# US 11,078,417 B2 · Low oxide trench dishing chemical mechanical polishing

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- Number: US 11,078,417 B2
- Document ID: US11078417B2
- Status: Granted
- Kind: B2
- Application number: 16/450,784
- Filed: 2019-06-24
- Published: 2020-01-02
- Granted: 2021-08-03
- Earliest claimed: 2018-06-29
- Assignees: Versum Materials US, LLC
- Applicants: Versum Materials US, LLC
- Inventors: Xiaobo Shi; Krishna P. Murella; Joseph D. Rose; Hongjun Zhou; Mark Leonard O'Neill
- Web page: https://patentgrep.com/patent/US11078417B2

## CPC

- C09G 1/02: containing abrasives or grinding agents {(abrasives as such C09K3/14; polishing of semi-conductors H10P52/40)}
- C09K 13/00: Etching, surface-brightening or pickling compositions (for glass C03C15/00, {C03C25/66; for mortars, concrete, artificial or natural stone or ceramics C04B41/5338}; for metallic material C23F, C23G1/00, C25F1/00; {for semi-conductors H10P52/40})
- C09K 13/02: containing an alkali metal hydroxide
- C09K 13/06: with organic material
- H10P 95/062: {involving a dielectric removal step}
- C09G: POLISHING COMPOSITIONS (French polish C09F11/00); SKI WAXES
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Chemical mechanical planarization (CMP) polishing compositions, methods and systems are provided to reduce oxide trench dishing and improve over-polishing window stability. High and tunable silicon oxide removal rates, low silicon nitride removal rates, and tunable SiO2: SiN selectivity are also provided. The compositions use unique chemical additives, such as maltitol, lactitol, maltotritol, ribitol, D-sorbitol, mannitol, dulcitol, iditol, D-(−)-Fructose, sorbitan, sucrose, ribose, Inositol, glucose, D-arabinose, L-arabinose, D-mannose, L-mannose, meso-erythritol, beta-lactose, arabinose, or combinations thereof as oxide trench dishing reducing additives.

## Claims

### Claim 1

A Chemical Mechanical Polishing(CMP) composition comprising:
abrasive particles selected from the group consisting of inorganic oxide particles, metal-coated inorganic oxide particles, organic polymer particles, metal oxide-coated organic polymer particles, and combinations thereof;
chemical additive;
solvent selected from the group consisting of deionized (DI) water, distilled water, and alcoholic organic solvents; and
optionally
biocide; and
pH adjuster;
wherein
the composition has a pH of 3 to 10;
the abrasive particles have a mean particle size of 120 to 500 nm and have a concentration from 0.05 wt. % to 10 wt. %;
the inorganic oxide particles are selected from the group consisting of ceria, colloidal silica, high purity colloidal silica, colloidal ceria, alumina, titania, zirconia particles, and combinations thereof;
the metal-coated inorganic oxide particles are selected from the group consisting of ceria-coated inorganic oxide particles selected from the group consisting of ceria-coated colloidal silica, ceria-coated high purity colloidal silica, ceria-coated alumina, ceria-coated titania, ceria-coated zirconia particles and combinations thereof;
the organic polymer particles are selected from the group consisting of polystyrene particles, polyurethane particles, polyacrylate particle, and combinations thereof;
the metal-coated organic polymer particles are selected from the group consisting of ceria-coated organic polymer particles, zirconia-coated organic polymer particles, silica-coated organic polymer particles, and combinations thereof;
the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤3.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under; and
the chemical additive ranges from 0.05 wt. % to 5 wt. %; and has
a molecular structure (a):
wherein the structure (a) has at least six hydroxyl functional groups in its molecular structure; and R1, R2, R3, R4 and R5 (Rs in group of R1 to R5) are selected as following
(i) at least one R in the group of R1 to R5 is a polyol molecular unit having a structure shown in (b):
wherein m or n is independently selected from 1 to 5; and each of R6, R7, R8 and R9 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof;
(ii) at least one R in the group of R1 to R5 is a six-member ring polyol as shown in (c):
wherein
one of OR in group of OR11, OR12, OR13 and OR14 will be replaced by O in structure (a); and
R10 and each of other R in group of R10, R11, R12, R13 and R14 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof;
and
(iii) each of other Rs in the group of R1 to R5 is independently selected from the group consisting of hydrogen, alkyl, alkoxy, organic group with one or more hydroxyl groups, substituted organic sulfonic acid or salt, substituted organic carboxylic acid or salt, organic carboxylic ester, organic amine, and combinations thereof.

### Claim 2 (depends on 1)

The Chemical Mechanical Polishing(CMP) composition of claim 1, wherein
the polyol molecular unit (b) which has n=2 and m=1; and rest of Rs in the group of R1 to R14 are all hydrogen atoms, as shown below:
and the solvent is deionized (DI) water, and
the abrasive particles have changes of mean particle size MPS (nm) and D99 (nm)≤2.0%.

### Claim 3 (depends on 1)

The Chemical Mechanical Polishing(CMP) composition of claim 1, wherein
the abrasive particles are ceria-coated colloidal silica particles or ceria particles.

### Claim 4 (depends on 1)

The chemical mechanical polishing composition of claim 1, wherein
the composition comprises ceria-coated colloidal silica particles or ceria particles; and
the ceria-coated colloidal silica particles or ceria particles have changes of mean particle size MPS (nm) and D99 (nm)≤2.0% over shelf time of ≥30 days at a temperature ranging from 20 to 60° C.; wherein D99 (nm) is a particle size that 99 wt. % of the particles fall on and under.

### Claim 5 (depends on 1)

The chemical mechanical polishing composition of claim 1, wherein the composition comprises one selected from the group consisting of from 0.0001 wt. % to 0.05 wt. % of the biocide having active ingredient selected from the group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and combinations thereof; from 0 wt. % to 1 wt. % of the pH adjusting agent selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, other inorganic or organic acids, and mixtures thereof for acidic pH conditions; or selected from the group consisting of sodium hydride, potassium hydroxide, ammonium hydroxide, tetraalkyl ammonium hydroxide, organic quaternary ammonium hydroxide compounds, organic amines, and combinations thereof for alkaline pH conditions; and combinations thereof.