# US 11,993,729 B2 · Chemical mechanical polishing composition

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- Number: US 11,993,729 B2
- Document ID: US11993729B2
- Status: Granted
- Kind: B2
- Application number: 16/765,665
- Filed: 2018-11-12
- Published: 2020-09-24
- Granted: 2024-05-28
- Earliest claimed: 2017-11-22
- Assignees: BASF SE
- Applicants: BASF SE
- Inventors: Christian Daeschlein; Max Siebert; Yongqing Lan; Michael Lauter; Sheik Ansar Usman Ibrahim; Reza M Golzarian; Te Yu Wei; Haci Osman Guevenc; Julian Proelss; Leonardus Leunissen
- Web page: https://patentgrep.com/patent/US11993729B2

## CPC

- C09G 1/02: containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)}
- H10P 52/403: {of conductive or resistive materials}
- C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

The presently claimed subject matter is directed to a chemical mechanical polishing (CMP) composition comprising inorganic particles, at least one organic compound comprising an amino group and/or at least one acid group (Y), potassium persulfate, at least one corrosion inhibitor and an aqueous medium for polishing substrates of the semiconductor industry comprising cobalt and/or a cobalt alloy and TiN and/or TaN.

## Claims

### Claim 1

A process for chemical mechanical polishing of a substrate comprising (i) cobalt and/or (ii) a cobalt alloy, and (iii) TiN and TaN, the process comprising contacting the substrate with a chemical mechanical polishing composition, comprising:
(A) ≥0.10 wt.-% to ≤4.00 wt.-% of inorganic particles,
(B) ≥0.10 wt.-% to ≤0.90 wt.-% of at least one organic compound comprising an amino group and/or at least one acid group (Y),
(C) ≥0.20 wt.-% to ≤0.90 wt.-% of potassium persulfate,
(D) ≥95.00 wt.-% to ≤99.58 wt.-% of an aqueous medium,
(E) ≥0.01 wt.-% to ≤0.50 wt.-% of at least one corrosion inhibitor, and
(K) ≥0.01 wt.-% to ≤1.50 wt.-% of at least one additive,
wherein the chemical mechanical polishing composition has a pH of ≥8.5 to ≤11.0, and
wt.-% is based on a total weight of the chemical mechanical polishing composition;
wherein the composition contains no oxidant other than (c); and
wherein a TiN:TaN ratio of material removal rate (MRR) is in a range of ≥0.5 to ≤2.0.

### Claim 2

A process for chemical mechanical polishing of a substrate comprising (i) cobalt and/or (ii) a cobalt alloy, and (iii) TiN and TaN, the process comprising contacting the substrate with a chemical mechanical polishing composition, comprising:
(A) ≥0.10 wt.-% to ≤4.00 wt.-% of inorganic particles,
(B) ≥0.10 wt.-% to ≤0.90 wt.-% of at least one organic compound comprising an amino group and/or at least one acid group (Y), (C) ≥0.20 wt.-% to ≤0.90 wt.-% of potassium persulfate, (D) ≥95.00 wt.-% to ≤99.58 wt.-% of an aqueous medium, (E) ≥0.01 wt.-% to ≤0.50 wt.-% of at least one corrosion inhibitor, and (K) ≥0.01 wt.-% to ≤1.50 wt.-% of at least one additive,
wherein wt.-% is based on a total weight of the chemical mechanical polishing composition, and wherein the chemical mechanical polishing composition has a pH of ≥8.5 to ≤10.0;
wherein the composition contains no oxidant other than (c): and
wherein a TiN:TaN ratio of material removal rate (MRR) is in a range of ≥0.5 to ≤2.0.

### Claim 3 (depends on 1)

The process of claim 1, wherein the chemical mechanical polishing composition comprises ≥0.30 wt.-% to ≤0.70 wt.-% of potassium persulfate (C).

### Claim 4 (depends on 1)

The process of claim 1, wherein the inorganic particles (A) are colloidal inorganic particles.

### Claim 5 (depends on 4)

The process of claim 4, wherein the colloidal inorganic particles are colloidal silica particles.

### Claim 6 (depends on 1)

The process of claim 1, wherein the at least one organic compound (B) is a non-polymeric compound with a molecular weight below 600 g/mol.

### Claim 7 (depends on 1)

The process of claim 1, wherein the at least one acid group (Y) of the at least one organic compound (B) is selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid.

### Claim 8 (depends on 1)

The process of claim 1, wherein the at least one organic compound (B) is selected from the group consisting of amino acids, substituted ethylenediamine and polycarboxylic acids.

### Claim 9 (depends on 1)

The process of claim 1, wherein the at least one organic compound (B) is selected from the group consisting of glycine, glutamic acid, aspartic acid, ethylenediaminetetraacetic acid, diethylene triamine pentaacetic acid, cysteic acid, aminotris(methylenephosphonic acid), diethylenetriamine penta(methylene phosphonic acid), ethylenediamine tetra(methylene phosphonic acid), malonic acid, citric acid and tartaric acid.

### Claim 10 (depends on 1)

The process of claim 1, wherein the aqueous medium is de-ionized water.

### Claim 11 (depends on 1)

The process of claim 1, wherein the at least one corrosion inhibitor (E) is selected from the group consisting of imidazole, benzimidazole, benzotriazole, 4-(dimethylamino) benzoic acid, terephthalic acid, isophthalic acid, 6,6′6″ -(1,3,5-triazine-2,4,6-triyltriimino)trihexanoic acid, phenyltetrazole, N-lauroylsarcosine, 4-dodecylbenzene sulfonic acid, phosphoric acid C6-C10 alkyl ester, polyaspartate and mixtures and salts thereof.

### Claim 12 (depends on 1)

The process of claim 1, wherein the at least one additive (K) is selected from the group consisting of surfactants (F), biocides (H), pH adjusting agents, buffer substances, stabilizers and friction reducing agents.

### Claim 13

A process for the manufacture of a semiconductor device, the process comprising chemical mechanical polishing of a substrate comprising
(i) cobalt, and/or
(ii) a cobalt alloy, and
(iii) TiN and TaN in the presence of a chemical mechanical polishing composition, comprising:
(A) ≥0.10 wt.-% to ≤4.00 wt.-% of inorganic particles,
(B) ≥0.10 wt.-% to ≤0.90 wt.-% of at least one organic compound comprising an amino group and/or at least one acid group (Y),
(C) ≥0.20 wt.-% to ≤0.90 wt.-% of potassium persulfate,
(D) ≥95.00 wt.-% to ≤99.58 wt.-% of an aqueous medium,
(E) ≥0.01 wt.-% to ≤0.50 wt.-% of at least one corrosion inhibitor, and
(K) ≥0.01 wt.-% to ≤1.50 wt.-% of at least one additive,
wherein the chemical mechanical polishing composition has a pH of ≥8.5 to ≤11.0, and
wt.-% is based on a total weight of the chemical mechanical polishing composition;
wherein the composition contains no oxidant other than (c).; and
wherein a TiN:TaN ratio of material removal rate (MRR) is in a range of ≥0.5 to ≤2.0.

### Claim 14 (depends on 1)

The process of claim 1, wherein the chemical mechanical polishing composition has a pH of ≥8.5 to <10.0.

### Claim 15 (depends on 13)

The process according to claim 13, wherein the chemical mechanical polishing composition has a pH of ≥8.5 to <10.0.

### Claim 16 (depends on 1)

The process of claim 1, wherein the chemical mechanical polishing composition has a pH of ≥8.5 to ≤9.0.

### Claim 17 (depends on 13)

The process according to claim 13, wherein the chemical mechanical polishing composition has a pH of ≥8.5 to ≤9.0.

### Claim 18 (depends on 1)

The process of claim 1, wherein the at least one organic compound (B) is glycine.

### Claim 19 (depends on 1)

The process according to claim 1, wherein the process has a material removal rate of TiN of ≥50 to ≤650 Å/min.

### Claim 20 (depends on 1)

The process according to claim 1, wherein a TiN:TaN ratio of material removal rate (MRR) is in a range of ≥0.5 to ≤1.4.

### Claim 21 (depends on 1)

The process according to claim 1, wherein the process results in a material removal rate (MRR) of Co in an amount of from 332 to 4268 Å/min, of TiN in an amount of from 32 to 520 A/min, and of TaN in an amount of from 56 to 390 Å/min.