Fabrication of polycrystalline thin films by pulsed laser processing

• US 5,714,404 A
• Filed: 11/18/1993
• Issued: 02/03/1998
• Est. Priority Date: 11/18/1993
• Status: Expired due to Term

• Current Assignee: Lawrence Livermore National Security LLC (Government of the United States of America)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Truher, Joel B., Kaschmitter, James L., Mitlitsky, Fred, Colella, Nicholas J.
• Primary Examiner(s): Thomas, Tom
• Assistant Examiner(s): MULPURI, SAVITRI
• Application Number:
  US08/154,347
• Time in Patent Office: 1,538 Days
• Field of Search: 437/233, 437/173, 437/101, 437/109, 437/2, 437/4, 257/75, 257/49, 257/51, 148/DIG. 1, 148/DIG. 90, 148/DIG. 93, 148/DIG. 122, 117/4, 117/7, 117/904, 136/261
• US Class Current: 438/94
• CPC Class Codes: H01L 31/182 Special manufacturing methods for polycrystalline Si, e.g. Si ribbon, poly Si ingots, thin films of polycrystalline Si
• CPC Class Codes: Y02E 10/546 Polycrystalline silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A method for fabricating polycrystalline thin films on low-temperature (or high-temperature) substrates which uses processing temperatures that are low enough to avoid damage to the substrate, and then transiently heating select layers of the thin films with at least one pulse of a laser or other homogenized beam source. The pulse length is selected so that the layers of interest are transiently heated to a temperature which allows recrystallization and/or dopant activation while maintaining the substrate at a temperature which is sufficiently low to avoid damage to the substrate. This method is particularly applicable in the fabrication of solar cells.

Claims

1. A method for fabricating polycrystalline thin films including the steps of:

forming a film of material on a substrate in a time period such that the temperature of the substrate is not raised above a temperature of about 450°

C. for a time period greater than about 100 μ

s; and

irradiating at least a portion of the thus formed film with at least one energy pulse to cause heating and recrystallization of at least a portion of the material of the film in a time period such that the temperature of the substrate is not raised above a temperature of about 180°

C. for said time period of greater than about 100 μ

s.

2. The method of claim 1, wherein the energy pulse is produced by a homogenized beam source selected from the group of dye lasers, excimer lasers, flashlamp-pumped lasers, and electron-beams.

3. The method of claim 2, wherein the homogenized beam source has the capability of applying up to about 100 μ

s pulses of 01.1-10 Jcm^-2 energy to the film of material.

4. The method of claim 1, additionally including the step of forming the substrate from a material incapable of withstanding processing temperatures of higher than about 180°

C. for longer than about 100 μ

s.

5. The method of claim 4, wherein said substrate is formed from low-temperature materials selected from the group consisting of E-CTFE, E-TFE, PES, PVDF, PTFE, FFP, and HDPE.

6. The method of claim 1, additionally including the step of providing dopant gases during the step of irradiation of the film, thereby producing a doped film.

7. The method of claim 1, additionally including the step of providing the film of material with semiconductor or component gases to control stoichiometry of semiconductor materials or to produce heterojunctions.

8. The method of claim 1, additionally including the step of providing the film of material with a metal containing gas to help form a contact.

18. Polycrystalline thin films formed by the method of claim 1.

9. A method for fabricating thin films for use in solar cells, including the steps of:

forming at least one film of material on a substrate at a temperature of not greater than about 450°

C.; and

directing at least one pulse of laser radiation onto at least a portion of the at least one film for causing recrystallization and increased crystal grain size of the film material without raising the temperature of the substrate above about 180°

C. for longer than about 100 μ

s.

10. The method of claim 9, wherein the at least one film of material was formed to a thickness of not greater than about 10 μ

m.

11. The method of claim 10, wherein the at least one film is formed from material selected from the group of amorphous silicon, cadmium-tellurium, copper-indium-selenium, gallium-arsenic, copper-indium-sulfur, and cadmium-sulfur.

12. The method of claim 11, wherein the at least one pulse of laser energy was produced by a laser selected from the group of dye, excimer, and flashlamp-pumped lasers, capable of producing a homogenized beam of up to about 100 μ

s duration with an energy of up to about 0.1-10 Jcm^-2 to the film material.

13. The method of claim 12, wherein the laser is a flashlamp-pumped dye laser, wherein the film of material is of copper-indium-selenium, and wherein the crystal grain size is increased from about 0.5-1 μ

m to about 2-4 μ

m by irradiation from the laser pulse.

14. The method of claim 12, wherein the laser is a flashlamp-pumped Ti:

sapphire laser, and wherein the film of material is of cadmium-tellurium.

15. The method of claim 12, wherein the laser is an XeCl excimer laser, wherein the film of material is of amorphous silicon, and wherein the amorphous silicon is crystallized by the laser pulse to form polycrystalline or microcrystalline silicon.

16. The method of claim 9, wherein the at least one pulse of laser radiation is produced by a laser operating at a wavelength in the range of about 197-1100 nm, and capable of producing pulses of up to about 100 μ

s and energy of up to about 10 Jcm^-2 to the film of material.

17. The method of claim 9, wherein the substrate is selected from the group of low-temperature materials consisting of E-CTFE, E-TFE, PES, PVDF, PTFE, FFP, and HDPE, and wherein the at least one film is formed on the substrate at a temperature of less than about 180°

C.