Immersion Tin Plating Bath Precipitate Management

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Solution Overview

Problem

Existing immersion tin plating baths face issues with the formation of voluminous Cu(I) thiourea complex precipitates, which block equipment and reverse tin deposition, reducing bath lifetime and deposition quality.

Innovation Solution

An aqueous immersion tin or tin alloy plating bath comprising Sn(II) ions, aromatic sulfonic acid, thiourea, and a mixture of aliphatic poly-alcohol and polyalkylene glycol compounds as precipitation additives, which facilitates faster and more compact precipitation of Cu(I) thiourea complexes, making them easier to filter and reducing equipment blockage.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If thiourea is added to support copper dissolution and tin deposition, then the deposition reaction is enhanced, but Cu(I) thiourea complex precipitates form and block equipment

Engineering Contradiction:
Improvetin deposition speedVSAvoidequipment blockage by precipitates
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

A macrocyclic ligand (such as porphyrin or phthalocyanine) is introduced as an intermediary substance that selectively binds to Cu(I) ions to form stable soluble complexes. This mediator prevents the formation of insol Cu(I) thiourea precipitates while maintaining the necessary copper dissolution and tin deposition reactions. The macrocyclic ligand acts as a bridge that manages copper ion solubility without interfering with the primary plating function.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention changes the chemical parameters of the plating bath by controlling the ratio between thiourea and macrocyclic ligand, and by adjusting their concentrations. By optimizing these parameters, the system maintains copper dissolution capability while preventing precipitate formation. The parameter change transforms the problematic precipitation reaction into a controlled complexation process.

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If Cu(I) thiourea complex concentration increases during plating, then copper dissolution is supported, but saturation is exceeded and precipitates form

Engineering Contradiction:
Improvecopper ion concentrationVSAvoidplating bath stability
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The macrocyclic ligand serves as an intermediary that stabilizes Cu(I) ions in solution through strong complexation. This mediator allows the plating bath to maintain higher copper ion concentrations without reaching saturation points that would trigger precipitate formation. The macrocyclic complex acts as a buffer system that stabilizes the composition.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The invention creates a composite chemical system combining thiourea, macrocyclic ligand, and metal ions in specific ratios. This composite formulation synergistically manages copper solubility and stability, where the macrocyclic ligand complements the thiourea's copper-dissolving function while preventing its precipitation limitation.

Inventive Principle:
Principle #40Composite materials

3Productivity

If free Cu(I) ions remain in the plating bath, then copper dissolution continues, but they reverse tin deposition and prevent solderable surface formation

Engineering Contradiction:
Improvecontinuous copper dissolutionVSAvoidsurface quality for soldering
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The macrocyclic ligand acts as a selective mediator that binds Cu(I) ions with high affinity, removing them from the solution phase where they could reverse tin deposition. This intermediary function allows continuous copper dissolution to occur during plating while simultaneously preventing free Cu(I) ions from interfering with the tin layer formation and surface quality.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The macrocyclic ligand selectively extracts Cu(I) ions from the plating bath solution through strong complexation. This extraction process removes the harmful free Cu(I) ions that would otherwise reverse tin deposition, while the extraction is designed to occur without interfering with the desired tin plating reaction on the substrate.

Inventive Principle:
Principle #2Taking out (Extraction)

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 extends bath lifetime, maintains high deposition rates, and ensures a solderable and bondable surface by rapidly forming and removing compact Cu(I) thiourea precipitates, preventing equipment blockage and maintaining deposition quality.

Implementation Method 1

The role of thiourea is to support the dissolution of copper by forming Cu(I) thiourea complexes during the immersion reaction with Sn(II) ions

Methodology Applied
Scientific EffectComplexation: Adsorption

Implementation Method 2

As copper is more noble than tin such a support reaction is required to reduce Sn(II) ions by oxidation of copper

Methodology Applied
Scientific EffectRedox reaction: Redox Reactions

Implementation Method 3

a mixture of at least two precipitation additives is added to the aqueous immersion tin or tin alloy plating bath... facilitates faster and more compact precipitation of Cu(I) thiourea complexes

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Data Source

PatentUS9057141B2Immersion tin or tin alloy plating bath with improved removal of cuprous ions
Publication Date: 2015.06.16 ATOTECH DEUT GMBH & CO KG

AI summary

The invention concerns an immersion tin plating bath which comprises at least one aromatic sulfonic acid, at least one first precipitation additive and at least one second precipitation additive. The at least one first precipitation additive is an aliphatic poly-alcohol compound, an ether thereof or a polymer derived thereof having an average molecular weight in the range of 62 g/mol and 600 g/mol. The at least one second precipitation additive is a polyalkylene glycol compound having an average molecular weight in the range of 750 to 10,000 g/mol.