IP Library Granted Patent US 8,366,954
Granted Patent B2
US 8,366,954 · App. 13/138,144 · Granted Feb 5, 2013

Solution for increasing wafer sheet resistance and/or photovoltaic cell power density level

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Quick Facts
Patent No.
US 8,366,954
App. No.
13/138,144
Granted
Feb 5, 2013
Kind
B2
Abstract

Treating thin film amorphous or mono- or multi-crystalline silicon wafer substrate for use in a photovoltaic cell, the wafer substrate having at least one of a pn- or np junction and a partial phosphosilicate or borosilicate glass layer on a top surface of the wafer substrate, to increase at least one of (a) the sheet resistance of he wafer and (b) the power density level of the photovoltaic cell made from said wafer. The treatment solution being an acidic treatment solution of a buffered oxide etch (BOE) solution of at least one tetraalkylammonium hydroxide, acetic acid, at least one non-ionic surfactant, at least one metal chelating agent, a metal free source of ammonia, a metal free source, of fluoride ions, and water, mixed with an oxidizer solution and optionally water.

Claims (41)

1. A method of treating a thin film amorphous or mono- or multi-crystalline silicon wafer substrate for use in a photovoltaic cell, the wafer substrate having at least one of a pn- or np junction and a partial phosphosilicate or borosilicate glass layer on a top surface of the wafer substrate, to increase at least one of (a) the sheet resistance and (b) the power density of the photovoltaic cell, the method comprising contacting the wafer substrate with an acidic treatment solution for a time and at a temperature sufficient to increase at least one of (a) the sheet resistance of the wafer and (b) the power density of the photovoltaic cell made from said wafer, the acidic treatment solution comprising:

a buffered oxide etch (BOE) solution of:

from about 0.1 to about 20% by weight of at least one tetraalkylammonium hydroxide,

from about 0.1 to about 5% by weight acetic acid,

from about 0.1 to about 5% by weight of at least one non-ionic surfactant,

about 0.1 to about 5% by weight of at least one metal chelating agent,

from about 0.1 to about 20% by weight of a metal free source of ammonium ions,

from about 0.01 to about 20% by weight of a metal free source of fluoride ions,

balance water to 100%,

mixed with a solution of oxidizer and optionally water in a ratio of oxidizer solution /water/BOE solution of 0.01-10/0-100/1.

2. A method according to claim 1 wherein the treatment occurs at a temperature of from about 20° to about 70° C.

3. A method according to claim 1 wherein BOE solution has a pH of from about 3 to about 6.

4. A method according to claim 3 wherein the BOE solution has a pH of from about 4.3 to about 5.

5. A method according to claim 1 wherein the oxidizer solution comprises hydrogen peroxide.

6. A method according to claim 1 wherein the BOE solution comprises tetramethylammonium hydroxide as the tetraalkylammonium hydroxide, 3,5-dimethylhex -1-yn3-ol as the at least one surfactant, and EDTA as the at least one metal chelating agent, and the oxidizer solution comprises hydrogen peroxide and water.

7. A method according to claim 6 wherein the BOE solution comprises about 3.1% tetramethylammonium hydroxide, about 1.2% acetic acid, about 2.1% HF, about 0.8% 3,5-dimethylhex -1-yn-3-ol about 0.8% ammonium hydroxide, about 0.6% EDTA, about 91.5% water.

8. A method according to claim 7 wherein the BOE solution is mixed with oxidiser solution in a ratio of BOE/water/30% hydrogen peroxide in the range 1/6/0.2-1.0.

9. A method according to claim 7 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/0.8.

10. A method according to claim 7 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/1.

11. A method according to claim 7 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/0.2.

12. A method according to claim 11 wherein the treatment occurs at a temperature of from about 20° to about 70° C.

13. A method according to claim 1 wherein the treatment also improves the efficiency of a photovoltaic cell made from this wafer.

14. An acidic treatment solution for treating a thin film amorphous or mono- or multi-crystalline silicon wafer substrates for use in a photovoltaic cell, the wafer substrate having at least one of a pn- or np junction and a partial phosphosilicate or borosilicate glass layer on a top surface of the wafer substrate, to increase at least one of (a) the sheet resistance of the wafer and (b) the power density of the photovoltaic cell made from said wafer, the acidic treatment solution comprising a mixture of:

a buffered oxide etch (BOE) solution of:

from about 0.1 to about 20% by weight of at least one tetraalkylammonium hydroxide,

from about 0.1 to about 5% by weight acetic acid,

from about 0.1 to about 5% by weight of at least one non-ionic surfactant,

about 0.1 to about 5% by weight of at least one metal chelating agent,

from about 0.1 to about 20% by weight of a metal free source of ammonia ions,

from about 0.01 to about 20% by weight of a metal free source of fluoride ions,

balance water to 100%,

mixed with a solution of oxidizer and optionally water in a ratio of oxidizer solution/water/BOE solution of 0.01-10/0-100/1.

15. An acidic treatment solution according to claim 14 wherein the oxidizer solution comprises hydrogen peroxide.

16. An acidic treatment solution according to claim 14 wherein BOE solution has a pH of from about 3 to about 6.

17. An acidic treatment solution according to claim 16 wherein the BOE solution has a pH of from about 4.3 to about 5.

18. An acidic treatment solution according to claims 14 wherein the BOE solution comprises tetramethylammonium hydroxide as the tetraalkylammonium hydroxide, 3,5-dimethylhex-1-yn-3-ol as the at least one surfactant, and EDTA as the at least one metal chelating agent, and the oxidizer solution comprises hydrogen peroxide and water.

19. An acidic treatment solution according to claim 18 wherein the BOE solution comprises about 3.1% tetramethylammonium hydroxide, about 1.2% acetic acid, about 2.1% HF, about 0.8% 3,5-dimethylhex-1-yn-3-ol about 0.8% ammonium hydroxide, about 0.6% EDTA, about 91.5% water.

20. An acidic treatment solution according to claim 19 wherein the BOE solution is mixed with the oxidiser solution in a ratio of BOE/water/30% hydrogen peroxide solution within the range 1/6/0.2-1.0.

21. An acidic treatment solution according to claim 19 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/0.2.

22. An acidic treatment solution according to claim 19 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/0.8.

23. An acidic treatment solution according to claim 19 wherein the BOE solution is mixed with oxidizer solution in a ratio of BOE/water/30% hydrogen peroxide solution of about 1/6/1.

Assignments (12)
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENTS Recorded Nov 16, 2020
From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
To: AVANTOR PERFORMANCE MATERIALS, LLC; NUSIL TECHNOLOGY LLC; APPLIED SILICONE COMPANY LLC; RELIABLE BIOPHARMACEUTICAL, LLC; THERAPAK, LLC
Reel/Frame 054440/0877 →
SECURITY AGREEMENT Recorded Nov 29, 2017
From: AVANTOR PERFORMANCE MATERIALS, LLC; NUSIL TECHNOLOGY LLC; APPLIED SILICONE COMPANY LLC; RELIABLE BIOPHARMACEUTICAL, LLC; THERAPAK, LLC
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 044528/0960 →
SECURITY AGREEMENT Recorded Nov 28, 2017
From: AVANTOR PERFORMANCE MATERIALS, LLC; NUSIL TECHNOLOGY LLC; APPLIED SILICONE COMPANY LLC; RELIABLE BIOPHARMACEUTICAL, LLC; THERAPAK, LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 044811/0400 →
RELEASE (REEL 041966 / FRAME 0247) Recorded Nov 27, 2017
From: JEFFERIES FINANCE LLC
To: NUSIL TECHNOLOGY, LLC; APPLIED SILICONE COMPANY LLC; AVANTOR PERFORMANCE MATERIALS, LLC (FORMERLY AVANTOR PERFORMANCE MATERIALS, INC.)
Reel/Frame 044810/0154 →
RELEASE (REEL 041966 / FRAME 0211) Recorded Nov 27, 2017
From: JEFFERIES FINANCE LLC
To: NUSIL TECHNOLOGY, LLC; APPLIED SILICONE COMPANY, LLC; AVANTOR PERFORMANCE MATERIALS, LLC (FORMERLY AVANTOR PERFORMANCE MATERIALS, INC.)
Reel/Frame 044810/0207 →
SECURITY INTEREST Recorded Mar 10, 2017
From: NUSIL TECHNOLOGY LLC; APPLIED SILICONE COMPANY LLC; AVANTOR PERFORMANCE MATERIALS, LLC (FORMERLY KNOWN AS AVANTOR PERFORMANCE MATERIALS, INC.)
To: JEFFERIES FINANCE LLC
Reel/Frame 041966/0211 →
SECURITY INTEREST Recorded Mar 10, 2017
From: NUSIL TECHNOLOGY LLC; APPLIED SILICONE COMPANY LLC; AVANTOR PERFORMANCE MATERIALS, LLC (FORMERLY KNOWN AS AVANTOR PERFORMANCE MATERIALS, INC.)
To: JEFFERIES FINANCE LLC
Reel/Frame 041966/0247 →
CHANGE OF NAME Recorded Mar 2, 2017
From: AVANTOR PERFORMANCE MATERIALS, INC.
To: AVANTOR PERFORMANCE MATERIALS, LLC
Reel/Frame 041442/0976 →
RELEASE OF SECURITY INTEREST Recorded Jun 21, 2016
From: CREDIT SUISSE, AG, CAYMAN ISLANDS BRANCH
To: AVANTOR PERFORMANCE MATERIALS, INC.
Reel/Frame 038976/0233 →
SECURITY INTEREST Recorded Oct 3, 2014
From: AVANTOR PERFORMANCE MATERIALS, INC.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
Reel/Frame 033882/0488 →
CORRECTIVE ASSIGNMENT TO CORRECT THE NAME OF THE ASSIGNEE TO READ AVANTOR PERFORMANCE MATERIALS, BV PREVIOUSLY RECORDED ON REEL 026640 FRAME 0823. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Dec 26, 2012
From: HOOGBOOM, JOANNES T.V.; OOSTERHOLT, JOHANNES A.E.; RITMEIJER, SABRINA; GROENEWOUD, LUCAS M.H.
To: AVANTOR PERFORMANCE MATERIALS, BV
Reel/Frame 029539/0787 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 12, 2011
From: HOOGBOOM, JOANNES T.V.; OOSTERHOLT, JOHANNES A.E.; RITMEIJER, SABRINA; GROENEWOUD, LUCAS M.H.
To: AVANTOR PERFORMANCE MATERIALS BV.
Reel/Frame 026640/0823 →