Copper CMP Composition for High Removal and Low Dishing

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Solution Overview

Problem

Existing copper chemical mechanical planarization (CMP) formulations struggle to achieve high removal rates and low dishing, particularly for advanced technology nodes, while maintaining selectivity to barrier materials and reducing defects.

Innovation Solution

A copper CMP composition comprising tris chelators, an organic quaternary ammonium salt, an abrasive, an oxidizing agent, and a corrosion inhibitor, with a pH range of 3.0 to 12.0, specifically using ethylenediamine and amino acids, to enhance removal rates and reduce dishing and defects.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional copper CMP formulations are used, then copper removal is achieved, but dishing increases and removal rates decrease for advanced technology nodes

Engineering Contradiction:
Improvedishing controlVSAvoidremoval rate
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent changes the chemical composition parameters by introducing a specific tri-s chelator system (combining glycine, alanine, and ethylenediamine) with controlled pH (7.0-7.35) and additive concentrations. This parameter optimization enables simultaneous achievement of high removal rates (50-150 nm/min) and low dishing (<5 nm), resolving the trade-off between productivity and manufacturing precision

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention uses a composite chelator system combining three different chelating agents (glycine, alanine, ethylenediamine) with specific oxidizing agents (H2O2, KI, KIO3) and corrosion inhibitors (benzotriazole derivatives). This composite chemical formulation creates synergistic effects that enhance copper removal while controlling dishing, achieving both high productivity and manufacturing precision

Inventive Principle:
Principle #40Composite materials

2Productivity

If copper CMP is performed with high removal rate formulations, then productivity increases, but selectivity to barrier material decreases

Engineering Contradiction:
Improveremoval rateVSAvoidselectivity to barrier material
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent optimizes pH to a narrow range (7.0-7.35) and carefully controls oxidizing agent concentrations (0.1-5 wt% H2O2, 0.01-1 wt% KI/KIO3) to achieve high copper removal rates while maintaining barrier material selectivity. The corrosion inhibitor concentration (0.01-1 wt% benzotriazole derivatives) is specifically tuned to protect barrier layers during high-rate copper removal

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The tri-s chelator system acts as an intermediary that selectively complexes with copper ions at the copper surface, enabling high-rate removal while the corrosion inhibitors (benzotriazole derivatives) serve as mediators that preferentially adsorb on barrier materials, protecting them during the aggressive copper removal process. This intermediary mechanism decouples copper removal rate from barrier material damage

Inventive Principle:
Principle #24Intermediary (Mediator)

3Manufacturing precision

If advanced node copper CMP is performed, then technology scaling is achieved, but defectivity increases

Engineering Contradiction:
Improveplanarization qualityVSAvoiddefectivity
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The patent uses precisely controlled pH (7.0-7.35) and additive concentrations to minimize defect generation during copper removal. The optimized chelator and oxidizer ratios prevent excessive copper oxidation and particle generation, while the corrosion inhibitors reduce etch pits and other defects on copper surfaces and barrier materials, achieving low defectivity at advanced technology nodes

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent converts the potentially harmful aggressive chemical reactions into beneficial controlled removal processes. The oxidizing agents that could cause excessive oxidation and defects are instead used in controlled amounts to create a thin oxidized copper layer that facilitates uniform mechanical removal. The corrosion inhibitors that could slow removal are used to selectively protect barrier materials, converting potential harm to benefit by preventing barrier damage and associated defects

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

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 composition achieves high and tunable copper removal rates, low dishing, and improved selectivity to dielectric and barrier films, with reduced defects and extended pad life, suitable for advanced technology nodes.

Implementation Method 1

0.1 wt. % to 18.0 wt. % tris chelators; wherein the first chelator is an organic amine selected from the group consisting of ethylenediamine, propylenediamine, and butylenediamine; and the second and third chelators are two different amino acids, two different amino acid derivatives

Methodology Applied
Scientific EffectChelation:

Implementation Method 2

0.1 wt.% to 10 wt.% oxidizing agent

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 3

0.0025 wt.% to 25 wt.% abrasive

Methodology Applied
Scientific EffectAbrasion: Abrasion

Implementation Method 4

0.005 wt.% to 0.5 wt.% corrosion inhibitor

Methodology Applied
Scientific EffectCorrosion inhibition:

Data Source

PatentEP3444309B1Chemical mechanical planarization (CMP) composition and methods therefore for copper and through silica via (TSV) applications
Publication Date: 2025.07.16 VERSUM MATERIALS US LLC
  • EP3444309B1 patent drawingFigure 1
  • EP3444309B1 patent drawingFigure 2
  • EP3444309B1 patent drawingFigure 3

AI summary

Provided are Chemical Mechanical Planarization (CMP) compositions that offer high and tunable Cu removal rates and low copper dishing for the broad or advanced node copper or Through Silica Via (TSV). The CMP compositions provide high selectivity of Cu film vs. other barrier layers, such as Ta, TaN, Ti, and TiN, and dielectric films, such as TEOS, low-k, and ultra low-k films. The CMP polishing compositions comprise solvent, abrasive, at least three chelators selected from the group consisting of amino acids, amino acid derivatives, organic amine, and combinations thereof; wherein at least one chelator is an amino acid or an amino acid derivative. Additionally, an organic quaternary ammonium salt, a corrosion inhibitor, an oxidizer, a pH adjustor and biocide are optionally used in the compositions.