Photochemical Structuring of Organometallic Oxide Layers

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Solution Overview

Problem

Current methods for producing structured piezoelectric layers, such as PZT and BTO, face challenges including instability of materials, complex processing steps, and limitations in achieving precise, small-scale structures due to the separation of components and destruction of ligands during photochemical structuring, which affects long-term stability and resolution.

Innovation Solution

A method involving a liquid precursor sol with photochemically active organometallic compounds that undergo addition polymerization upon actinic radiation, allowing for the formation of stable, structured oxide layers without by-products, enabling sintering into polycrystalline or nanocrystalline oxides for functional applications, and utilizing multiphoton absorption for 3D structurability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional photochemical structuring methods are used on PZT precursor sols, then structuring capability is achieved, but component separation and ligand destruction occur leading to reduced long-term stability

Engineering Contradiction:
Improvestructuring capabilityVSAvoidlong-term stability
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The patent introduces a chelating agent as an intermediary substance that forms stable complexes with metal ions in the precursor sol. This chelating agent acts as a mediator that prevents direct photochemical degradation of the metal precursors while still allowing structured formation through controlled polymerization of the organic component, thereby maintaining long-term stability during photochemical structuring

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent creates a composite precursor system combining inorganic metal ions (Pb, Zr, Ti) with organic chelating agents and polymerizable compounds. This composite structure allows the organic component to provide structural stability and control during photochemical processing, while the inorganic component maintains its piezoelectric functionality, resolving the contradiction between structuring capability and stability

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If conventional PZT sol methods are used, then material availability is improved, but complex processing steps and component separation occur

Engineering Contradiction:
Improvematerial availabilityVSAvoidprocessing steps
Core Design Contradiction:
Ease of manufactureVSDevice complexity

Solution Approach 1:

The patent combines multiple functions into a single precursor sol formulation: the chelating agent simultaneously stabilizes metal ions, controls hydrolysis rate, and provides polymerizable groups for structuring. This merging of functions eliminates the need for separate stabilization and structuring steps, reducing overall process complexity while maintaining ease of manufacture

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The patent modifies key parameters of the precursor sol by introducing chelating agents with specific stability constants and polymerizable functional groups. This parameter change allows the sol to remain stable during storage and application, then undergo controlled structuring upon photochemical exposure, simplifying the processing workflow while maintaining material availability

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If higher resolution structures are produced, then manufacturing precision is improved, but material and energy requirements increase

Engineering Contradiction:
ImproveresolutionVSAvoidmaterial requirements
Core Design Contradiction:
Manufacturing precisionVSQuantity of substance

Solution Approach 1:

The patent replaces mechanical mixing and thermal processing with photochemical polymerization initiated by light exposure. This substitution allows for precise spatial control of structuring through photomasks or direct laser writing, achieving high resolution structures with minimal material consumption since polymerization occurs only in exposed regions rather than requiring bulk material processing

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

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 allows for the production of stable, functional oxide layers and bodies with precise 3D structures, enhancing the resolution and stability of piezoelectric materials, suitable for ultrasonic arrays and other applications, while reducing material and energy requirements.

Implementation Method 1

photochemically active groups are converted into an organic network via addition polymerization

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Implementation Method 2

the photochemically active groups are converted into an organic network via addition polymerization without by-products being formed

Methodology Applied
Scientific EffectPhotochemical crosslinking: Photopolymerisation

Implementation Method 3

utilizing multiphoton absorption for 3D structurability

Methodology Applied
Scientific EffectMultiphoton absorption: Absorption (EM radiation)

Implementation Method 4

enabling sintering into polycrystalline or nanocrystalline oxides for functional applications

Methodology Applied
Scientific EffectSintering: Sintering

Data Source

PatentEP2576481B1Structured layers of crosslinked or crosslinkable organometallic compounds, formed objects comprising said layers and methods to produce them
Publication Date: 2015.12.16 FRAUNHOFER GESELLSCHAFT ZUR FORDERUNG DER ANGEWANDTEN FORSCHUNG EV
  • EP2576481B1 patent drawingFigure 1~2
  • EP2576481B1 patent drawingFigure 3

AI summary

The invention relates to a process for producing a structured shaped body or a layer of this type from a precursor for an oxide or mixed oxide of one or more metals selected from among magnesium, strontium, barium, aluminum, gallium, indium, silicon, tin, lead and the transition metals, which comprises the steps: (a) dissolution of at least one compound of the one or more metals in an organic solvent and/or replacement of a ligand of the, or one of the, dissolved metal compound(s) with a stabilizing ligand; (b) addition to the solution of a ligand which has at least one photochemically polymerizable group and at least one such group which makes stable complexation possible and formation of a sol containing or composed of the product of this reaction (precursor); (c) application of the sol to a substrate; (d) anisotropic illumination of the sol in such a way that polymerization of photochemically polymerizable groups takes place in the illuminated regions, the sol, in step (c), being applied in structured form and/or the unilluminated regions of the sol being removed after polymerization to leave the shaped body or the layer. The body or the layer can subsequently be sintered until the organic constituents have been removed, a corresponding oxide body or an oxide layer being formed.