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

Patent metadata

Field	Value
Publication number	US-2017298525-A1
Application number	US-201715488056-A
Country	US
Kind code	A1
Filing date	Apr 14, 2017
Priority date	Apr 15, 2016
Publication date	Oct 19, 2017
Grant date	—

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 (Cu 2+ ) 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 metallisation by copper of a conductive metal oxide substrate as well as the surfaces of a modified and metallised conductive metal oxide substrate thus obtained.

First claim

1 . Method for modifying the surface of an electrically conductive metal oxide substrate, said method comprising the following steps consisting in:
i) bringing into contact the surface of said electrically conductive metal oxide 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 electrically conductive metal oxide substrate thus obtained; ii) bringing into contact the surface of said electrically conductive metal oxide substrate obtained following step (i) with a solution containing sodium tetraborohydride then washing and optionally drying the surface of said electrically conductive metal oxide substrate.

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, advantageously selected from the group consisting of a nitrate, a sulphate, an acetate, a halide, a tetrafluoroborate and any of the hydrated forms thereof.

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 and advantageously between 0.06 and 0.2 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 and advantageously between 1.5 and 5 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., advantageously between 15° C. and 25° C. and, more particularly, at room temperature and generally for 1 min to 1 h, notably for 5 min to 30 min and, in particular, of the order of 15 min.

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, advantageously between 0.06 and 0.1 mol/L and, in particular, of the order of 0.08 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., advantageously between 35° C. and 50° C. and, more particularly, at a temperature of the order of 40° C. and generally for 1 to 15 min, notably for 2 and 10 min and, in particular, of the order of 5 min.

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 . Modified surface of an electrically conductive metal oxide substrate capable of being obtained following the modification method such as defined in claim 1 .

13 . Surface of an electrically conductive metal oxide substrate coated with a film of copper metal optionally according to a predetermined pattern capable of being obtained following the metallisation method such as defined in claim 8 .

14 . Use of a modified surface of an electrically conductive metal oxide substrate according to claim 12 in the field of photovoltaic cells; liquid crystal screens, plasma screens, touch screens; OLEDs; antistatic deposits as well as optical, reflective coverings, and anti-reflection coatings.

15 . Method according to claim 1 , characterised in that said electrically conductive metal oxide is ITO.

Assignees

• Commissariat Energie Atomique

Inventors

• Bourlier Yoan
• Berthelot Thomas

Classifications

• C25D3/38 Primary

  of copper · CPC title

• C25D5/022

  using masking means · CPC title

• C25D5/38

  of refractory metals or nickel · CPC title

• H01B1/026

  Alloys based on copper · CPC title

• C25D7/126

  for solar cells · CPC title