# US 11,999,876 B2 · Bulk ruthenium chemical mechanical polishing composition

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- Number: US 11,999,876 B2
- Document ID: US11999876B2
- Status: Granted
- Kind: B2
- Application number: 17/669,519
- Filed: 2022-02-11
- Published: 2022-05-26
- Granted: 2024-06-04
- Earliest claimed: 2018-03-28
- Assignees: Fujifilm Electronic Materials U.S.A., Inc.
- Applicants: Fujifilm Electronic Materials U.S.A., Inc.
- Inventors: David (Tawei) Lin; Bin Hu; Liqing (Richard) Wen; Yannan Liang; Ting-Kai Huang
- Web page: https://patentgrep.com/patent/US11999876B2

## CPC

- C09G 1/02: containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)}
- C23F 1/00: Etching metallic material by chemical means (manufacture of printing surfaces B41C; manufacture of printed circuits H05K)
- C23F 1/44: Compositions for etching metallic material from a metallic material substrate of different composition
- H10P 52/402: {of semiconductor materials}
- H10P 52/403: {of conductive or resistive materials}
- C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

The compositions of the present disclosure polish surfaces or substrates that at least partially include ruthenium. The composition includes a synergistic combination of ammonia and oxygenated halogen compound. The composition may further include abrasive and acid(s). A polishing composition for use on ruthenium materials may include ammonia, present in an amount of 0.01 wt % to 10 wt %, based on the total weight of the composition; hydrogen periodate, present in an amount of 0.01 wt % to 10 wt %, based on the total weight of the composition; silica, present in an amount of 0.01 wt % to 12 wt %, based on the total weight of the composition; and organic sulfonic acid, present in an amount of 0.01 wt % to 10 wt %, based on the total weight of the composition, wherein the pH of the composition is between 6 and 8.

## Claims

### Claim 1

A method of removing ruthenium material from a substrate, wherein the substrate comprises the ruthenium material and a second material selected from the group consisting of tetraethylorthosilicate (TEOS), a titanium material, and a combination thereof, and wherein the ruthenium material is applied with a chemical vapor deposition process or a physical vapor deposition process, the method comprising the steps of:
applying a composition to the substrate while polishing the substrate with a polishing pad, thereby removing the ruthenium material and the second material;
removing the ruthenium material at a first rate of removal; and
removing the second material at a second rate of removal, wherein the first rate of removal is greater than the second rate of removal,
the composition comprising:
ammonia, present in an amount of about 0.03 wt % to about 0.05 wt %, based on the total weight of the composition;
an oxygenated halogen compound present in an amount of about 0.01 wt % to about 10 wt %, based on the total weight of the composition, wherein the oxygenated halogen compound comprises a halogen selected from the group consisting of iodine, bromine, chlorine, and any combinations thereof;
an abrasive;
optionally, an acid;
water; and
less than about 1 wt % of any additional components,
wherein the pH of the polishing composition is between about 6 and 8, and
wherein when the polishing of the substrate with a polishing pad is at a downforce of 1.5 psi and a composition flow rate of 175 mL/min, a ratio of the first rate of removal to the second rate of removal is at least 522/33.

### Claim 2 (depends on 1)

The method of claim 1, wherein the oxygenated halogen compound is hydrogen periodate.

### Claim 3 (depends on 1)

The method of claim 1, wherein the abrasive is silica.

### Claim 4 (depends on 1)

The method of claim 1, wherein the abrasive is present in an amount of about 0.01 wt % to about 12 wt %, based on the total weight of the composition.

### Claim 5 (depends on 1)

The method of claim 1, wherein the acid is selected from the group consisting of a carboxylic acid, an organic sulfonic acid, an organic phosphonic acid, or any combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the acid is selected from the group consisting of 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxylamine O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholesulfonic acid, P-toluenesulfonic acid, and trifluoromethane-sulfonic acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrilotri(methylphosphonic acid), diethylenetriaminepentakis (methylphosphonic acid), N,N,N′N′-ethylenediaminetetrakis(methylene phosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, and any combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the acid is present in an amount of about 0.01 wt % to about 10 wt %, based on the total weight of the composition.

### Claim 8 (depends on 1)

The method of claim 1, wherein the composition is substantially free of azoles.

### Claim 9 (depends on 1)

The method of claim 1, wherein the pH of the composition is from 6 to 8.

### Claim 10 (depends on 1)

The method of claim 1, wherein the composition consists of the ammonia, the oxygenated halogen compound, the abrasive, water, and optionally the acid.