Lead-Free Resistive Composition for Stable Thick Film Resistors

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Solution Overview

Problem

Existing resistive compositions struggle to form thick film resistors without lead components, particularly in high resistance ranges, due to decomposition of ruthenium composite oxides and difficulties in maintaining a stable conductive network, leading to inferior resistance and current noise characteristics.

Innovation Solution

A resistive composition comprising ruthenium dioxide conductive particles and a lead-free glass frit, with specific glass composition and additives, forms a stable conductive network, achieving resistance values and TCR characteristics comparable to lead-containing resistors.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If lead oxide-containing glass is used to achieve favorable fluidity, wettability, and adhesiveness, then the forming characteristics of thick film resistor are improved, but toxicity and environmental pollution increase

Engineering Contradiction:
Improveforming characteristicsVSAvoidtoxicity
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention extracts and removes the harmful lead oxide component from the glass composition while retaining the essential functional characteristics. The lead-free glass composition uses alternative oxides (B2O3, SiO2, Al2O3, CaO, ZnO, MgO) to achieve the same fluidity, wettability, and adhesiveness properties without the toxic effects of lead oxide.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention employs a composite glass composition made from multiple oxide components that work synergistically to replace lead oxide. The specific combination of B2O3 (20-40 mol%), SiO2 (30-50 mol%), Al2O3 (5-15 mol%), CaO (5-15 mol%), ZnO (5-15 mol%), and MgO (5-15 mol%) creates a composite material that matches the functional properties of lead oxide-containing glass without the harmful effects.

Inventive Principle:
Principle #40Composite materials

2Reliability

If lead component is used to achieve good wettability to alumina substrate, then adhesiveness is improved, but excessive spreading and shape distortion occur

Engineering Contradiction:
ImproveadhesivenessVSAvoidresistor shape
Core Design Contradiction:
ReliabilityVSShape

Solution Approach 1:

The invention removes the lead component responsible for excessive wettability while preserving adequate adhesiveness through the lead-free glass composition. The alternative oxide combination provides controlled wettability that prevents both poor adhesion and excessive spreading.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention changes the chemical composition parameters of the glass by replacing lead oxide with a multi-component oxide system. This parameter change modifies the wettability characteristics to achieve optimal balance between adhesiveness and shape control during the firing process.

Inventive Principle:
Principle #35Parameter changes

3Reliability

If ruthenium composite oxides are used in high resistance range to achieve higher resistivity, then resistance value is improved, but decomposition to ruthenium dioxide occurs at high temperature

Engineering Contradiction:
Improveresistance valueVSAvoidcompositional stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The invention uses a composite conductive system combining ruthenium dioxide with other metal oxides (IrO2, PtO2, RhO2, PdO2, OsO2, RuO3, Ru2O3, Ru3O4). This composite structure provides high resistivity while enhancing thermal stability and preventing decomposition during the firing process.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The lead-free glass composition acts as an intermediary medium that stabilizes the ruthenium-based conductive particles during high-temperature firing. The glass matrix protects the conductive oxides from decomposing into less stable forms while maintaining the desired high resistance characteristics.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Object-affected harmful factors

If lead-free glass is used to eliminate toxicity, then environmental compatibility is improved, but decomposition of conductive component and instability of conductive network occur

Engineering Contradiction:
ImprovetoxicityVSAvoidconductive network stability
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The invention employs a composite glass composition with multiple stabilizing oxides that work together to maintain conductive network stability without lead. The combination of B2O3, SiO2, Al2O3, CaO, ZnO, and MgO creates a chemically stable matrix that prevents decomposition of ruthenium-based conductors during firing.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention optimizes the compositional parameters of the lead-free glass to achieve appropriate melting temperature, viscosity, and chemical stability. The specific oxide ratios are tuned to ensure the glass remains stable at firing temperatures while maintaining the conductive network integrity of the thick film resistor.

Inventive Principle:
Principle #35Parameter changes

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 enables the formation of stable, high-resistance resistors with improved current noise and process stability, free from lead-related toxicity, and maintains uniformity across a wide resistance range.

Implementation Method 1

The resistive composition is printed on an alumina substrate and then fired at a high temperature of 600°C to 900°C

Methodology Applied
Scientific EffectSintering: Sintering

Implementation Method 2

having favorable fluidity, wettability with the conductive component, superior adhesiveness to a substrate

Methodology Applied
Scientific EffectWettability: Wetting

Implementation Method 3

fired at a high temperature of 600°C to 900°C

Methodology Applied
Scientific EffectThermal processing: Heating

Data Source

PatentEP3193341B1Resistive composition
Publication Date: 2026.03.11 SHOEI CHEM IND CO LTD
  • EP3193341B1 patent drawingFigure 1A~1B
  • EP3193341B1 patent drawingFigure 1C
  • EP3193341B1 patent drawing

AI summary

An object of the present invention is to provide a resistive composition that can form a thick film resistor excluding a toxic lead component from a conductive component and glass and having characteristics equivalent to or superior to conventional resistors in terms of, in a wide resistance range, resistance values, TCR characteristics, current noise characteristics, withstand voltage characteristics and the like. The resistive composition of the present invention includes: ruthenium-based conductive particles including ruthenium dioxide; a glass frit that is essentially free of a lead component; and an organic vehicle, wherein the glass frit is a glass frit which is constituted such that in a case where a fired product of a mixture of the glass frit and the ruthenium dioxide has in a range of 1 kΩ/□ to 1 MΩ/□, the fired product exhibits a temperature coefficient of resistance in a plus range.