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US20090061224A1 - Ribbon Crystal String with Extruded Refractory Material - Google Patents

Ribbon Crystal String with Extruded Refractory Material Download PDF

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Publication number
US20090061224A1
US20090061224A1 US12/201,180 US20118008A US2009061224A1 US 20090061224 A1 US20090061224 A1 US 20090061224A1 US 20118008 A US20118008 A US 20118008A US 2009061224 A1 US2009061224 A1 US 2009061224A1
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US
United States
Prior art keywords
string
refractory material
substrate
ribbon
ribbon crystal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US12/201,180
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English (en)
Inventor
Christine Richardson
Lawrence Felton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evergreen Solar Inc
Original Assignee
Evergreen Solar Inc
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Filing date
Publication date
Application filed by Evergreen Solar Inc filed Critical Evergreen Solar Inc
Priority to US12/201,180 priority Critical patent/US20090061224A1/en
Assigned to EVERGREEN SOLAR, INC. reassignment EVERGREEN SOLAR, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FELTON, LAWRENCE, RICHARDSON, CHRISTINE
Publication of US20090061224A1 publication Critical patent/US20090061224A1/en
Assigned to U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT reassignment U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGENT SECURITY AGREEMENT Assignors: EVERGREEN SOLAR, INC.
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/34—Edge-defined film-fed crystal-growth using dies or slits
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62847—Coating fibres with oxide ceramics
    • C04B35/62849—Silica or silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62847—Coating fibres with oxide ceramics
    • C04B35/62852—Alumina or aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/6286—Carbides
    • C04B35/62863—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
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    • C04B35/62857—Coating fibres with non-oxide ceramics
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
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    • C04B35/62857—Coating fibres with non-oxide ceramics
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/62873—Carbon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62894—Coating the powders or the macroscopic reinforcing agents with more than one coating layer
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/36—Single-crystal growth by pulling from a melt, e.g. Czochralski method characterised by the seed, e.g. its crystallographic orientation
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1032—Seed pulling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the invention generally relates to string ribbon crystals and, more particularly, the invention also relates to string used to form string ribbon crystals.
  • String ribbon crystals such as those discussed in U.S. Pat. No. 4,689,109 (issued in 1987 and naming Emanuel M. Sachs as the sole inventor), can form the basis of a variety of electronic devices.
  • Evergreen Solar, Inc. of Marlborough, Mass. forms solar cells from conventional string ribbon crystals.
  • a method of making string for string ribbon crystal provides a substrate having an outer surface, and extrudes refractory material over the substrate.
  • the refractory material substantially covers the outer surface of the substrate. The method then cures the refractory material.
  • the substrate may be formed from a carbon filament or a tow, while the extruded refractory material may include silicon carbide.
  • the method also may form an exterior reduced wetting layer radially outward of the refractory material.
  • the substrate and refractory material form a generally elongated cross-sectional shape, and/or are generally concentric.
  • a string for forming a ribbon crystal has a substrate, and an extruded refractory material layer substantially covering the substrate.
  • FIG. 1 schematically shows a string ribbon crystal that may be formed from strings configured in accordance with illustrative embodiments of the invention.
  • FIG. 2 schematically shows an illustrative furnace used to form string ribbon crystals.
  • FIG. 3 schematically shows a cross-sectional view of a portion of a prior art ribbon crystal with a prior art string.
  • FIG. 4A schematically shows a string formed in accordance with illustrative embodiments of the invention.
  • FIG. 4B schematically shows eight cross-sectional views of the string of FIG. 4A along line B-B in accordance with various embodiment of the invention.
  • FIG. 5 shows an illustrative process of forming a string ribbon crystal using strings configured in accordance with illustrative embodiments of the invention.
  • FIGS. 6A , 6 B, and 6 C schematically show cross-sectional views of ribbon crystals in accordance with an embodiment using strings with an elongated cross-section.
  • FIGS. 7A and 7B schematically show cross-sectional views of ribbon crystals with multiple strings used to perform the function of a single string.
  • FIGS. 8A and 8B schematically show a ribbon crystal with a string having a generally concave cross-sectional shape.
  • Illustrative embodiments extrude a refractory material over a core/substrate to form string used to grow ribbon crystals. This process beneficially avoids use of complex prior art processes that require hazardous chemicals (e.g., CVD processes). Details of various embodiments are discussed below.
  • hazardous chemicals e.g., CVD processes
  • FIG. 1 schematically shows a string ribbon crystal 10 configured in accordance illustrative embodiments of the invention.
  • this ribbon crystal 10 has a generally rectangular shape and a relatively large surface area on its front and back faces.
  • the ribbon crystal 10 may have a width of about 3 inches, and a length of about 6 inches.
  • the length can vary significantly.
  • the width can vary depending upon the separation of its two strings 12 (see FIG. 2 ) forming the ribbon crystal width boundaries. Accordingly, discussion of specific lengths and widths are illustrative and not intended to limit various embodiments the invention.
  • the thickness of the ribbon crystal 10 may vary and be very small relative to its length and width dimensions.
  • the string ribbon crystal 10 may have a thickness ranging from about 60 microns to about 320 microns across its width. Despite this varying thickness, the string ribbon crystal 10 may be considered to have an average thickness across its length and/or width.
  • the ribbon crystal 10 may be formed from any of a wide variety of materials (often referred to generally as “ribbon material” or “crystal material”), depending upon the application.
  • ribbon material when grown for a photovoltaic application, the ribbon crystal 10 may be formed from a single element, such as silicon, or a compound, such as a silicon-based material (e.g., silicon germanium).
  • Other illustrative ribbon materials may include gallium arsenide, or indium phosphide.
  • the ribbon material may be any of a variety of crystal types, such as multi-crystalline, single crystalline, polycrystalline, microcrystalline or semi-crystalline.
  • the ribbon crystal 10 is formed from a pair of strings 12 generally embedded/encapsulated by the ribbon material.
  • the ribbon crystal 10 is discussed as being formed from polysilicon ribbon material. It nevertheless should be reiterated that discussion of polysilicon is not intended to limit all embodiments.
  • FIG. 2 schematically shows a silicon ribbon crystal growth furnace 14 that may be used to form the string ribbon crystal 10 in accordance with illustrative embodiments of the invention.
  • the furnace 14 has, among other things, a housing 16 forming a sealed interior that is substantially free of oxygen (to prevent combustion). Instead of oxygen, the interior has some concentration of another gas, such as argon, or a combination of gasses.
  • the housing interior also contains, among other things, a crucible 18 and other components for substantially simultaneously growing four silicon ribbon crystals 10 .
  • a feed inlet 20 in the housing 16 provides a means for directing silicon feedstock to the interior crucible 18 , while an optional window 22 permits inspection of the interior components.
  • the crucible 18 which is supported on an interior platform within the housing 16 , has a substantially flat top surface.
  • This embodiment of the crucible 18 has an elongated shape with a region for growing silicon ribbon crystals 10 in a side-by-side arrangement along its length.
  • the crucible 18 is formed from graphite and resistively heated to a temperature capable of maintaining silicon above its melting point.
  • the crucible 18 has a length that is much greater than its width.
  • the length of the crucible 18 may be three or more times greater than its width.
  • the crucible 18 is not elongated in this manner.
  • the crucible 18 may have a somewhat square shape, or a nonrectangular shape.
  • the furnace 14 has a plurality of holes 24 (shown in phantom) for receiving string 12 .
  • the furnace 14 of FIG. 2 has eight string holes 24 for receiving four pairs of strings 12 .
  • Each pair of strings 12 passes through molten silicon in the crucible 18 to form a single ribbon crystal 10 .
  • FIG. 3 schematically shows a cross-sectional view of a portion of a prior art ribbon crystal 10 P having a prior art string 12 P.
  • This prior art ribbon crystal 10 P has a thin neck portion 36 between the string 12 P and a wider portion 38 of the ribbon crystal 10 . If the neck portion 36 is too thin, then the ribbon crystal 10 P may be very fragile and more prone to breaking, thus leading to yield losses. For example, if the coefficient of thermal expansion differential between the string 12 and ribbon material forming the ribbon crystal 10 P (e.g., polysilicon) is sufficiently large, the ribbon crystal 10 P may be more prone to breaking at the neck portion 36 .
  • the coefficient of thermal expansion differential between the string 12 and ribbon material forming the ribbon crystal 10 P e.g., polysilicon
  • one such solution adds gas jets (not shown) to the furnace 14 . These gas jets direct relatively cool gas streams toward the neck portion 36 , thus decreasing the temperature in that area to increase neck thickness.
  • Other solutions involve adding specialized meniscus shapers.
  • illustrative embodiments of the invention engineer the cross-sectional dimension of the string 12 in a prescribed manner.
  • the string 12 then is positioned within the crystal growth furnace 14 in a manner that increases the size of the neck portion 36 of the growing ribbon crystal 10 .
  • the resulting ribbon crystal 10 with an average thickness of about 190 microns may have a neck portion 36 with a minimum thickness of about 60 microns, which may suffice in certain applications.
  • This innovation consequently should reduce yield loss, thus reducing production costs.
  • FIG. 4A schematically shows a string 12 that may be formed in accordance with illustrative embodiments of the invention. Although this figure appears to show a generally convex or rounded cross-section, it should be considered merely schematic and not representative of any specific cross-sectional shape.
  • FIG. 4B schematically shows eight different possible cross-sectional views of the string 12 of FIG. 4A along cross-line B-B in accordance with a number of different embodiments of the invention. For example, some of the shapes are generally elongated, such as the irregular shape of string one, the rectangular shape of string two, and the somewhat elliptical shape of string three.
  • the various strings 12 may be categorized as being either generally concave or generally convex.
  • a cross-sectional shape is generally concave when any portion of its perimeter forms at least one non-negligible concavity.
  • string one is considered to be generally concave despite its other convex portions.
  • a cross-sectional shape is considered to be generally convex when its perimeter forms no non-negligible concavities.
  • string two and string three of FIG. 4B a generally convex.
  • FIG. 4B shows a number of other cross-sectional string shapes that are generally concave. In fact, some may be considered elongated and concave. For example, string four is generally “C” shaped, concave, and elongated, while string five is generally cross shaped, concave, but not elongated. The shape of string five (cross shaped) is not elongated because it is generally symmetrical—both the horizontal and vertical portions of the cross are about the same size. Depending upon its actual dimensions, string eight, which is generally “T” shaped, may or may not be considered elongated. For example, if the portion of the “T” shape extending downwardly is longer than its horizontal portion, then string eight may be considered elongated. In either case, string eight is considered to be generally concave.
  • strings 12 use plural strings 12 to form one edge of a ribbon crystal 10 .
  • Strings six and seven show two such embodiments. Specifically, string six shows one embodiment where the individual strings 12 physically contact each other in the final ribbon crystal 10 , while string seven shows another embodiment where the individual strings 12 are spaced from each other in the final ribbon crystal 10 . It should be noted that embodiments using plural strings 12 may use more than two strings 12 .
  • individual strings 12 of this plural string embodiment may have the same or different cross-sectional shapes (e.g., a first elliptically shaped string 12 and another cross or circular shaped string 12 ).
  • FIG. 4B merely are examples of a variety of different cross-sectional string shapes.
  • some embodiments use strings that have a generally circular cross-sectional shape. Accordingly, those skilled in the art should understand that other string shapes fall within the scope of various embodiments.
  • FIG. 5 shows an illustrative process of forming a string ribbon crystal 10 with strings 12 configured in accordance with illustrative embodiments of the invention.
  • this process is discussed with reference to string two of FIG. 4B only—because string two is the only string 12 in that figure explicitly showing various string layers discussed in this process. It nevertheless should be noted that the discussed principles apply to strings 12 having other cross-sectional shapes, or other strings formed by other processes.
  • the process begins at step 500 by forming a core/substrate 28 , which acts as a substrate to receive a refractory material layer.
  • the core 28 can be formed from carbon by conventional extruding processes. In other embodiments, however, the core 28 may be a wire, filament, or plurality of small conductive fibers wound together as a tow.
  • post-fabrication processes could form a monofilament through a known fabrication process, such as oxidation, carbonization, or infiltration.
  • the core 28 may have the desired cross-sectional shape.
  • the core 28 of string two is generally rectangular.
  • the core 28 may have a different cross-sectional shape, while refractory material application equipment may be specially configured to form the desired cross-sectional shape.
  • the extrusion equipment may be specially configured to form the cross-sectional shape from a core material having a prespecified cross-sectional shape that is the same as or different than that of the final cross-sectional string shape.
  • the process forms a first coating/layer, which acts as the above noted refractory material layer 30 (step 502 ).
  • the first coating 30 may include silicon carbide, tungsten, or a combination of silicon carbide and tungsten.
  • this outer surface 30 should be very smooth to minimize nucleations that may occur when it contacts molten ribbon material within the furnace 24 . Fewer nucleations desirably should produce fewer grains and thus, fewer grain boundaries. Consequently, such strings 12 should be more electrically efficient than those with more grains and more grain boundaries.
  • Illustrative embodiments solve these problems. Specifically, to avoid the use of such complex machinery and hazardous chemicals of a CVD process (or other similar process), illustrative embodiments extrude the refractory material directly onto the core/substrate 28 , thus covering substantially the entire outer (circumferential) surface of the core 28 . This is contrary to prior art teachings, however, because it is expected to yield a less smooth surface. The inventors nevertheless anticipate that such a string can produce satisfactory results in a much less costly manner and with fewer safety risks.
  • Formation of the extruded refractory material layer 30 may involve, among other things, a pulltrusion process, or both spinning of a refractory material with a polymer component, which subsequently is baked off.
  • Processes may use at least one component of carbon, silicon, silicon carbide, silicon nitride, aluminum, mullite, silicon dioxide, BN particles, or fibers mixed with a polymer binder, coupled with extrusion/pulltrusion. This also may involve bicomponent extrusion of a core 28 with at least one silicon carbide, carbon, silicon, and a sheath with a least one of oxide, mullite, carbon, and/or silicon carbide.
  • the core 28 effectively acts as a substrate for supporting the refractory material layer 30 .
  • the refractory material layer 30 may be, or may not be, generally concentric with the core 28 . After it is extruded onto the core 28 , the refractory material layer 30 is allowed to harden/cure for a sufficient amount of time.
  • some embodiments form one or more layers radially outward of the refractory material layer 30 .
  • Such layers can be smoother, or take on a roughness that is similar to that of this layer 30 .
  • the base string portion 26 has a combined coefficient of thermal expansion that preferably generally matches the coefficient of thermal expansion of the ribbon material.
  • the thermal expansion characteristics of the string 12 should be sufficiently well matched to the ribbon material so that excessive stress does not develop at the interface. Stress is considered excessive if the string 12 exhibits a tendency to separate from the ribbon during reasonable subsequent ribbon crystal handling and processing steps, or if the string 12 exhibits a tendency to curl outwardly or inwardly from the ribbon crystal edge. In other embodiments, however, the coefficient of thermal expansion of the base string portion 26 does not generally match that of the ribbon material.
  • the string 12 may have a non-wetting/reduced wetting layer 32 to increase the grain size of the ribbon material.
  • the process continues to step 504 , which forms an exposed non-wetting/reduced layer 32 on the base string portion 26 .
  • this layer 32 preferably is very thin so that it has a negligible impact on the overall string coefficient of thermal expansion.
  • the reduced wetting layer 32 should be much thinner than that of the refractory material layer 30 .
  • the contact angle with the ribbon material of its exterior surface should be carefully controlled to cause the molten ribbon material to adhere to it—otherwise, the process cannot form the ribbon crystal 10 .
  • contact angles with silicon of between about 15 and 120° degrees should produce satisfactory results. Such angles of greater than 25 degrees may produce better results.
  • the non-wetting layer 32 may be formed by CVD processes, dip coating or other methods.
  • the base string portion 26 may be CVD coated by applying electrical contacts in a deposition chamber while it is being fed through the chamber—thus heating the base string portion 26 itself.
  • the base string portion 26 may be heated by induction heating through the chamber.
  • the string 12 also may have a handling layer 34 radially outward of the refractory material layer 30 to maintain the integrity of the base string portion 26 .
  • the handling layer 34 provides a small compressive stress to the base string portion 26 , thus improving robustness to the overall string 12 . Accordingly, if the base string portion 26 develops a crack, the compressive stress of the handling layer 34 should reduce the likelihood that the string 12 will break.
  • the handling layer 34 may be a thin layer of carbon (e.g., one or two microns thick for strings 12 having generally known sizes).
  • some embodiments may form a handling layer 34 that is separate from the produced nonwetting layer 32 (e.g., see string two of FIG. 4B ).
  • the nonwetting layer 32 substantially covers the handling layer 34 .
  • the nonwetting layer 32 covers the outer, circumferential surface of the handling layer 34 .
  • the coated string 12 has filaments extending through the nonwetting layer 32 (such filaments are referred to herein as “whiskers”). This can occur, for example, when a tow of filaments forms the core 28 . If the coated string 12 has whiskers, then the process shaves them off at step 508 . The process then may loop back to step 504 , which re-applies the nonwetting layer 32 .
  • step 510 which provides the string 12 to the furnace 14 as shown in FIG. 2 .
  • some embodiments provide a single string 12 for each ribbon crystal edge, or multiple strings 12 for each ribbon crystal edge (e.g., strings six and seven of FIG. 6B ).
  • the string 12 may be formed by other methods.
  • Illustrative embodiments orient the strings 12 in the furnace 14 in a manner that increases the thickness of the ribbon crystal neck portion 36 .
  • FIGS. 6A-6C schematically show cross-sectional views of three ribbon crystals 10 with strings 12 having elongated, generally elliptical, generally convex cross-sectional shapes.
  • these embodiments orient their respective generally longitudinal axes 42 so that they diverge with the width dimension of their respective ribbon crystals 10 .
  • the longitudinal axis 42 is not parallel with the width dimension—instead, the longitudinal axis 42 and width dimension intersect.
  • each string 12 has a largest dimension, each of which is shown as double-head arrows in FIGS. 6A-6C .
  • the longitudinal axis 42 of each of these elongated cross-sectional shapes thus is considered to be co-linear with the largest dimension.
  • FIG. 6A orients the longitudinal axis 42 substantially perpendicular to the width dimension
  • FIG. 6C orients the longitudinal axis 42 to form a shallow angle with the width dimension
  • FIG. 6B orients the longitudinal axis 42 between the extremes of FIGS. 6A and 6C .
  • orientations other than those shown in FIGS. 6A-6C also should provide satisfactory results.
  • orienting the longitudinal axis 42 in a manner so that is rotated about 90 degrees (either clockwise or counterclockwise) from the angle shown in FIG. 6B also should increase neck size.
  • FIGS. 8A and 8B schematically show two ribbon crystals 10 with strings 12 having a generally concave cross-sectional shape.
  • the strings 12 are oriented so that their concavities either are oriented completely toward or completely away from the wafer width (i.e., in the X-direction).
  • the concavity is generally symmetrically oriented, e.g., the concavity forms a mirror image above and below the X-axis. Significant rotation from these orientations (either clockwise or counterclockwise), however, may impact the meniscus shape to impede appropriate crystal growth.
  • Those in the art can apply this concept to a string 12 having multiple concavities or concavities on opposing sides of the cross-sectional shape (e.g., a cross-shape).
  • the process passes two strings 12 (together forming the ultimate ribbon crystal width) through the furnace 14 and crucible 18 , thus forming the string ribbon crystal 10 (step 512 ).
  • illustrative embodiments of the invention extrude the refractory material layer 30 on the core 28 , thus avoiding problems associated with prior art deposition techniques and reducing production costs.

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  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Crystals, And After-Treatments Of Crystals (AREA)
  • Silicon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
US12/201,180 2007-08-31 2008-08-29 Ribbon Crystal String with Extruded Refractory Material Abandoned US20090061224A1 (en)

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US12/200,996 Expired - Fee Related US7651768B2 (en) 2007-08-31 2008-08-29 Reduced wetting string for ribbon crystal
US12/633,951 Expired - Fee Related US7842270B2 (en) 2007-08-31 2009-12-09 Ribbon crystal having reduced wetting string
US13/079,838 Abandoned US20110247546A1 (en) 2007-08-31 2011-04-05 Ribbon Crystal String for Increasing Wafer Yield
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US13/079,838 Abandoned US20110247546A1 (en) 2007-08-31 2011-04-05 Ribbon Crystal String for Increasing Wafer Yield
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US20090061163A1 (en) * 2007-08-31 2009-03-05 Evergreen Solar, Inc. Ribbon Crystal String for Increasing Wafer Yield
WO2012094169A3 (en) * 2011-01-06 2012-08-23 1366 Technologies Inc. Crystal ribbon fabrication with multi-component strings
CN102729846A (zh) * 2011-03-29 2012-10-17 现代自动车株式会社 用于机动车辆座椅的底架

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US20120164379A1 (en) * 2010-12-22 2012-06-28 Evergreen Solar, Inc. Wide Sheet Wafer
US8912083B2 (en) 2011-01-31 2014-12-16 Nanogram Corporation Silicon substrates with doped surface contacts formed from doped silicon inks and corresponding processes
CN111172588A (zh) * 2020-01-20 2020-05-19 江苏双良新能源装备有限公司 一种用于生长大表面带状硅的引晶拉制方法
KR20250030222A (ko) * 2023-08-24 2025-03-05 한화솔루션 주식회사 태양광 인터커넥터 및 이를 구비하는 태양 전지 모듈

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CA2697403A1 (en) 2009-03-05
EP2183411B1 (en) 2013-08-21
US20110247546A1 (en) 2011-10-13
JP2010537934A (ja) 2010-12-09
CN101821433A (zh) 2010-09-01
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US20090060823A1 (en) 2009-03-05
ES2386999T3 (es) 2012-09-10
ES2436293T3 (es) 2013-12-30
US7842270B2 (en) 2010-11-30
MX2010002309A (es) 2010-03-22
EP2186139A1 (en) 2010-05-19
US20130047914A1 (en) 2013-02-28
EP2183411A1 (en) 2010-05-12
US20100092776A1 (en) 2010-04-15
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EP2650406A1 (en) 2013-10-16
CA2697374A1 (en) 2009-03-05
WO2009029741A1 (en) 2009-03-05
US20090061163A1 (en) 2009-03-05
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WO2009029761A1 (en) 2009-03-05
US7651768B2 (en) 2010-01-26

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