Polythiol Quantum Dot Ligands for Resin-Soluble Stable Nanostructures

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Solution Overview

Problem

Existing quantum dots have hydrophobic ligands that limit their solubility in a wide range of organic media, leading to instability and deterioration of optical properties when exposed to resin formulations, necessitating improved nanostructure compositions and resin mixes for enhanced stability and optical performance.

Innovation Solution

The use of polythiol ligands with pendant moieties, such as those described by formula I, are dispersed on the surface of nanostructures to enhance solubility and stability, allowing for ligand exchange to replace hydrophobic ligands with more stable and soluble alternatives.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If hydrophobic ligands are used on quantum dot surfaces, then colloidal stability is achieved, but solubility in organic media is limited and optical properties deteriorate in resin formulations

Engineering Contradiction:
Improvecolloidal stabilityVSAvoidsolubility in organic media
Core Design Contradiction:
Stability of the object's compositionVSAdaptability or versatility

Solution Approach 1:

The patent changes the chemical parameters of the ligands by introducing polythiol compounds with specific molecular structures (formula I) that have both binding capability to the quantum dot surface and solubilizing pendant moieties. This parameter change enables the ligands to provide both colloidal stability and enhanced solubility in a wide range of organic media, resolving the contradiction between stability and adaptability.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses composite ligand structures combining polythiol backbones with various solubilizing pendant moieties (such as carboxylic acid, ester, amine, or hydrocarbon groups). These composite ligand molecules integrate multiple functions: binding to the quantum dot surface while simultaneously providing solubility in different organic solvents and resin formulations, thus resolving the contradiction between colloidal stability and solubility versatility.

Inventive Principle:
Principle #40Composite materials

2Adaptability or versatility

If carboxylic acid functionalized polymeric ligands are used, then solubility in resin formulations is achieved, but optical properties deteriorate due to displacement by thiol groups

Engineering Contradiction:
Improvesolubility in resin formulationsVSAvoidoptical properties
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent introduces polythiol ligands as intermediary molecules that mediate between the quantum dot surface and the resin formulation. These polythiol ligands have a dual function: they bind strongly to the quantum dot surface (preventing displacement by resin thiols) while simultaneously providing solubility in resin formulations through their pendant moieties. This intermediary role resolves the contradiction between solubility and optical property stability.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent applies preliminary anti-action by using polythiol ligands that preemptively bind to the quantum dot surface, creating a protective layer that prevents subsequent displacement by thiol groups from the resin formulation. This preliminary binding action counteracts the harmful effect of thiol displacement before it can occur, thereby maintaining optical properties while achieving solubility.

Inventive Principle:
Principle #9Preliminary anti-action

3Adaptability or versatility

If ligand exchange is performed to improve solubility, then solubility in organic media increases, but full width at half-maximum broadens and burn-in variations occur

Engineering Contradiction:
Improvesolubility in organic mediaVSAvoidfull width at half-maximum
Core Design Contradiction:
Adaptability or versatilityVSManufacturing precision

Solution Approach 1:

The patent optimizes the parameters of the polythiol ligands, including the length and structure of the pendant moieties and the number of thiol groups, to achieve the right balance between solubility and optical property stability. By carefully controlling these parameters, the patent enables ligand exchange that improves solubility while minimizing FWHM broadening and burn-in variations, thus resolving the contradiction between solubility and manufacturing precision.

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 polythiol ligands improve the solubility and stability of nanostructures in various solvents and resins, maintaining optical properties and reducing the risk of aggregation, thereby enhancing the performance of nanostructure films.

Implementation Method 1

Ligand exchange procedures have been performed using either a polyethylene glycol (PEG) based polymeric ligand functionalized with an amine or a carboxylic acid

Methodology Applied
Scientific EffectLigand exchange: Chemical Bonding

Implementation Method 2

Metal thiolate bonds have been found to be stronger than both metal carboxylate and metal phosphonate bonds

Methodology Applied
Scientific EffectCoordination bonding: Chemical Bonding

Implementation Method 3

The polythiol ligand with pendant moieties increase the solubility of the nanostructures in solvents and resins

Methodology Applied
Scientific EffectSolubility enhancement: Solvation

Implementation Method 4

a series of poly(ethylene glycol)-based bidentate ligands were produced that showed a strong interaction with CdSe/ZnS (core/shell) quantum dots and gold nanoparticles and promoted their dispersion in aqueous solutions

Methodology Applied
Scientific EffectHydrophilic interaction: Hydrophile

Implementation Method 5

Organic molecules bind to the inorganic surfaces of quantum dots providing both colloidal stability and terminating the crystalline lattice of the material reducing the number of surface trap states caused by dangling bonds

Methodology Applied
Scientific EffectSurface termination: Surface Tension

Data Source

PatentEP4217439B1Thermally stable polythiol ligands with pendant solubilizing moieties
Publication Date: 2026.02.18 SHOEI CHEM IND CO LTD
  • EP4217439B1 patent drawingFigure 1
  • EP4217439B1 patent drawingFigure 2
  • EP4217439B1 patent drawing

AI summary

The present invention provides nanostructure compositions and methods of producing nanostructure compositions. The nanostructure compositions comprise a population of nanostructures comprising polythiol ligands with pendant moieties. The polythiol ligand with pendant moieties increase the solubility of the nanostructures in solvents and resins. The present invention also provides nanostructure films comprising the nanostructure compositions and methods of making nanostructure films using the nanostructure compositions.