Aqueous CMP Slurry for Selective Nitride Removal

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Solution Overview

Problem

Conventional aqueous chemical mechanical planarization (CMP) polishing compositions lack sufficient selectivity for removing silicon nitride without damaging underlying oxide layers, particularly in advanced front-end of line (FEOL) structures like self-aligned contact (SAC) capping, where high nitride removal rate with low oxide removal rate is critical to prevent electrical shorts and ensure pattern density clearance.

Innovation Solution

Aqueous CMP polishing compositions comprising colloidal silica particles, amine carboxylic acids with an isoelectric point below 5, and ethoxylated anionic surfactants, optimized to achieve a pH of 3 to 5, providing a high nitride to oxide removal rate selectivity ratio through controlled zeta potential and abrasive particle size distribution.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional aqueous CMP polishing compositions are used, then oxide removal occurs, but nitride removal rate is insufficient and selectivity is poor

Engineering Contradiction:
Improvenitride removal selectivityVSAvoidnitride removal rate
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent modifies the chemical parameters of the CMP slurry by incorporating amine carboxylic acids with specific isoelectric points (pI < 5) and controlling the slurry pH to 3-5. This parameter change creates a chemical environment that selectively enhances nitride removal rate while maintaining controlled oxide removal, achieving the desired selectivity and productivity balance

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite polishing slurry system combining colloidal silica particles (abrasive component) with amine carboxylic acids (chemical component) and ethoxylated anionic surfactants (stability component). This composite formulation synergistically combines mechanical abrasion with chemical etching to achieve high nitride removal selectivity and rate

Inventive Principle:
Principle #40Composite materials

2Reliability

If high nitride removal rate is achieved, then oxide layers may be damaged, but if low oxide removal rate is maintained, then nitride removal is insufficient

Engineering Contradiction:
Improveoxide layer integrityVSAvoidnitride removal selectivity
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The amine carboxylic acids exhibit local chemical reactivity that is selective to silicon nitride surfaces rather than silicon oxide surfaces. The chemical composition creates locally differentiated etching behavior where nitride regions are actively removed while oxide regions remain protected, achieving high selectivity without compromising oxide layer integrity

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

By precisely controlling the pH parameter to the 3-5 range and selecting amine carboxylic acids with specific isoelectric points below 5, the patent creates optimal chemical conditions that favor nitride removal while minimizing oxide attack. This parameter optimization ensures reliable oxide protection alongside effective nitride removal

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If complete nitride layer clearing is performed, then oxide etching may be blocked, but if nitride removal is excessive, then electrical shorts may occur

Engineering Contradiction:
Improvepattern density clearanceVSAvoidelectrical short risk
Core Design Contradiction:
Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The CMP process using this slurry formulation provides self-regulating feedback through the selective chemistry. As polishing progresses and nitride is removed, the underlying oxide surface becomes exposed, which has different chemical reactivity. This naturally slows further removal, preventing over-polishing and electrical shorts while ensuring complete pattern density clearance

Inventive Principle:
Principle #23Feedback

Solution Approach 2:

The controlled pH range (3-5) and specific amine carboxylic acid selection create a chemical environment that is aggressive enough to remove nitride completely for pattern clearance but self-limiting to prevent excessive removal that would cause electrical shorts. The isoelectric point parameter of the additives is critical for achieving this precise control

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The compositions achieve a nitride to oxide removal rate selectivity ratio of 8:1 to 200:1, ensuring precise nitride removal without excessive oxide loss, thereby preventing electrical shorts and ensuring planarization of substrates in FEOL structures.

Implementation Method 1

providing a high nitride to oxide removal rate selectivity ratio through controlled zeta potential

Methodology Applied
Scientific EffectZeta potential control: Electrostatics

Implementation Method 2

controlled zeta potential and abrasive particle size distribution

Methodology Applied
Scientific EffectAdhesion: Adhesive

Implementation Method 3

ethoxylated anionic surfactants, optimized to achieve a pH of 3 to 5

Methodology Applied
Scientific EffectSurfactant action: Surfactant

Implementation Method 4

aqueous chemical mechanical planarization (CMP) polishing compositions comprising an abrasive of one or more dispersions of colloidal silica particles

Methodology Applied
Scientific EffectAbrasion: Abrasion

Data Source

PatentUS10584265B2Aqueous silica slurry and amine carboxylic acid compositions selective for nitride removal in polishing and methods of using them
Publication Date: 2020.03.10 DUPONT ELECTRONIC MATERIALS HLDG INC

AI summary

The present invention provides aqueous chemical mechanical planarization polishing (CMP polishing) compositions comprising one or more dispersions of aqueous colloidal silica particles, preferably, spherical colloidal silica particles, one or more amine carboxylic acids having an isolectric point (pI) below 5, preferably, an acidic amino acid or a pyridine acid, and one or more ethoxylated anionic surfactants having a C6 to C10 alkyl, aryl or alkylaryl hydrophobic group, wherein the compositions have a pH of from 3 to 5. The compositions enable good silicon nitride removal and selectivity of nitride to oxide removal in polishing.