Alkaline Cleaning Composition for Semiconductor Copper Wiring

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Solution Overview

Problem

Current cleaning liquids for semiconductor substrates with copper wiring after CMP treatments fail to effectively remove metallic impurities and particulates without causing copper corrosion or damaging low permittivity interlayer insulating films.

Innovation Solution

A cleaning liquid composition with a pH of 8 to 10, containing a basic compound and a phosphonic acid-based chelating agent like glycine-N,N-bis(methylenephosphonic acid) or nitrilotris(methylenephosphonic acid), which does not include aqueous hydrogen peroxide or carboxylic acid-based chelating agents, effectively removes metallic impurities and particulates while preventing copper corrosion by forming a thin oxide film.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If an acidic cleaning liquid is used to remove metal contamination, then metal impurity removal is improved, but copper corrosion increases and surface roughness increases

Engineering Contradiction:
Improvemetal impurity removalVSAvoidcopper corrosion
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent changes the pH parameter from acidic to alkaline (pH 9.0-11.0) and modifies the chemical composition by using specific alkaline cleaners with controlled metal ion concentrations (0.01-5.0 ppm), thereby achieving effective cleaning without copper corrosion

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces metal ion complexing agents as intermediaries that bind to metal ions in the cleaning solution, preventing them from corroding copper surfaces while maintaining cleaning effectiveness

Inventive Principle:
Principle #24Intermediary (Mediator)

2Reliability

If a basic cleaning liquid is used to remove particulate contamination, then particle removal is improved, but low-k interlayer insulating film damage increases

Engineering Contradiction:
Improveparticle removalVSAvoidlow-k film damage
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent precisely controls the pH parameter within a narrow range (9.0-11.0) and limits metal ion concentrations (0.01-5.0 ppm) to achieve sufficient particle removal while minimizing damage to low-k films

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a moderate alkaline environment rather than strong alkali, applying partial action to achieve cleaning effectiveness while avoiding excessive damage to sensitive low-k materials

Inventive Principle:
Principle #16Partial or excessive action

3Productivity

If conventional cleaning liquids are used for post-CMP cleaning, then cleaning capability is improved, but contamination control fails due to inadequate removal of both particulates and metal impurities

Engineering Contradiction:
Improvecleaning capabilityVSAvoidcontamination control
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent develops a cleaning solution that simultaneously performs multiple functions: removing particulate contamination, dissolving metal impurities, and protecting copper surfaces, thereby achieving comprehensive contamination control in a single step

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

Solution Approach 2:

The patent creates a composite cleaning solution containing multiple components including alkaline cleaners, metal ion complexing agents, and controlled metal ion concentrations, which work synergistically to address multiple contamination types simultaneously

Inventive Principle:
Principle #40Composite materials

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 solution provides excellent removability of metallic impurities and particulates without damaging copper surfaces or low-k materials, suppressing surface oxidation and ensuring flatness and cleanliness.

Implementation Method 1

containing one or more phosphonic acid-based chelating agent

Methodology Applied
Scientific EffectChelation:

Implementation Method 2

having a hydrogen ion concentration (pH) of 8 to 10

Methodology Applied
Scientific EffectpH adjustment:

Implementation Method 3

preventing copper corrosion by forming a thin oxide film

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentEP2602309B1Method of cleaning an electronic device with an alkaline liquid composition comprising a phosphonic acid derivative chelating agent
Publication Date: 2017.05.03 KANTO CHEM CO INC
  • EP2602309B1 patent drawingFigure 1~2
  • EP2602309B1 patent drawingFigure 3~4
  • EP2602309B1 patent drawingFigure 5

AI summary

To provide a cleaning liquid composition that has excellent removability for metallic impurities and particulates, does not cause corrosion of Cu, and can clean a semiconductor substrate having copper wiring in a production process for an electronic device such as a semiconductor device. [Solution means] A cleaning liquid composition for cleaning a semiconductor substrate having copper wiring, the cleaning liquid composition containing one or more types of basic compound containing no metal, and one or more types of phosphonic acid-based chelating agent, and having a hydrogen ion concentration (pH) of 8 to 10.