Selective Copper Etching Using Hydrogen Peroxide and Citric Acid

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Solution Overview

Problem

Conventional semiconductor device manufacturing methods fail to selectively etch copper without etching nickel, leading to insufficient performance in downsized and high-integration semiconductor devices.

Innovation Solution

A method using an etchant containing hydrogen peroxide and a specified hydroxy acid, such as citric acid or malic acid, in specific compositions to selectively etch copper without etching nickel, ensuring stable etching rates and performances.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional etchants are used to etch copper, then copper etching is achieved, but nickel is also etched unintentionally

Engineering Contradiction:
Improveselectivity of copper etchingVSAvoidunintentional nickel etching
Core Design Contradiction:
Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The patent modifies the chemical composition parameters of the etchant by incorporating specific organic acids (oxalic acid, malic acid, or citric acid) along with hydrogen peroxide and water. This parameter change enables selective etching of copper while preventing nickel etching, achieving the desired selectivity without harmful side effects.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces organic acids as intermediary substances that mediate the etching process. These intermediaries selectively interact with copper to facilitate etching while being inert toward nickel, thus enabling precise control over which metal is etched and preventing unintentional nickel removal.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Productivity

If conventional etching methods are used, then etching process is completed, but nickel layer integrity is compromised

Engineering Contradiction:
Improveetching process efficiencyVSAvoidnickel layer integrity
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent changes the chemical parameters of the etching solution by formulating a specific composition containing organic acids and hydrogen peroxide. This modified composition maintains high etching efficiency for copper while ensuring nickel layer integrity, thus simultaneously achieving productivity and reliability.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent converts the potential harm of nickel etching into a benefit by using organic acids that selectively target copper. The etching process, which could potentially damage nickel, is transformed into a selective copper removal process that actually protects nickel layer integrity while maintaining efficient copper etching.

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 method allows for the selective etching of copper without damaging nickel, enhancing the performance of semiconductor devices by maintaining the integrity of nickel layers during the etching process, thus addressing the limitations of conventional methods.

Implementation Method 1

an etchant which contains hydrogen peroxide and, as an organic acid component, citric acid or malic acid that is a specified hydroxy acid and has a specified composition

Methodology Applied
Scientific EffectChemical etching: Oxidation

Data Source

PatentEP2515326B1Method for manufacturing semiconductor device using an etchant
Publication Date: 2018.09.26 MITSUBISHI GAS CHEM CO INC
  • EP2515326B1 patent drawingFigure 1A(a)~1A(h)
  • EP2515326B1 patent drawingFigure 2A(i)~2A(p)
  • EP2515326B1 patent drawingFigure 3B(a)~3B(g)

AI summary

Disclosed are an etchant which is used for redistribution of a semiconductor substrate having an electrode and which is capable of selectively etching copper without etching nickel; and a method for manufacturing a semiconductor device using the same. Specifically disclosed are an etchant which is used for redistribution of a semiconductor substrate and which contains hydrogen peroxide and citric acid and has a content of hydrogen peroxide of from 0.75 to 12 % by mass and a content of citric acid of from 1 to 20 % by mass, with a molar ratio of hydrogen peroxide and citric acid being in the range of from 0.3 to 5; an etchant for selective etching of copper which is used for redistribution of a semiconductor substrate and which contains hydrogen peroxide and malic acid and has a content of hydrogen peroxide of from 0.75 to 12 % by mass and a content of malic acid of from 1.5 to 25 % by mass, with a molar ratio of hydrogen peroxide and malic acid being in the range of from 0.2 to 6; and a method for manufacturing a semiconductor device using such an etchant.