Barrier chemical mechanical planarization composition and method thereof

Patent metadata

Field	Value
Publication number	US-9574110-B2
Application number	US-201414502186-A
Country	US
Kind code	B2
Filing date	Sep 30, 2014
Priority date	Oct 11, 2013
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

A barrier chemical mechanical planarization polishing composition is provided that includes suitable chemical additives. The suitable chemical additives are organic polymer molecules containing ethylene oxide repeating units having the general molecular structure of

where n refers to the total numbers of the repeating unit giving the molecular weights of polyethylene oxide ranging from 100,000 to 8,000,000. There is also provided a chemical mechanical polishing method using the barrier chemical mechanical planarization polishing composition.

First claim

The invention claimed is:

1. A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface having conductive metal lines, vias or trenches, a metal-containing barrier layer and a dielectric layer, comprising the steps of:
a) contacting the at least one surface with a polishing pad;
b) delivering a barrier polishing composition to the at least one surface, the polishing composition consisting essentially of:
abrasive;
organic polymer containing ethylene oxide repeating units having the general molecular structure of

wherein n refers to the total numbers of the repeating unit giving molecular weights ranging from 100,000 to 8,000,000 and concentration ranging from about 5 ppm to about 5,000 ppm;

oxidizing agent;
corrosion inhibitor;
chelator selected from the group consisting of benzosulfonic acid, 4-tolyl sulfonic acid, 2,4-diamino-benzosulfonic acid, itaconic acid, gluconic acid, mandelic acid, and combinations thereof; and
water;

and
c) polishing at least the metal-containing barrier layer on the substrate with the barrier polishing composition.

2. The method of claim 1 wherein the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 400,000 to 1,500,000; and concentration ranging from about 25 ppm to about 2,000 ppm.

3. The method of claim 1 wherein the abrasive is selected from the group consisting of colloidal silica, alumina, ceria, germania, silica, titania, zirconia, alumina dopes colloidal silica in lattices, organic polymer particles, composite particles comprising organic and inorganic particles, surface modified organic or inorganic particles, and combinations thereof; and is present in an amount ranging from about 0.1% to about 15 wt %.

4. The method of claim 1 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, amine compounds, and combinations thereof; and is present in an amount ranging from about 0.01 wt % to about 10 wt %.

5. The method of claim 1 wherein the corrosion inhibitor is selected from the group consisting of benzotriazole or benzotriazole derivative, 3-amino-1, 2, 4-triazole, 3, 5-diamine-1, 2, 4-triazole, and combinations thereof; and is present in an amount ranging from about 0.001 wt % to about 1.0 wt %.

6. The method of claim 1 wherein the chelator is present in an amount ranging from about 0.01 wt % to about 3.0 wt %.

7. The method of claim 1 wherein the conductive metal is copper; the metal-containing barrier layer is a tantalum-containing barrier layer; the dielectric layer is selected from the group consisting of TEOS, and low-k material.

8. A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface having conductive metal lines, vias or trenches, a metal-containing barrier layer and a dielectric layer, comprising the steps of:
a) contacting the at least one surface with a polishing pad;
b) delivering a barrier polishing composition to the at least one surface, the polishing composition consisting essentially of:
abrasive;
organic polymer containing ethylene oxide repeating units having the general molecular structure of

wherein n refers to the total numbers of the repeating unit giving molecular weights ranging from 100,000 to 8,000,000 and concentration ranging from about 5 ppm to about 5,000 ppm;

oxidizing agent;
corrosion inhibitor;
chelator selected from the group consisting of benzosulfonic acid, 4-tolyl sulfonic acid, 2,4-diamino-benzosulfonic acid, itaconic acid, gluconic acid, mandelic acid, and combinations thereof;
a pH adjustor, present in an amount ranging from about 0.0001 wt % to 2 wt %, selected from the group consisting of (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, fatty acid, polycarboxylic acid and combinations thereof to lower pH of the polishing composition; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof to raise pH of the polishing composition; and,
water;
wherein the polishing composition has a pH from about 2 to about 12; and,

c) polishing at least the metal-containing barrier layer on the substrate with the barrier polishing composition.

9. A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface having conductive metal lines, vias or trenches, a metal-containing barrier layer and a dielectric layer, comprising the steps of:
a) contacting the at least one surface with a polishing pad;
b) delivering a barrier polishing composition to the at least one surface, the polishing composition consisting essentially of:
abrasive;
organic polymer containing ethylene oxide repeating units having the general molecular structure of

wherein n refers to the total numbers of the repeating unit giving molecular weights ranging from 100,000 to 8,000,000 and concentration ranging from about 5 ppm to about 5,000 ppm;

oxidizing agent;
corrosion inhibitor;
chelator selected from the group consisting of benzosulfonic acid, 4-tolyl sulfonic acid, 2,4-diamino-benzosulfonic acid, itaconic acid, gluconic acid, mandelic acid, and combinations thereof;
a surfactant selected from the group consisting of nonionic, anionic, cationic or amphoteric surfactants, and combinations thereof; and is present in an amount ranging from about 0.0001 wt % to about 1.0 wt %; and,
water;

and
c) polishing at least the metal-containing barrier layer on the substrate with the barrier polishing composition.

10. The method of claim 9 wherein the abrasive is colloidal silica and is present in an amount ranging from about 1 wt % to about 3 wt %; the oxidizing agent is hydrogen peroxide and is present in an amount ranging from about 0.5 wt % to about 2 wt %; the corrosion inhibitor is benzotriazole or benzotriazole derivative and is present in an amount ranging from about 0.01 wt % to about 0.1 wt %; the chelator is benzosulfonic acid and is present in an amount ranging from about 0.4 wt % to about 1.5 wt %; the organic polymer contains ethylene oxide repeating units having molecular weights ranging from 300,000 to 1,000,000, and is present in an amount ranging from about 50 ppm to about 1,000 ppm; the surfactant is tricosaethylene glycol dodecyl ether and is present in an amount ranging from about 0.010% to about 0.1%; the metal-containing barrier layer is a tantalum-containing barrier layer; the dielectric layer is selected from the group consisting of TEOS, and low-k material; and the composition has a pH from about 9 to about 11.5.

11. The method of claim 10 wherein the polishing composition providing a TaN to TEOS selectivity about 1.5 to about 0.84.

Assignees

• Air Prod & Chem
• Air Prod & Chem

Inventors

• Graham Maitland Gary
• Schlueter James Allen
• Shi Xiaobo

Classifications

• H10P52/403

  of conductive or resistive materials · CPC title

• H10P52/402

  of semiconductor materials · CPC title

• C09G1/18

  on other substances · CPC title

• C09G1/02 Primary

  containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)} · CPC title

• C09K3/1463

  Aqueous liquid suspensions · CPC title