Thick-film pastes containing lead- and tellurium-oxides, and their use in the manufacture of semiconductor devices

Patent metadata

Field	Value
Publication number	US-10069020-B2
Application number	US-201313800592-A
Country	US
Kind code	B2
Filing date	Mar 13, 2013
Priority date	May 4, 2010
Publication date	Sep 4, 2018
Grant date	Sep 4, 2018

Abstract

The present invention provides a thick-film paste for printing the front-side of a solar cell device having one or more insulating layers. The thick-film paste comprises an electrically conductive metal, and a lead-tellurium-oxide dispersed in an organic medium.

First claim

What is claimed is:

1. A thick-film paste composition for use in forming an electrical connection in a photovoltaic device comprising a semiconductor substrate having at least one insulating layer on a main surface thereof, the composition comprising:
a) 96.55 to 99.5% by weight of an electrically conductive metal or derivative thereof, based on total solids in the composition;
b) 0.5 to 3.45% by weight based on solids of a lead-tellurium-oxide, wherein the lead-tellurium-oxide comprises at least 35 mole % of TeO 2 and the weight ratio of elemental lead to elemental tellurium in the lead-tellurium-oxide is within the range of 0.87 to 9.51; and
c) an organic medium;
wherein the thick-film paste, when fired, is capable of penetrating the at least one insulating layer.

2. The thick-film paste of claim 1 , wherein the electrically conductive metal comprises silver.

3. The thick-film paste of claim 1 , wherein the organic medium comprises a polymer.

4. The thick-film paste of claim 3 , wherein the organic medium further comprises one or more additives selected from the group consisting of solvents, stabilizers, surfactants, and thickeners.

5. The thick-film paste of claim 1 , wherein the Pb—Te—O is at least partially crystalline.

6. The thick-film paste of claim 1 , further comprising an additive selected from the group consisting of: TiO 2 , Li 2 O, B 2 O 3 , PbF 2 , SiO 2 , Na 2 O, K 2 O, Rb 2 O, Cs 2 O, Al 2 O 3 , MgO, CaO, SrO, BaO, V 2 O 5 , ZrO 2 , MoO 3 , Mn 2 O 3 , Ag 2 O, ZnO, Ga 2 O 3 , GeO 2 , In 2 O 3 , SnO 2 , Sb 2 O 3 , Bi 2 O 3 , BiF 3 , P 2 O 5 , CuO, NiO, Cr 2 O 3 , Fe 2 O 3 , CoO, Co 2 O 3 , and CeO 2 .

7. The thick film paste of claim 1 , wherein the lead-tellurium oxide further comprises one or more elements selected from the group consisting of: Si, Sn, Li, Ti, Ag, Na, K, Rb, Cs, Ge, Ga, In, Ni, Zn, Ca, Mg, Sr, Ba, Se, Mo, W, Y, As, La, Nd, Co, Pr, Gd, Sm, Dy, Eu, Ho, Yb, Lu, Bi, Ta, V, Fe, Hf, Cr, Cd, Sb, Bi, F, Zr, Mn, P, Cu, Ce, and Nb.

8. A process comprising:
(a) providing a semiconductor substrate comprising one or more insulating films deposited onto at least one surface of a semiconductor substrate;
(b) applying a thick-film paste composition onto at least a portion of the insulating film to form a layered structure,
wherein the thick-film paste composition comprises:
i) 96.55% to 99.5% by weight of an electrically conductive metal or derivative thereof, based on total solids in the composition;
ii) 0.5 to 3.45% by weight based on solids of a lead-tellurium-oxide, wherein the lead-tellurium-oxide comprises at least 35 mole % of TeO 2 and the weight ratio of elemental lead to elemental tellurium in the lead-tellurium-oxide is within the range of 0.87 to 9.51; and
iii) an organic medium; and

(c) firing the semiconductor substrate, one or more insulating films, and thick-film paste, forming an electrode in contact with the one or more insulating layers and in electrical contact with the semiconductor substrate.

9. The process of claim 8 , wherein the thick-film paste composition is applied pattern-wise onto the insulating film.

10. The process of claim 8 , wherein the firing is carried out in air or an oxygen-containing atmosphere.

11. An article comprising:
a) a semiconductor substrate;
b) one or more insulating layers on the semiconductor substrate; and
c) an electrode in contact with the one or more insulating layers and in electrical contact with the semiconductor substrate, the electrode comprising 96.55 to 99.5% by weight based on solids of an electrically conductive metal and 0.5 to 3.45% by weight based on solids of lead-tellurium-oxide, wherein the lead-tellurium-oxide comprises at least 35 mole % of TeO 2 and the weight ratio of elemental lead to elemental tellurium in the lead-tellurium-oxide is within the range of 0.87 to 9.51.

12. The article of claim 11 , wherein the article is a semiconductor device.

13. The article of claim 12 , wherein the semiconductor device is a solar cell.

14. The thick film paste of claim 1 , wherein the lead-tellurium-oxide comprises one or more glass frits.

15. The process of claim 8 , wherein the lead-tellurium-oxide comprises one or more glass frits.

16. The thick film paste of claim 2 , wherein the silver comprises at most 9.5% silver flakes by weight of the total solids.

Assignees

• Du Pont

Inventors

• Carroll Alan Frederick
• Hang Kenneth Warren
• Laughlin Brian J
• Mikeska Kurt Richard
• Torardi Carmine
• Vernooy Paul Douglas

Classifications

• B22F7/04

  with one or more layers not made from powder, e.g. made from solid metal · CPC title

• H01B1/16

  the conductive material comprising metals or alloys · CPC title

• B22F2007/047

  non-pressurised baking of the paste or slurry containing metal powder · CPC title

• H01B1/22 Primary

  the conductive material comprising metals or alloys · CPC title

• C04B35/01

  based on oxide ceramics · CPC title