Post-CMP Cleaning Composition for Copper Surface Passivation Removal

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Solution Overview

Problem

Current post-CMP cleaning compositions fail to effectively remove benzotriazole residues and contaminants from copper-containing surfaces without increasing surface roughness or introducing environmental and safety concerns, and often require multiple steps and organic solvents.

Innovation Solution

A post-CMP cleaning composition comprising cysteine, glutathione, or thiourea, along with a sugar alcohol and a metal chelating agent, applied in a moderate pH range of 4 to 7, which efficiently removes benzotriazole films and other contaminants without increasing surface roughness or using organic solvents.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional post-CMP cleaning compositions are used, then cleaning action is provided, but benzotriazole residues and contaminants cannot be effectively removed and surface roughness increases

Engineering Contradiction:
Improvesurface roughnessVSAvoidcleaning efficacy
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The invention changes the chemical composition parameters of the cleaning solution by incorporating specific sulfur-containing compounds (cysteine, glutathione, or thiourea) at controlled concentrations (0.01-5 wt%, preferably 0.1-1 wt%). This compositional parameter change enables effective removal of benzotriazole residues while maintaining surface smoothness, resolving the contradiction between cleaning efficacy and surface roughness control.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite cleaning solution by combining sulfur-containing compounds with sugar alcohols (0.1-5 wt%) and metal chelating agents (0.01-1 wt%). This composite formulation synergistically achieves both effective contaminant removal and surface roughness control, addressing the contradiction between cleaning performance and surface quality.

Inventive Principle:
Principle #40Composite materials

2Reliability

If multiple cleaning steps and organic solvents are used, then cleaning completeness is improved, but environmental and safety concerns increase and process complexity increases

Engineering Contradiction:
Improvecleaning completenessVSAvoidenvironmental and safety concerns
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention extracts and eliminates harmful organic solvents from the cleaning process by using a water-based formulation with sulfur-containing compounds. This single-step aqueous solution achieves complete cleaning without the environmental and safety issues associated with organic solvents, resolving the contradiction between cleaning completeness and harmful factors.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention changes the fundamental parameter of the cleaning medium from organic-based to water-based, using sulfur-containing compounds dissolved in water. This parameter change eliminates environmental and safety concerns while maintaining or improving cleaning effectiveness through the unique chemical properties of the sulfur compounds.

Inventive Principle:
Principle #35Parameter changes

3Productivity

If stronger cleaning agents are used, then contaminant removal efficiency is improved, but surface roughness increases and corrosion risk increases

Engineering Contradiction:
Improvecontaminant removal efficiencyVSAvoidsurface roughness
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The invention changes the chemical nature of the cleaning agent from strong conventional cleaners to mild sulfur-containing compounds (cysteine, glutathione, or thiourea). These compounds achieve high contaminant removal efficiency through specific chemical interactions with benzotriazole residues while being gentle enough to prevent surface roughening and corrosion.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The sulfur-containing compounds act as intermediary substances that mediate between the cleaning requirement and surface protection. They chemically interact with and remove benzotriazole contaminants while simultaneously protecting the copper surface from corrosion and roughness increase, resolving the contradiction between removal efficiency and surface quality.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Reliability

If conventional cleaning compositions are used, then general cleaning is achieved, but copper surface corrosion is not effectively prevented

Engineering Contradiction:
Improvecorrosion preventionVSAvoidcleaning performance
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The sulfur-containing compounds (cysteine, glutathione, or thiourea) serve as dual-function intermediaries: they clean the copper surface by removing contaminants while simultaneously acting as corrosion inhibitors. The sulfur groups in these compounds bind to copper ions, preventing corrosion without compromising cleaning performance.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention makes the cleaning solution multi-functional by incorporating sulfur-containing compounds that simultaneously provide cleaning action and corrosion protection. This single composition achieves both contaminant removal and surface protection, resolving the contradiction between corrosion prevention and cleaning effectiveness.

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 effectively prevents corrosion and removes passivation films, ensuring clean copper surfaces and reducing defects, suitable for high-precision fabrication methods like copper damascene processes, while being environmentally friendly and requiring minimal steps.

Implementation Method 1

a post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound... efficiently removes benzotriazole films and other contaminants

Methodology Applied
Scientific EffectChemical complexation: Chemical Bonding

Implementation Method 2

The sulfur-containing compound... prevents corrosion and removes passivation films

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 3

along with a sugar alcohol and a metal chelating agent... effectively prevents corrosion and removes passivation films

Methodology Applied
Scientific EffectChelation: Chemical Bonding

Data Source

PatentEP3385363B1A post chemical-mechanical-polishing (post-CMP) cleaning composition comprising a specific sulfur-containing compound
Publication Date: 2022.03.16 BASF SE
  • EP3385363B1 patent drawingFigure 1
  • EP3385363B1 patent drawingFigure 2
  • EP3385363B1 patent drawingFigure 3

AI summary

A post chemical-mechanical-polishing (post-CMP) cleaning composition comprising: (A) is cysteine, glutathione, N-acetylcysteine, thiourea, (L) at least one oligomeric or polymeric polycarboxylic acid, and (C) water, wherein the post-CMP cleaning composition has a pH-value in the range of from 4 to not more than 7. The use of the composition for removing residues and contaminants from the surface of semiconductor substrates useful for manufacturing microelectronic devices. A process for manufacturing microelectronic devices from semiconductor substrates comprising the step of removing residues and contaminants from the surface of the semiconductor substrates by contacting them at least once with the post-CMP cleaning composition.