of supporting
substantially all of a melt of a source material (302) both laterally and vertically by
capillary attachment to the top surface and edges (304) of the crucible (300); and
a pair of side walls extending downward from opposing edges (304) of the top surface.
12. The apparatus as claimed in claim 11 further comprising:
a pair of apertures (804) defined in the crucible body (300), extending from the top
surface to a bottom surface through the crucible body (300); and
a pair of strings (806) extending through the pair of apertures (804), each string (806)
positioned along an edge of the crystalline ribbon (800), the pair of strings (806) defining a
region within which a crystalline ribbon (800) is formed.
13. The apparatus as claimed in claim 11, wherein the crucible (300) adapts a portion of a
boundary profile (808) of the melt (302) to be concave downward prior to forming a
crystalline ribbon (800).
14. The apparatus as claimed in claim 11, wherein the crucible (300) adapts a portion of a
boundary profile (808) of the melt (302) to be concave downward outside the region of a
crystalline ribbon (800).
15. The apparatus as claimed in claim 11, wherein pulling a crystalline ribbon (800) from the
melt forms an inflection point in a cross-sectional boundary profile (808) of the melt (302).
16. The apparatus as claimed in claim 11, wherein a substantial portion of the melt (302) is
above the edges (304) of the crucible (300).
17. The apparatus as claimed in claim 12, further comprising:
more than one pair of apertures (1302) defined in the crucible body (300), each pair
extending from the top surface to a bottom surface through the crucible body (300); and a
pair of strings (806) extending through each pair of apertures (1302), each string (800)
positioned along an edge of a discrete crystalline ribbon (800), each pair of strings (806)
defining a region within which each discrete crystalline ribbon (800) is formed.
18. The apparatus as claimed in claim 11, wherein the crucible (300) comprises graphite.
19. The apparatus as claimed in claim 11, wherein the edges (304) of the crucible (300) define
a recessed top surface (1202) of the crucible (300).
20. The apparatus as claimed in claim 11, wherein the width of the crucible (300) is between
about 15 min and at 30 mm.
21. The apparatus as claimed in claim 11, further comprising means for replenishing the melt
(302) on the top surface of the crucible (300) for continuous crystalline ribbon (800)
growth.
22. The apparatus as claimed in claim 11, further comprising means for controlling the
temperatures of the crucible (300) while forming a crystalline ribbon (800).
23. The method as claimed in claim 1 wherein the crucible (300) is a mesa crucible
24. The method as claimed in claim 1, wherein the edges (340) of the crucible (300) define a
recessed top surface (1202) of the crucible (300).
25. The apparatus as claimed in claim 1, wherein the crucible (300) is a mesa crucible.

The invention generally relates to robust and efficient methods for producing sheets
of crystalline material from a molten substance. In particular, the invention relates to a
method for producing ribbons of crystalline silicon for use in solar cells. There is a need to
produce these sheets of silicon having improved flatness, at a lower cost. A melt (302) is
retained by capillary attachment to edge features (304) of a crucible (300). The boundary
profile (808) of the resulting melt surface results in an effect which induces a ribbon (800)
grown from the surface of the melt (302) to grow as a flat body. Further, the size of the
melt (302) is substantially reduced by bringing these edges (304) close to the ribbon (80),
thereby reducing the materials cost and electric power cost associated with the process.

Documents:

838-kolnp-2005-abstract.pdf

838-kolnp-2005-assignment.pdf

838-kolnp-2005-claims.pdf

838-kolnp-2005-correspondence.pdf

838-kolnp-2005-description (complete).pdf

838-kolnp-2005-drawings.pdf

838-kolnp-2005-examination report.pdf

838-kolnp-2005-form 1.pdf

838-kolnp-2005-form 13.pdf

838-kolnp-2005-form 18.pdf

838-KOLNP-2005-FORM 27.pdf

838-kolnp-2005-form 3.pdf

838-kolnp-2005-form 5.pdf

838-kolnp-2005-gpa.pdf

838-kolnp-2005-pa.pdf

838-kolnp-2005-reply to examination report.pdf

838-kolnp-2005-specification.pdf


Patent Number 235065
Indian Patent Application Number 838/KOLNP/2005
PG Journal Number 26/2009
Publication Date 26-Jun-2009
Grant Date 24-Jun-2009
Date of Filing 09-May-2005
Name of Patentee EVERGREEN SOLAR, INC.
Applicant Address 138 BARTLETT ST, MARLBOROUGH, MA
Inventors:
# Inventor's Name Inventor's Address
1 SACHS EMANUEL MICHAEL 18 MORELAND AVENUE, NEWTON, MA 02459
PCT International Classification Number C30B 15/00
PCT International Application Number PCT/US2003/032851
PCT International Filing date 2003-10-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/419,769 2002-10-18 U.S.A.