Reactive Colloidal Nanocrystals with Polythiol Ligands

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Solution Overview

Problem

Current methods for producing nanocrystal-polymer composites face challenges such as reduced photoluminescence quantum yield due to agglomeration and incompatibility of hydrophobic ligands with polymer matrices, leading to low NC content and homogeneous dispersion issues.

Innovation Solution

Development of reactive colloidal nanocrystals with a core comprising semiconductive compounds like Zn, In, Cu, S, and Se, surrounded by polythiol ligands, which are directly crosslinked with a polymer matrix without ligand exchange, allowing for high loading and stable dispersion.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If hydrophobic ligands (octylamine or tri-octylphosphine oxide) are used to stabilize nanocrystals, then chemical attacks to the surface of the NC are avoided, but photoluminescence quantum yield is reduced by agglomeration due to phase segregation processes

Engineering Contradiction:
Improvechemical stabilityVSAvoidphotoluminescence quantum yield
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent changes the chemical parameters of the ligands from hydrophobic (octylamine, tri-octylphosphine oxide) to polar ligands (amines, carboxylates, or thiols). This parameter change improves photoluminescence quantum yield by preventing agglomeration while maintaining chemical stability through appropriate ligand selection.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite ligand systems combining different functional groups (polar groups for compatibility and stability, plus additional stabilizing groups). This composite approach allows the nanocrystals to maintain chemical stability while achieving better dispersion and higher photoluminescence quantum yield in polymer matrices.

Inventive Principle:
Principle #40Composite materials

2Adaptability or versatility

If polar ligands (amines, carboxylates or thiols) are used to exchange with organic ligands, then compatibility with polymer matrices is improved and homogeneous dispersion is achieved, but defects on the surface of the NC increase which negatively affect photoluminescence and electroluminescence

Engineering Contradiction:
Improvecompatibility with polymer matrixVSAvoidphotoluminescence and electroluminescence properties
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent applies local quality by using different types of polar ligands at different locations or roles: some ligands provide compatibility with the polymer matrix while other ligands maintain surface quality and prevent defect formation. This selective ligand placement allows simultaneous achievement of good dispersion and high photoluminescence/electroluminescence properties.

Inventive Principle:
Principle #3Local quality

3Quantity of substance

If in-situ synthesis of semiconductor nanocrystals is performed in the presence of polymers, then nanometer-sized crystals are obtained, but control over the size and shape of NCs cannot be achieved and photoluminescence is very low

Engineering Contradiction:
Improvenanocrystal contentVSAvoidcontrol over size and shape
Core Design Contradiction:
Quantity of substanceVSManufacturing precision

Solution Approach 1:

The patent applies preliminary action by pre-synthesizing nanocrystals with controlled size and shape using conventional high-quality methods, then subsequently introducing them into the polymer matrix. This two-step approach allows precise control over nanocrystal dimensions while achieving high nanocrystal content in the final composite material.

Inventive Principle:
Principle #10Preliminary action

4Ease of manufacture

If direct polymerization reaction is performed in the presence of semiconductor nanocrystals, then NC-polymer hybrid materials are formed in-situ, but chemical attack from radicals during polymerization and aggregation of NCs cause photoluminescence quenching

Engineering Contradiction:
Improvein-situ hybrid material formationVSAvoidphotoluminescence properties
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent applies preliminary anti-action by using stabilizing ligands that prevent chemical attack from polymerization radicals before the damage occurs. The ligands form a protective layer around the nanocrystals, counteracting the harmful effects of radical species generated during polymerization and preventing both chemical degradation and aggregation-induced photoluminescence quenching.

Inventive Principle:
Principle #9Preliminary anti-action

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 maintains the optical properties of nanocrystals, achieves high loadings, and enhances thermal and moisture stability, resulting in improved photoluminescence and electroluminescence performance with increased NC content.

Implementation Method 1

reactive colloidal nanocrystals comprising a core comprising a semiconductive compound and at least one polythiol ligand, wherein said core is surrounded by at least one polythiol ligand

Methodology Applied
Scientific EffectChemical bonding: Chemical Bonding

Implementation Method 2

ready to react directly with the polymer matrix and being crosslinked with the polymer matrix to form high quality and stable nanocrystal composites

Methodology Applied
Scientific EffectCrosslinking: Chemical Bonding

Data Source

PatentEP3189118B1Reactive colloidal nanocrystals and nanocrystal composites
Publication Date: 2019.12.11 HENKEL KGAA
  • EP3189118B1 patent drawingFigure 1~2
  • EP3189118B1 patent drawingFigure 3~4
  • EP3189118B1 patent drawingFigure 5

AI summary

The present invention relates to reactive colloidal nanocrystal comprising a core comprising a metal or a semiconductive compound or a mixture thereof and at least one polythiol ligand, wherein said core is surrounded by at least one polythiol ligand. Reactive colloidal nanocrystals according to the present invention can be prepared with one pot synthesis and are ready to react directly with the polymer matrix and being crosslinked with the polymer matrix to form high quality and stable nanocrystal composites. Furthermore, the present invention relates to nanocrystal composite comprising nanocrystals according to the present invention and a polymer matrix.