Method for modifying an electrically conductive oxide surface, use for electrodeposition of copper on said surface

Patent metadata

Field	Value
Publication number	US-10428435-B2
Application number	US-201715488056-A
Country	US
Kind code	B2
Filing date	Apr 14, 2017
Priority date	Apr 15, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

The present invention relates to a method for modifying the surface of a substrate made of electrically conductive metal oxide and notably made of ITO, comprising the following steps consisting in: (i) bringing into contact said surface with a solution containing copper ions (Cu2+) and ammonia then washing and optionally drying the surface thus obtained; and (ii) bringing into contact the surface obtained following step (i) with a solution containing sodium tetraborohydride then washing and optionally drying the surface of said conductive metal oxide substrate. The present invention relates to the use of such a method within the scope of the metallization by copper of a conductive metal oxide substrate as well as the surfaces of a modified and metallized conductive metal oxide substrate thus obtained.

First claim

The invention claimed is:

1. Method for modifying the surface of an Indium Tin Oxide (ITO) substrate, said method comprising the following steps consisting in:
i) bringing into contact the surface of said ITO substrate with a solution containing at least one copper ion (Cu 2+ ) and at least ammonia then washing and optionally drying the surface of said ITO substrate thus obtained;
ii) bringing into contact the surface of said ITO substrate obtained following step (i) with a solution containing sodium tetraborohydride then washing and optionally drying the surface of said ITO substrate, whereby the ITO substrate surface that is obtained after step (ii) is a modified surface that does not present nanoparticles or clusters of copper.

2. Method according to claim 1 , characterised in that, during said step (i), the Cu 2+ ion is, in said solution, in the form of a copper salt.

3. Method according to claim 2 , characterised in that said copper salt is present, in said solution, in a quantity comprised between 0.05 and 0.25 mol/L.

4. Method according to claim 1 , characterised in that, during said step (i), ammonia is present, in said solution, in a quantity comprised between 1 and 6 mol/L.

5. Method according to claim 1 , characterised in that said step (i) is carried out at a temperature comprised between 10° C. and 30° C.

6. Method according to claim 1 , characterised in that, during said step (ii), sodium tetraborohydride is present in a quantity comprised between 0.03 and 0.15 mol/L.

7. Method according to claim 1 , characterised in that said step (ii) is carried out at a temperature comprised between 30° C. and 60° C.

8. Method for forming a film of copper metal on the surface of an electrically conductive metal oxide substrate, said method comprising the following steps consisting in:
a) preparing a surface of an electrically conductive metal oxide substrate modified in accordance with the modification method such as defined in claim 1 ;
b) electrodepositing copper metal on the surface of the modified substrate prepared during said step (a).

9. Method according to claim 8 , characterised in that said step (b) implements an electrodeposition bath comprising Cu 2+ ions being in the form of a copper salt.

10. Method according to claim 9 , characterised in that said electrodeposition bath is an aqueous acid solution containing Cu 2+ ions.

11. Method according to claim 8 , characterised in that the film of copper metal is formed on the surface of the electrically conductive metal oxide substrate according to a predetermined pattern and in that said method comprises:
prior to said step (a), steps consisting in depositing on the surface of the electrically conductive metal oxide substrate a layer of photosensitive resin then eliminating, by photolithography, the resin layer at given sites thus creating said pattern and
once said step (b) has been carried out, a step consisting in eliminating the remaining photosensitive resin whereby the electrically conductive metal oxide substrate no longer has resin on the surface thereof.

12. Method according to claim 1 , characterised in that, during said step (i), the Cu 2+ ion is, in said solution, selected from a group consisting of a nitrate, a sulphate, an acetate, a halide, a tetrafluoroborate and any of the hydrated forms thereof.

13. Method according to claim 2 , characterised in that said copper salt is present, in said solution, in a quantity comprised between 0.06 and 0.2 mol/L.

14. Method according to claim 1 , characterised in that, during said step (i), ammonia is present, in said solution, in a quantity comprised between 1.5 and 5 mol/L.

15. Method according to claim 1 , characterised in that said step (i) is carried out at a temperature comprised between 15° C. and 25° C. for 15 min.

16. Method according to claim 1 , characterised in that, during said step (ii), sodium tetraborohydride is present in a quantity of 0.08 mol/L.

17. Method according to claim 1 , characterised in that said step (ii) is carried out at a temperature of 40° C. for 5 min.

Assignees

• Commissariat Energie Atomique

Inventors

• Bourlier Yoan
• Berthelot Thomas

Classifications

• C25D5/38

  of refractory metals or nickel · CPC title

• C25C5/02

  from solutions · CPC title

• C25D7/126

  for solar cells · CPC title

• C25D5/022

  using masking means · CPC title

• H01B1/026

  Alloys based on copper · CPC title