# US 7,410,899 B2 · Defectivity and process control of electroless deposition in microelectronics applications

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- Number: US 7,410,899 B2
- Document ID: US7410899B2
- Status: Granted
- Kind: B2
- Application number: 11/230,912
- Filed: 2005-09-20
- Published: 2007-03-22
- Granted: 2008-08-12
- Earliest claimed: 2005-09-20
- Assignees: Enthone Inc.
- Inventors: Qingyun Chen; Charles Valverde; Vincent Paneccasio; Nicolai Petrov; Daniel Stritch; Christian Witt; Richard Hurtubise
- Web page: https://patentgrep.com/patent/US7410899B2

## CPC

- C09D 5/10: containing metal dust
- C23C 18/34: using reducing agents
- C23C 18/50: with alloys based on iron, cobalt or nickel
- H10P 14/46: using a liquid
- H10W 20/037: {the barrier, adhesion or liner layers being on top of a main fill metal}
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

Methods and compositions for electrolessly depositing Co, Ni, or alloys thereof onto a substrate in manufacture of microelectronic devices. Grain refiners, levelers, oxygen scavengers, and stabilizers for electroless Co and Ni deposition solutions.

## Claims

### Claim 1

A method for electrolessly depositing Co, Ni, or alloys thereof onto a substrate in manufacture of microelectronic devices, the method comprising:
contacting the substrate with an electroless deposition composition comprising (a) a grain refiner comprising a grain refiner compound selected from the group consisting of a polyphosphoric acid, a polyphosphate salt, and a combination thereof wherein said grain refiner compound is a compound having a formula M(n+2)PnO(3n+1) or (MPO3)n, where M represents a counter ion, and n=3 to 600; and (b) a source of deposition ions selected from the group consisting of Co ions and Ni ions.

### Claim 2 (depends on 1)

The method of claim 1 wherein the grain refiner compound is ammonium polyphosphate.

### Claim 3 (depends on 1)

The method of claim 1 wherein the grain refiner compound is sodium polyphosphate.

### Claim 4 (depends on 1)

The method of claim 1 wherein the grain refiner compound is polyphosphoric acid.

### Claim 5 (depends on 1)

The method of claim 1 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 1 g/L and about 100 g/L.

### Claim 6 (depends on 1)

The method of claim 1 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 4 g/L and about 50 g/L.

### Claim 7 (depends on 1)

The method of claim 1 wherein the electroless deposition composition further comprises a reducing agent.

### Claim 8 (depends on 1)

The method of claim 1 wherein the electroless deposition composition further comprises an oxygen scavenger compound selected from the group consisting of ascorbic acid, SO32−, HSO3−, hydroquinone, catechol, resorcinol, hydrazine, and combinations thereof.

### Claim 9 (depends on 1)

The method of claim 1 wherein the electroless deposition composition further comprises a stabilizer compound selected from the group consisting of an aminobenzoic acid, an hydroxybenzoic acid, a molybdenum oxide, a vanadium oxide, a rhenium oxide, salts thereof, derivatives thereof, and combinations thereof.

### Claim 10 (depends on 1)

The method of claim 1 wherein the electroless deposition composition further comprises a leveler selected from the group consisting of diphenyl oxide disulfonic acids, triethanolamine salts of lauryl sulfate, ammonium laureth sulfates, alkylbenzene sulfonates, dodecylbenzene sulfonic acids, alkyldiphenyloxide disulfonate, low molecular weight polypropylene glycol, and combinations thereof.

### Claim 11 (depends on 1)

The method of claim 1 wherein the substrate is a copper metal layer located in a semiconductor integrated circuit device.

### Claim 12 (depends on 1)

The method of claim 1 wherein the electroless deposition composition further comprises an oxime-based stabilizer compound selected from the group consisting of salicylaldoxime, syn-2-pyridinealdoxime, dimethylglyoxime, 1,2-cyclohexanedione dioxime, diphenyl glyoxime, pyridyl diglyoxime, and combinations thereof.

### Claim 13

An electroless plating solution for plating a metal capping layer onto a metal-filled interconnect in a microelectronic device, the solution comprising:
a source of deposition ions selected from the group consisting of Co ions and Ni ions;
a reducing agent; and
a grain refiner compound selected from the group consisting of a polyphosphoric acid, a polyphosphate salt, and a combination thereof wherein said grain refiner compound is a compound having a formula M(n+2)PnO(3n+1) or (MPO3)n, where M represents a counter ion, and n=2 to 600.

### Claim 14 (depends on 13)

The plating solution of claim 13 wherein the grain refiner compound is ammonium polyphosphate.

### Claim 15 (depends on 13)

The plating solution of claim 13 wherein the grain refiner compound is sodium polyphosphate.

### Claim 16 (depends on 13)

The plating solution of claim 13 wherein the grain refiner compound is polyphosphoric acid.

### Claim 17 (depends on 13)

The plating solution of claim 13 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 1 g/L and about 100 g/L.

### Claim 18 (depends on 13)

The plating solution of claim 13 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 4 g/L and about 50 g/L.

### Claim 19 (depends on 13)

The plating solution of claim 13 wherein the electroless deposition composition further comprises an oxygen scavenger compound selected from the group consisting of ascorbic acid, SO32−, HSO3−, hydroquinone, catechol, resorcinol, hydrazine, and combinations thereof.

### Claim 20 (depends on 13)

The plating solution of claim 13 wherein the electroless deposition composition further comprises a stabilizer compound selected from the group consisting of an aminobenzoic acid, an hydroxybenzoic acid, a molybdenum oxide, a vanadium oxide, rhenium oxide, salts thereof, derivatives thereof, and combinations thereof.

### Claim 21 (depends on 13)

The plating solution of claim 13 wherein the electroless deposition composition further comprises a leveler selected from the group consisting of diphenyl oxide disulfonic acids, triethanolamine salts of lauryl sulfate, ammonium laureth sulfates, alkylbenzene sulfonates, dodecylbenzene sulfonic acids, alkyldiphenyloxide disulfonate, low molecular weight polypropylene glycol, and combinations thereof.

### Claim 22 (depends on 13)

The electroless plating solution of claim 13 further comprising an oxime-based stabilizer compound selected from the group consisting of salicylaldoxime, syn-2-pyridinealdoxime, dimethylglyoxime, 1,2-cyclohexanedione dioxime, diphenyl glyoxime, pyridyl diglyoxime, and combinations thereof.