Surface-Modified Nanoparticles With Crosslinked Ligand Shells

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Solution Overview

Problem

Current methods for modifying the surface of nanoparticles to enhance compatibility with various media often result in reduced quantum yield and larger particle sizes, and fail to maintain the integrity and photophysical properties of semiconductor nanoparticles, particularly cadmium-free nanoparticles, which are prone to degradation and agglomeration.

Innovation Solution

The method involves associating a ligand interactive agent with the nanoparticle, crosslinking it with a melamine-based crosslinking agent, and binding a surface modifying ligand to improve compatibility with specific solvents or media, using agents like C8-C20 fatty acids or esters, and incorporating functional groups that enhance stability and dispersibility in polar solvents.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a core-shell structure is used to passivate surface defects, then quantum efficiency is improved, but surface compatibility with various media deteriorates

Engineering Contradiction:
Improvequantum efficiencyVSAvoidsurface compatibility
Core Design Contradiction:
ReliabilityVSAdaptability or versatility

Solution Approach 1:

The patent applies composite materials by combining the inorganic core-shell structure (CdSe/ZnS) with organic ligand layers (phosphine oxides, carboxylic acids, amines) to create a hybrid surface modification system. This composite approach maintains the quantum efficiency benefits of the core-shell structure while adding surface compatibility through the organic ligand shell that can interact with various media.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent changes surface chemical parameters by introducing different types of ligands with varying functional groups (phosphine oxides, carboxylic acids, amines) that have different polarities and binding affinities. This allows tuning of surface properties to achieve compatibility with different media while preserving the underlying core-shell quantum efficiency.

Inventive Principle:
Principle #35Parameter changes

2Adaptability or versatility

If nanoparticles are dispersed in media for application, then compatibility is improved, but agglomeration occurs leading to reduced quantum yield

Engineering Contradiction:
Improvemedia compatibilityVSAvoidquantum yield
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent uses organic ligands as intermediary molecules between the inorganic nanoparticle core and the external media. These ligands form a protective shell that mediates interaction with the surrounding environment, preventing direct contact between nanoparticles that would cause agglomeration, while still allowing optical properties to be maintained.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent employs thin organic ligand shells surrounding the nanoparticle core. These flexible molecular layers provide steric stabilization and prevent agglomeration by creating a physical barrier between particles, while being thin enough to not significantly interfere with the optical properties and quantum yield of the core.

Inventive Principle:
Principle #30Flexible shells and thin films

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 surface-functionalized nanoparticles with increased stability, reduced susceptibility to degradation, and higher quantum yields, enabling effective dispersion in aqueous and organic media while maintaining fluorescence properties, particularly for cadmium-free nanoparticles.

Implementation Method 1

associating a first type of molecule, referred to herein as a ligand interactive agent, with the surface of the nanoparticle. The ligand interactive agent is then reacted with a linking/crosslinking agent

Methodology Applied
Scientific EffectChemical bonding: Chemical Bonding

Implementation Method 2

because of quantum confinement effects, the band gap typically gradually becomes larger as the size of the nanoparticle decreases. This effect is a consequence of the confinement of an 'electron in a box,' giving rise to discrete energy levels

Methodology Applied
Scientific EffectQuantum confinement:

Implementation Method 3

Semiconductor nanoparticles tend to exhibit a narrow bandwidth emission that is dependent upon the particle size and composition of the nanoparticle material

Methodology Applied
Scientific EffectPhotoluminescence: Photoluminescence

Data Source

PatentEP2794464B1Surface modified nanoparticles
Publication Date: 2023.11.22 SAMSUNG ELECTRONICS CO LTD
  • EP2794464B1 patent drawingFigure 1~2
  • EP2794464B1 patent drawingFigure 3
  • EP2794464B1 patent drawingFigure 4

AI summary

Surface-modified nanoparticles are produced by associating ligand interactive agents with the surface of a nanoparticle. The ligand interactive agents are bound to surface modifying ligands that are tailored to impart particular solubility and/or compatibility properties. The ligand interactive agents are crosslinked via a linking/crosslinking agent, such as hexamethoxymethylmelamine or a derivative thereof. The linking/crosslinking agent may provide a binding site for binding the surface modifying ligands to the ligand interactive agents.