Columnar-grained polycrystalline solar cell and process of manufacture
The invention relates to techniques for manufacturing columnar-grained polycrystalline sheets which have particular utility as substrates or wafers for solar cells. The sheet is made by applying granular silicon to a setter material which supports the granular material. The setter material and granular silicon are subjected to a thermal profile all of which promote columnar growth by melting the silicon from the top downwardly. The thermal profile sequentially creates a melt region at the top of the granular silicon and then a growth region where both liquid and a growing polycrystalline sheet layer coexist. An annealing region is created where the temperature of the grown polycrystalline silicon sheet layer is controllably reduced to effect stress relief.
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Claims
1. A process of making an improved columnar-grained polycrystalline sheet for functioning as a substrate for a solar cell, comprising (a) applying granular silicon to a setter material having a release coating at its upper surface and which supports the granular silicon, (b) preheating the setter material and granular silicon in a preheat zone, (c) subjecting the setter material and granular silicon to a thermal profile which causes melting of the granular silicon from the top downwardly, wherein 25 to 90% of the granular silicon depth is melted and the partially melted silicon below the melted material functions as a net to stabilize the melt and to minimize molten silicon contact with the underlying setter material and release coating and to nucleate subsequent crystal growth, (d) transporting the melt pool on the silicon net into a growth zone wherein a thermal profile is created to promote columnar growth of a columnar grain size greater than 20 microns in a direction approximately perpendicular to the plane of the setter material and where both liquid and a growing polycrystalline layer coexist and where the entire layer experiences a liquid state prior to solidification, (e) transporting the grown sheet into an anneal zone wherein a linear temperature gradient along the direction of setter material motion is provided to promote low stress cooling of the sheet, (f) removing the polycrystalline sheet from the setter material, facilitated by a release agent, and (g) reusing the setter material for the making of further columnar-grained polycrystalline sheet.
2. The process of claim 1 including achievement of any or all of the preheat, melting, growth, and anneal thermal profiles for the granular silicon and resultant sheet by focused light energy.
3. The process of claim 1 including creating an electrical resistivity in the sheet layer in the range of 0.1 to 10 ohm-cm by adding separate constituents to the granular silicon.
4. The process of claim 1 including the use of granular silicon sized between 100 to 1000 micrometers, which has a purity between metallurgical grade and electronic grade silicon.
5. The process of claim 1 including stabilizing the outer edges of the melt zone by thermal shunts, or reduced energy intensity at the edge of the melt.
6. The process of claim 1 including forming nucleation sites in the setter material to commence growth by locally placing thermal shunts in the setter materialk to provide a thermal conduction path between the top and the bottom of the setter material.
7. The process of claim 1 wherein multi-grained or single crystal granular silicon is used to nucleate columnar grains having an average gain size of 0.002 to 1 cm in the subsequent sheet.
8. The process of claim 1 wherein the setter material is selected from the group consisting of quartz, silica, alumina, graphite, and SiC.
9. The process of claim 1 wherein the setter material is replaced by a thin belt material which supports the sheet during formation and thermal processing, and does not chemically interact with, or adhere to, the silicon material.
10. The process of claim 1 wherein the resulting silicon sheet has the characteristics of flatness, a smooth surface, minority carrier diffusion length greater than 10 microns, low residual stress, and relatively inactive grain boundaries.
11. The process of claim 1 including utilizing the sheet as a substrate for a solar cell by forming the additional solar cell layers on the substrate.
12. A solar cell made by the process of claim 11.
13. A substrate made by the process of claim 1.
14. The process of claim 1 wherein the partially melted silicon net and the setter material are replaced by a non-melting, non-reusable, thermal coefficient-matched substrate which is wetted by and stabilizes the molten silicon over-layer, nucleates subsequent growth, and serves as a supporting substrate during subsequent solar cell processing of the grown sheet.
15. The process of claim 14 including utilizing the sheet as a substrate for a solar cell by forming the additional solar cell layers on the substrate.
16. A solar cell made by the process of claim 15.
17. A substrate made by the process of claim 14.
18. The process of claim 14 wherein graphite is used as the substrate.
19. The process of claim 1 including achievement of any or all of the preheat, melting, growth, and anneal thermal profiles for the granular silicon and resultant sheet by graphite based heater technology.
20. A process in claim 1 where an overpressure consisting of at least 10% nitrogen (by volume) is employed in any or all of the pre-heat, melting, growth and anneal zones.
21. A process of making an improved columnar-grained polycrystalline sheet for functioning as a substrate for a solar cell, comprising (a) applying a net to a setter material, (b) applying granular silicon to the setter material and the net whereby to support the granular silicon, (c) preheating the setter material and the net and the granular silicon in a preheat zone, (d) subjecting the setter material and the net and the granular silicon to a thermal profile which causes melting of the granular silicon from the top downwardly, wherein 25 to 90% of the granular silicon depth is melted and the partially melted silicon below the melted material functions as a nucleation site to nucleate subsequent crystal growth and the net functions to stabilize the melt and to minimize molten silicon contact with underlying setter and the net functions as a release coating, (e) transporting the melt pool on the net into a growth zone wherein a thermal profile is created to promote columnar growth of a columnar grain size greater than 20 microns in a direction approximately perpendicular to the plane of the setter material and where both liquid and a growing polycrystalline layer coexist and where the entire layer experiences a liquid state prior to solidification, (f) transporting the grown sheet into an anneal zone wherein a linear temperature gradient along the direction of setter material motion is provided to promote low stress cooling of the sheet, (g) removing the polycrystalline sheet from the setter material, facilitated by a release agent, and (h) reusing the setter material for the making of further columnar-grained polycrystalline sheets.
22. The process of claim 22 wherein the net is made from a graphite material.
23. The process of claim 22 including achievement of any or all of the preheat, melting, growth, and anneal thermal profiles for the granular silicon and resultant sheet by graphite based heater technology.
24. The process of claim 21 wherein the net is made from silicon carbide.
25. The process of claim 21 including achievement of any or all of the preheat, melting, growth, and anneal thermal profiles for the granular silicon and resultant sheet by graphite based heater technology.
26. The process of claim 21 including utilizing the sheet as a substrate for a solar cell by forming the additional solar cell layers on the substrate.
27. A solar cell made by the process of claim 26.
28. A substrate made by the process of claim 21.
29. A process in claim 21 where an overpressure consisting of at least 10% nitrogen (by volume) is employed in any or all of the pre-heat, melting, growth and anneal zones.
30. A process of making an improved columnar-grained polycrystalline sheet for functioning as a substrate for a solar cell, comprising (a) providing a layer of graphite material, (b) applying granular silicon to the graphite material whereby to support the granular silicon, (c) preheating the graphite material and the granular silicon in a preheat zone, (d) subjecting the graphite material and the granular silicon to a thermal profile which causes melting of the granular silicon from the top downwardly, wherein 25 to 90% of the granular silicon depth is melted and the partially melted silicon below the melted material functions as a nucleation site to nucleate subsequent crystal growth and the graphite material functions as a release coating, (e) transporting the melt pool on the graphite material into a growth zone wherein a thermal profile is created to promote columnar growth of a columnar grain size greater than 20 microns in a direction approximately perpendicular to the plane of the graphite material and where both liquid and a growing polycrystalline layer coexist and where the entire layer of experiences a liquid state prior to solidification, (f) transporting the grown sheet into an anneal zone wherein a linear temperature gradient along the direction of graphite material motion is provided to promote low stress cooling of the sheet, (g) removing of the polycrystalline sheet from the graphite material, and (h) reusing the graphite material for the making of further columnar-grained polycrystalline sheets.
31. The process of claim 30 including utilizing the sheet as a substrate for a solar cell by forming the additional solar cell layers on the substrate.
32. A solar cell made by the process of claim 31.
33. A substrate made by the process of claim 30.
34. A process in claim 30 where an overpressure consisting of at least 10% nitrogen (by volume) is employed in any or all of the pre-heat, melting, growth and anneal zones..Iadd.
35. A sheet of silicon, said silicon sheet having a pair of opposing manor surfaces, said silicon of said sheet being of elongated columnar grain form with the grains having an average width in the range of 0.002 to 1 cm in size with the columnar axis thereof extending in the direction of their columnar axis from major surface to major surface, and said sheet having a thickness of from 350 to 1000 microns..Iaddend..Iadd.36. The sheet of claim 35 wherein said grain size is greater than 80 microns..Iaddend..Iadd.37. The sheet of claim 36 wherein said sheet has an electrical resistivity in the range of 0.1 to 10 ohm-cm.
.Iaddend..Iadd. The sheet of claim 37 having the characteristics of flatness, a smooth surface, minority carrier diffusion length greater than 10 microns, low residual stress, and low activity grain boundaries..Iaddend..Iadd.39. The sheet of claim 38 wherein said minority carrier diffusion length is greater than 40 microns..Iaddend..Iadd.40. The sheet of claim 38 wherein the minimum grain dimension is at least two times said minority carrier diffusion length..Iaddend..Iadd.41. The sheet of claim 40 wherein said sheet is sized to function as a substrate.
.Iaddend..Iadd. 2. The sheet of claim 35 wherein said sheet has an electrical resistivity in the range of 0.1 to 10 ohm-cm..Iaddend..Iadd.43. The sheet of claim 35 having the characteristics of flatness, a smooth surface, minority carrier diffusion length greater than 10 microns, low residual stress, and low activity grain boundaries..Iaddend..Iadd.44. The sheet of claim 43 wherein the minimum grain dimension is at least two times said minority carrier diffusion length.
.Iaddend..Iadd.45. The sheet of claim 35 wherein said sheet is sized to function as a substrate..Iaddend..Iadd.46. The sheet of claim 35 wherein said grains from at one of said surfaces having features of a silicon net.
.Iaddend..Iadd.47. A substrate made from a sheet of silicon, said silicon sheet having a pair of opposing major surfaces, said silicon sheet being of elongated columnar grain form with the grains having an average width in the range of 0.002 to 1 cm in size with the columnar axis thereof extending in the direction of their columnar axis from one of said surfaces to the other of said surfaces, and said silicon sheet having a thickness of from 350 to 1000 microns..Iaddend..Iadd.48. The substrate of claim 47 wherein said grain size is greater than 80 microns.
.Iaddend..Iadd.49. In a solar cell having a substrate, the improvement being in that said substrate comprises a sheet of silicon, said silicon sheet having a pair of opposing major surfaces, said silicon sheet being of elongated columnar grain form with the grains having an average width in the range of 0.002 to 1 cm in size with the columnar axis thereof extending in the direction of their columnar axis from one of said surfaces to the other of said surfaces, and said silicon sheet having a thickness of from 350 to 1000 microns..Iaddend..Iadd.50. The solar cell of claim 49 wherein said substrate has a thickness in the range of 0.01 to 0.10 cm, and said solar cell being capable of achieving voltages in excess of 560 mV and fill factors in excess of 0.72..Iaddend..Iadd.51. The solar cell of claim 50 wherein said solar cell includes a plurality of layers made entirely of silicon supported by said substrate..Iaddend.
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Type: Grant
Filed: Jan 24, 1997
Date of Patent: Mar 23, 1999
Assignee: Astropower, Inc. (Newark, DE)
Inventors: Robert B. Hall (Newark, DE), Allen M. Barnett (Newark, DE), Sandra R. Collins (Chesapeake City, MD), Joseph C. Checchi (Newark, DE), David H. Ford (Wilmington, DE), Christopher L. Kendall (Wilmington, DE), Steven M. Lampo (Elkton, MD), James A. Rand (Oxford, PA)
Primary Examiner: Nam Nguyen
Law Firm: Connolly & Hutz
Application Number: 8/788,660
International Classification: H01L 310392; H01L 310368; H01L 3118;
