Lead-Free Piezoelectric Precursor Solution via Anhydrous Sol-Gel

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Solution Overview

Problem

Existing methods for preparing lead-free BZT-BCT piezoelectric materials are complex and use toxic solvents like 2-methoxyethanol, leading to unstable precursor solutions and suboptimal thin film properties, which are not environmentally friendly and do not adequately control stoichiometry for improved ferroelectric performance.

Innovation Solution

A method involving the preparation of a precursor solution using anhydrous alkyl alcohols and chelating agents to create a homogeneous, water-free solution for BZT-αBXT ceramics, where X is selected from Ca, Sn, Mn, and Nb, allowing for reduced crystallization temperatures and improved electrical properties in thin films.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional sol-gel methods using 2-methoxyethanol are used to prepare BZT-BCT precursor solutions, then the preparation process is simple, but the precursor solutions are unstable and lead to suboptimal thin film properties

Engineering Contradiction:
Improvestability of precursor solutionVSAvoidcomplexity of preparation method
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent changes the chemical parameters of the precursor solution by using anhydrous conditions and specific chelating agents (acetylacetone, acetic acid) instead of conventional solvents like 2-methoxyethanol. This parameter change stabilizes the precursor solution and improves thin film properties while maintaining process simplicity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces chelating agents (acetylacetone, acetic acid) as intermediaries that mediate between the metal alkoxides and water during hydrolysis. These intermediaries control the reaction kinetics and stabilize the precursor solution, preventing premature gelation while ensuring reproducible thin film formation

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-affected harmful factors

If toxic solvents like 2-methoxyethanol are used in the preparation process, then the preparation method is established and simple, but the process becomes environmentally harmful and toxic

Engineering Contradiction:
Improveenvironmental friendlinessVSAvoidsimplicity of preparation process
Core Design Contradiction:
Object-affected harmful factorsVSEase of manufacture

Solution Approach 1:

The patent converts the potential harm of using conventional solvents into a benefit by deliberately using anhydrous conditions and controlling water addition. This approach eliminates toxic solvent exposure while maintaining process simplicity through controlled hydrolysis and sol-gel transitions that are inherently safe and environmentally friendly

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

Solution Approach 2:

The patent replaces expensive and toxic conventional solvents with simpler, safer alternatives like anhydrous alcohols and common chelating agents (acetylacetone, acetic acid). These substitutes are less hazardous, environmentally friendly, and maintain effective precursor solution stability without requiring complex handling procedures

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

3Manufacturing precision

If conventional preparation methods are used, then the process is established, but the stoichiometry control is insufficient for improved ferroelectric performance

Engineering Contradiction:
Improvestoichiometry controlVSAvoidcomplexity of preparation procedure
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent performs preliminary action by pre-mixing metal alkoxides with chelating agents in anhydrous conditions before controlled water addition. This preliminary complexation ensures uniform distribution of metal ions and precise stoichiometry control during subsequent hydrolysis, leading to homogeneous thin films with improved ferroelectric performance

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes the chemical parameters by using anhydrous conditions and specific chelating agents that control the hydrolysis rate and metal ion distribution. This parameter control ensures precise stoichiometry in the final thin film, improving ferroelectric properties without requiring complex multi-step procedures

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

This approach results in stable, well-crystallized, and dense thin films with enhanced ferroelectric properties, including higher piezoelectric coefficients and dielectric constants, while avoiding the use of carcinogenic and mutagenic solvents, thus offering a more environmentally friendly and effective synthesis method.

Implementation Method 1

The sol-gel process involves the hydrolysis and condensation of metal alkoxides

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Implementation Method 2

The sol-gel process involves the hydrolysis and condensation of metal alkoxides

Methodology Applied
Scientific EffectCondensation: Condensation

Implementation Method 3

The resulting sol can be dried and calcined to obtain a crystalline ceramic

Methodology Applied
Scientific EffectEvaporation: Evaporation

Data Source

PatentEP4074672A1Method for the preparation of a lead-free piezoelectric material and precursor solution
Publication Date: 2022.10.19 STMICROELECTRONICS SRL
  • EP4074672A1 patent drawingFigure 1~2
  • EP4074672A1 patent drawingFigure 3
  • EP4074672A1 patent drawingFigure 4~6B

AI summary

The present invention relates to a method for the preparation of a precursor solution for a ceramic of the BZT-αBXT type wherein X is selected from Ca, Sn, Mn and Nb and α is a molar fraction selected in the range between 0.10 and 0.90 comprising the steps of: a) dissolving at least one barium precursor compound and at least one precursor compound selected from the group consisting of a calcium precursor compound, a tin precursor compound, a manganese precursor compound and a niobium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms and, after dissolution, dehydrating by stripping, to obtain a first solution; b) dissolving at least one zirconium precursor compound and at least one titanium precursor compound in a linear or branched anhydrous alkyl alcohol containing from 2 to 6 carbon atoms in the presence of an anhydrous chelating agent to obtain a second solution; c) joining said first and second solutions in an anhydrous environment and dehydrating by stripping to obtain said precursor solution. It also relates to a precursor solution, to a method for the preparation of a film of a piezoelectric material, to a piezoelectric material and to an electronic device comprising this piezoelectric material.