IP Library Granted Patent US 7,354,792
Granted Patent B2
US 7,354,792 · App. 10/950,248 · Granted Apr 8, 2008

Manufacture of silicon-based devices having disordered sulfur-doped surface layers

Assignee: President and Fellows of Harvard College
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Quick Facts
Patent No.
US 7,354,792
App. No.
10/950,248
Granted
Apr 8, 2008
Kind
B2
Abstract

The present invention provides methods of fabricating a radiation-absorbing semiconductor wafer by irradiating at least one surface location of a silicon substrate, e.g., an n-doped crystalline silicon, by a plurality of temporally short laser pulses, e.g., femtosecond pulses, while exposing that location to a substance, e.g., SF 6 , having an electron-donating constituent so as to generate a substantially disordered surface layer (i.e., a microstructured layer) that incorporates a concentration of that electron-donating constituent, e.g., sulfur. The substrate is also annealed at an elevated temperature and for a duration selected to enhance the charge carrier density in the surface layer. For example, the substrate can be annealed at a temperature in a range of about 700 K to about 900 K.

Claims (49)

1. A method of fabricating a radiation-absorbing semiconductor structure, comprising:

irradiating each of a plurality of locations on a surface of a silicon substrate with one or more femtosecond laser pulses while exposing said surface to a sulfur-containing substance so as to generate a plurality of sulfur inclusions in a surface layer of said substrate, and

annealing said substrate at a temperature in a range of about 500 K to about 1100 K for a time duration in a range of about a few seconds to about a few hours.

2. The method of claim 1 , further comprising selecting a duration of each laser pulse to be in a range of about 50 femtoseconds to about 500 femtoseconds.

3. The method of claim 1 , further comprising selecting a fluence of each pulse to be in a range of about 1 kJ/m 2 to about 15 kJ/m 2 .

4. The method of claim 1 , further comprising selecting a central wavelength of said laser pulses to be in a range of about 200 nm to about 800 nm.

5. The method of claim 1 , wherein said irradiating step comprises exposing each location to a number of laser pulses ranging from 2 to about 500.

6. The method of claim 1 , further comprising subjecting each of said surface locations to successive laser pulses separated from one another by a time interval in a range of about 1 microsecond to about 1 millisecond.

7. The method of claim 1 , further comprising performing said annealing step in any of an inert atmosphere or a low-pressure atmosphere.

8. The method of claim 1 , further comprising selecting said sulfur-containing substance to be any of SF 6 and H 2 S.

9. The method of claim 1 , wherein said semiconductor structure absorbs radiation having wavelength components in a range of about 0.25 to about 10 microns.

10. The method of claim 1 , wherein said semiconductor structure absorbs radiation having wavelength components in a range of about 0.35 to about 2.5 microns.

11. The method of claim 1 , wherein said semiconductor structure exhibits a substantially uniform absorption for wavelength components in a range of about 1.2 to about 2.5 microns.

12. A method of fabricating a photodetector, comprising:

forming a semiconductor structure absorbing radiation in a wavelength range of about 0.25 to about 3.5 microns and exhibiting a diodic current-voltage characteristic in said wavelength range, said forming step comprising:

irradiating a surface of a silicon substrate at one or more locations thereof with one or more laser pulses having short pulse widths while exposing said surface to a sulfur-containing gas to generate a micro-structured layer having sulfur inclusions,

annealing said substrate at a temperature in a range of about 500 K to about 1000 K for a time duration in a range of about a few seconds to about a few hours, and

depositing a plurality of metallic contacts on selected portions of said semiconductor structure to allow applying a reverse bias voltage thereto.

13. The method of claim 12 , wherein said pulse widths are selected to be in a range of about tens of femtoseconds to about tens of nanoseconds.

14. The method of claim 12 , further comprising selecting said sulfur-containing substance to be any of SF 6 and H 2 S.

15. The method of claim 12 , further comprising performing said annealing step in an inert atmosphere.

16. The method of claim 12 , wherein said depositing step comprises thermally evaporating one or more selected metals on said selected portions of the semiconductor structure.

17. The method of claim 12 , further comprising selecting a thickness of said metal contacts to be in a range of about 5 nm to about 100 nm.

18. The method of claim 16 , wherein said depositing step comprises thermally evaporating a chromium layer followed by thermally evaporating a gold layer on a selected portion of said semiconductor structure to generate at least one of said metal contacts.

19. The method of claim 18 , further comprising selecting a thickness of said chromium layer to be in a range of about 1 nm to about 5 nm.

20. The method of claim 19 , further comprising selecting a thickness of said gold layer to be in a range of about 4 nm to about 100 nm.

21. The method of claim 12 , further comprising configuring said metal contacts so as to ensure that at least a portion of said micro-structured layer remains capable of receiving an external radiation.

22. A method of fabricating a semiconductor structure, comprising

irradiating a plurality of locations on a surface of a silicon substrate with one or more laser pulses having pulse widths in a range of about 50 to about 500 femtoseconds while exposing said surface to a substance having an electron-donating constituent so as to generate a micro-structured surface layer comprising inclusions incorporating said electron-donating constituent, and

annealing said substrate at an elevated temperature in a range of about 500 K to about 1100 K for a selected time period.

23. The method of claim 22 , further comprising selecting said electron-donating constituent to be any of chlorine (Cl 2 ), nitrogen (N 2 ) and air.

24. The method of claim 22 , wherein said irradiating step further comprises directing said laser pulses at said surface along a direction substantially perpendicular to said surface.

25. The method of claim 22 , wherein said selected annealing period is in a range of about a few seconds to about a few hours.

26. The method of claim 22 , wherein said annealing step is performed in an inert atmosphere.

27. A method of fabricating a radiation-absorbing semiconductor wafer, comprising:

irradiating at least one surface location of a silicon substrate with a plurality of temporally short laser pulses while exposing said location to a substance having an electron-donating constituent so as to generate a substantially disordered surface layer incorporating a concentration of said electron-donating constituent, and

annealing said substrate at an elevated temperature and for a duration selected to enhance charge carrier density in said substantially disordered surface layer.

28. The method of claim 27 , wherein said elevated temperature and duration are selected to cause re-arrangement of atomic bonds in said surface layer so as to increase concentration of carrier electrons in surface layer.

29. The method of claim 27 , wherein said elevated temperature and duration are selected to enhance electron carrier density in the surface layer by a factor of about 10% to about 200% relative to a pre-annealing level.

30. The method of claim 27 , wherein said elevated temperature and duration are selected to cause said surface layer to form a diode junction with underlying silicon substrate.

31. The method of claim 27 , wherein said elevated temperature and duration are selected such that said annealed substrate exhibits a responsivity in a range of about 1 A/W to about 200 A/W upon exposure of said surface layer to radiation having wavelengths in a range of about 250 nm to about 1100 nm and application of a reverse bias in a range of about 0.1 V to about 15 V to said wafer.

32. The method of claim 27 , wherein said elevated temperature is selected to be in a range of about 500 K to about 1100 K.

33. The method of claim 32 , wherein said duration is selected to be in a range of about a few seconds to about few hours.

34. The method of claim 27 , further comprising selecting said short laser pulses to have pulse widths in a range of about tens of femtoseconds to about tens of nanoseconds.

35. The method of claim 27 , further comprising selecting a fluence of said pulses and a partial pressure of said substance having an electron-donating constituent such that the concentration of said electron-donating constituent incorporated in said surface layer ranges from about 0.5 to about 5 atom percent.

36. A method of enhancing responsivity of a radiation-absorbing semiconductor wafer to incident radiation, comprising

irradiating at least one surface location of a silicon substrate with temporally short laser pulses while exposing the substrate to a substance having an electron-donating constituent so as to generate a microstructured surface layer having inclusions containing the electron-donating constituent, and

annealing the substrate at an elevated temperature and for a duration selected to enhance a responsivity of the microstructured substrate to radiation having at least one wavelength in a range of about 250 nm to about 1100 nm incident on the microstructured surface layer by at least a factor of about 10.

37. The method of claim 36 , wherein the annealing temperature lies in a range of about 700 K to about 900 K.

Assignments (2)
CONFIRMATORY LICENSE Recorded May 10, 2019
From: HARVARD UNIVERSITY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 049150/0249 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 14, 2005
From: MAZUR, ERIC; CAREY III, JAMES E.
To: PRESIDENT & FELLOWS OF HARVARD COLLEGE
Reel/Frame 016257/0644 →
Continuity (3)
Continuation In Part 1015542900 · May 24, 2002
Provisional Application 6029359000 · May 25, 2001
Related Publication 20080044943A1 · Feb 21, 2008