IP Library Granted Patent US 9,450,115
Granted Patent B2
US 9,450,115 · App. 14/212,584 · Granted Sep 20, 2016

Method of manufacturing a photovoltaic device

Inventors: Scott Christensen (Perrysburg, OH); Pawel Mrozek (Waterville, OH); Gang Xiong (Santa Clara, CA); San Yu (Perrysburg, OH)
Assignee: First Solar, Inc.
H01L31/022425H01L31/03925H01L31/073Y02E10/543
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 9,450,115
App. No.
14/212,584
Granted
Sep 20, 2016
Kind
B2
Abstract

A method to improve CdTe-based photovoltaic device efficiency is disclosed, the method including steps for removing surface contaminants from a semiconductor absorber layer prior to the deposition or formation of a back contact layer on the semiconductor absorber layer, the surface contaminants removed using at least one of a dry etching process and a wet etching process.

Claims (30)

1. A method of manufacturing a photovoltaic device comprising the steps of:

depositing a semiconductor absorber layer adjacent to a substrate;

cleaning the semiconductor absorber layer to remove contaminants therefrom using in succession a dry etch followed by a wet etch, the wet etch performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl;

in a desorption step, placing the semiconductor layer and the substrate in a vacuum and applying thermal energy to remove surface moisture from the semiconductor absorber layer; and

depositing a back contact layer adjacent to the semiconductor absorber layer;

wherein the cleaning the semiconductor absorber layer step and the desorption step are performed prior to the deposition of the back contact layer.

2. The method of claim 1 , wherein the back contact layer is formed from one of the group of a polycrystalline zinc telluride, ZnTe:Cu, CdZnTe, and a multi-layer stack including at least two of CdTe, CdZnTe, ZnTe, and ZnTe:Cu.

3. The method of claim 1 , wherein the wet etch is performed using an HCl-containing solution chosen from a list consisting of a solution having about 8500 ppm HCl, about 0.09% to about 3.7% HCl, about 0.09% to about 3.7% HCl, 3.7% HCl (10/1 HCl), a two-step wet etch with a NH 4 OH/H 2 O 2 mixture and HCl, and an HNO 3 /HCl mixture.

4. The method of claim 1 , wherein the dry etch utilizes an oxygen plasma etching process removes hydrocarbons and other carbon-containing contaminants from the semiconductor absorber layer.

5. The method of claim 4 , wherein the wet etch of the semiconductor absorber layer removes oxidized material utilizing a HCl-containing solution.

6. The method of claim 4 , further comprising a step of rinsing the semiconductor absorber layer after the cleaning step with one of the group of a deionized water and a purified water.

7. The method of claim 6 , further comprising a step of removing surface moisture from the semiconductor absorber layer prior to the depositing of the back contact layer step.

8. The method of claim 1 , wherein the wet etch is performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl at about 0.09% to about 3.7% HCl.

9. A method of manufacturing a photovoltaic device comprising the steps of:

depositing a semiconductor absorber layer adjacent to a substrate;

cleaning the semiconductor absorber layer to remove contaminants therefrom using a dry etch of the semiconductor absorber layer followed in succession by a wet etch of the semiconductor absorber layer, the wet etch performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl;

in a desorption step, placing the semiconductor layer and the substrate in a vacuum and applying thermal energy to remove surface moisture from the semiconductor absorber layer after the cleaning step; and

depositing a back contact layer adjacent to the semiconductor absorber layer.

10. The method of claim 9 , wherein the back contact layer is formed from one of the group of a polycrystalline zinc telluride, ZnTe:Cu, CdZnTe, and a multi-layer stack including at least two of CdTe, CdZnTe, ZnTe, and ZnTe:Cu.

11. The method of claim 9 , wherein the wet etch is performed using an HCl-containing solution chosen from a list consisting of a solution having about 8500 ppm HCl, about 0.09% to about 3.7% HCl, 3.7% HCl (10/1 HCl), a two-step wet etch with a NH 4 OH/H 2 O 2 mixture and HCl, and an HNO 3 /HCl mixture.

12. The method of claim 9 , wherein the dry etch utilizes an oxygen plasma etching process removing hydrocarbons and other carbon-containing contaminants from the semiconductor absorber layer.

13. The method of claim 9 , further comprising the step of rinsing the semiconductor absorber layer after the cleaning step with one of the group of a deionized water and a purified water.

14. The method of claim 9 , wherein the wet etch is performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl at about 0.09% to about 3.7% HCl.

15. A method of manufacturing a photovoltaic device comprising the steps of:

depositing a CdTe semiconductor absorber layer adjacent to a substrate;

cleaning the CdTe semiconductor absorber layer to remove contaminants therefrom using a dry etch followed in succession by a wet etch, the wet etch performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl;

in a desorption step, placing the semiconductor layer and the substrate in a vacuum and applying thermal energy to remove surface moisture from the CdTe semiconductor absorber layer; and

depositing a ZnTe back contact layer adjacent to the CdTe semiconductor absorber layer.

16. The method of claim 15 , wherein the dry etch utilizes an oxygen plasma etching process removes hydrocarbons and other carbon-containing contaminants from the semiconductor absorber layer and the wet etch utilizes a HCl-containing solution chosen from a list consisting of a solution having about 8500 ppm HCl, about 0.09% to about 3.7% HCl, 3.7% HCl (10/1 HCl), a two-step wet etch with a NH 4 OH/H 2 O 2 mixture and HCl, an HNO 3 /HCl mixture, and an HCl/H 3 PO 4 mixture.

17. The method of claim 15 , wherein the wet etch is performed using a solution including HCl/H 3 PO 4 that results in the semiconductor absorber layer having a Te-rich surface and a Cd/Te ratio that is lower than the Cd/Te ratio obtained when the wet etch is performed using a solution including only HCl at about 0.09% to about 3.7% HCl.

Assignments (5)
RELEASE OF SECURITY INTEREST Recorded Feb 13, 2026
From: JPMORGAN CHASE BANK, N.A.
To: FIRST SOLAR, INC.
Reel/Frame 074858/0364 →
SECURITY INTEREST Recorded Jul 10, 2023
From: FIRST SOLAR, INC.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 064237/0462 →
TERMINATION AND RELEASE OF SECURITY INTEREST IN PATENT RIGHTS Recorded Nov 15, 2021
From: JPMORGAN CHASE BANK, N.A.
To: FIRST SOLAR, INC.
Reel/Frame 058132/0566 →
PATENT SECURITY AGREEMENT Recorded Jul 12, 2017
From: FIRST SOLAR, INC.
To: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 043177/0581 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 20, 2014
From: CHRISTENSEN, SCOTT; MROZEK, PAWEL; YU, SAN; XIONG, GANG
To: FIRST SOLAR, INC.
Reel/Frame 032482/0264 →
Continuity (2)
Provisional Application 61791442 · Mar 15, 2013
Related Publication 20140273334A1 · Sep 18, 2014