Vapor deposition method of forming low cost semiconductor solar cells including reconstitution of the reacted gases

• US 3,969,163 A
• Filed: 09/19/1974
• Issued: 07/13/1976
• Est. Priority Date: 09/19/1974
• Status: Expired due to Term

• Current Assignee: Texas Instruments, Inc.
• Original Assignee: Texas Instruments, Inc.
• Inventors: Wakefield, Gene Felix
• Primary Examiner(s): Rutledge, L. Dewayne
• Assistant Examiner(s): Saba, W. G.
• Application Number:
  US05/507,329
• Time in Patent Office: 663 Days
• Field of Search: 148/174, 148/175, 136/89, 357/30, 156/613, 423/341-344, 423/348-350, 423/489, 427/86, 427/113, 427/248, 118/48-49.5, 29/572
• US Class Current: 438/62
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: H01L 31/035281 Shape of the body
• CPC Class Codes: H01L 31/068 the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
• CPC Class Codes: H01L 31/1804 comprising only elements of Group IV of the Periodic Table
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 148/006 Apparatus
• CPC Class Codes: Y10S 148/12 Photocathodes-Cs coated and solar cell
• CPC Class Codes: Y10S 148/122 Polycrystalline
• CPC Class Codes: Y10S 148/13 Purification
• CPC Class Codes: Y10S 438/907 Continuous processing

Abstract

The disclosure relates to a method of upgrading metallurgical grade silicon to semiconductor grade for making low cost silicon devices and particularly solar cells. This is accomplished by passing conductive fibers such as graphite or the like which are compatible with the later processing steps through an area which is cooled below 700° C and which contains silicon difluoride and a proper N-type dopant. At these temperatures, the silicon difluoride gas will break down into pure silicon which will deposit onto the fiber with the formation of silicon tetrafluoride gas which is then recycled into a further chamber. In the further chamber, the gaseous silicon tetrafluoride is mixed with the impure metallurgical grade silicon at temperatures above 700° C to form the silicon difluoride gas which is then fed into the former chamber for deposition of pure silicon onto the continuously moving fibers of graphite or the like. A p-type layer can then be formed over the n-type layer in any standard manner, such as by then passing the coated fibers through a further reaction chamber wherein p-type dopant is diffused into the top surface of the n-type layer that has been formed. The dopants alternatively could be added in the gas stream of SiF₄ or the p-layer formed by ion implantation. In this way, relatively inexpensive p-n junction devices are formed without the requirement of purifying, cutting and polishing a silicon slice in the standard manner.

Claims

1. A method of forming semiconductor grade silicon from lower grade silicon, which comprises the steps of:

a. providing a first chamber having at least a zone thereof maintained at a temperature below about 700°

C,

b. passing a graphite fiber substrate through said zone,

c. passing a gaseous mixture of silicon difluoride and a suitable dopant into said first chamber including said zone whereby said silicon difluoride decomposes to pure silicon which deposits on said substrate and gaseous silicon tetrafluoride,

d. removing said silicon tetrafluoride from said first chamber,

e. providing a second chamber containing impure silicon,

f. heating said chamber to a temperature in the range of 750°

to about 1200°

C, and

g. passing silicon tetrafluoride, including at least a portion of the silicon tetrafluoride removed from said first chamber, into said second chamber to form additional silicon difluoride which is then introduced into said first chamber.

2. A method as set forth in claim 1 further including the step of forming a region on the surface of said silicon of conductivity type opposite to said predetermined conductivity type.

3. A method as set forth in claim 2 wherein the temperature of said zone in said first chamber is about 600°

C.

4. A method as set forth in claim 2 wherein the temperature in said second chamber is about 900°

C.

5. A method as set forth in claim 3 wherein the temperature in said second chamber is about 900°

C.