Quantum Dot Core-Shell Preparation via Organic Acid Passivation

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Solution Overview

Problem

Existing methods for preparing core-shell quantum dots using continuous shell-source precursor injection result in poor solubility and increased lattice stress, leading to reduced fluorescence intensity due to fewer surface ligands and more surface lattice defects.

Innovation Solution

A method involving the use of organic carboxylic acids and amines to bond with the surface of initial QD cores, followed by a shell-growth reaction system that includes these organic compounds, which helps in forming a desired epitaxial interface and passivating the surface, thereby reducing defects and improving monodispersity and fluorescence intensity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If continuous shell-source precursor injection is used for shell growth, then the shell layer can be formed, but the solubility deteriorates and surface ligands decrease

Engineering Contradiction:
Improveshell layer formationVSAvoidsolubility
Core Design Contradiction:
ReliabilityVSEase of operation

Solution Approach 1:

The patent applies preliminary action by pre-modifying the QD core surface with organic carboxylic acid before shell growth. This preliminary surface modification creates favorable conditions for subsequent shell formation, ensuring better ligand coverage and solubility while maintaining reliable shell layer formation. The pre-treatment step addresses the solubility issue before the shell growth process begins.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent uses organic carboxylic acid as an intermediary substance that mediates between the QD core and the shell layer. This intermediary agent facilitates better interface compatibility, improves surface ligand coverage, and enhances solubility without compromising the shell layer formation. The carboxylic acid acts as a bridge that resolves the contradiction between shell formation reliability and solubility.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Reliability

If continuous shell-source precursor injection is used for shell growth, then the shell layer can be formed, but lattice stress increases and fluorescence intensity decreases

Engineering Contradiction:
Improveshell layer formationVSAvoidlattice stress and fluorescence intensity
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent applies preliminary action by pre-modifying the QD core surface with organic carboxylic acid before shell growth. This preliminary treatment reduces lattice stress at the core-shell interface and minimizes defect formation, thereby maintaining high fluorescence intensity while ensuring reliable shell layer formation. The pre-treatment prevents harmful effects before they occur during shell growth.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The organic carboxylic acid serves as an intermediary that reduces lattice stress between the core and shell layers. This mediator minimizes interface defects and maintains structural integrity, preventing the harmful effects of high lattice stress and preserving fluorescence intensity while still achieving reliable shell formation.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Ease of manufacture

If simple shell-source precursor injection is used, then the preparation process is simple, but surface ligands are insufficient and solubility is poor

Engineering Contradiction:
Improvepreparation process simplicityVSAvoidsolubility
Core Design Contradiction:
Ease of manufactureVSEase of operation

Solution Approach 1:

The patent applies preliminary action by adding a surface modification step with organic carboxylic acid before shell growth. Although this adds one step to the process, it significantly improves surface ligand coverage and solubility. The preliminary treatment ensures better overall results while maintaining relatively simple preparation conditions.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The organic carboxylic acid acts as an intermediary that enhances surface ligand coverage and solubility without requiring complex preparation procedures. This intermediary substance improves the quality of QDs while keeping the overall process relatively simple, resolving the contradiction between manufacturing simplicity and solubility performance.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Quantity of substance

If more surface ligands are to be obtained, then shell growth control must be improved, but the preparation process becomes more complex

Engineering Contradiction:
Improvesurface ligandsVSAvoidpreparation process complexity
Core Design Contradiction:
Quantity of substanceVSDevice complexity

Solution Approach 1:

The patent applies preliminary action by pre-modifying the QD core surface with organic carboxylic acid before shell growth. This preliminary step ensures adequate surface ligand coverage is achieved early in the process, eliminating the need for complex multi-step shell growth control procedures. The pre-treatment simplifies subsequent shell growth while maintaining high surface ligand quantity.

Inventive Principle:
Principle #10Preliminary 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

The method enhances the solubility and fluorescence intensity of core-shell structure quantum dots by reducing defect states and lattice stress, resulting in more uniform particle sizes and improved film-forming quality.

Implementation Method 1

mixing the initial QD cores with an organic carboxylic acid, so that the organic carboxylic acid is bonded to the surface of the initial QD cores

Methodology Applied
Scientific EffectSurface bonding/Passivation: Chemical Bonding

Implementation Method 2

preparing a shell layer on the surface of the initial QD cores... helping in forming a desired epitaxial interface

Methodology Applied
Scientific EffectEpitaxial growth: Epitaxy

Implementation Method 3

mixing and heating the solution system... with an organic amine... or... with an organic phosphine

Methodology Applied
Scientific EffectSurface bonding/Passivation: Chemical Bonding

Data Source

PatentEP3865556B1Preparation method for quantum dots
Publication Date: 2024.01.10 TCL TECHNOLOGY GROUP CORPORATION
  • EP3865556B1 patent drawingFigure 1~2

AI summary

The present application discloses a preparation method for quantum dots (QDs), including: providing initial QD cores, mixing the initial QD cores with an organic carboxylic acid to bond the organic carboxylic acid to the surface of the initial QD cores; preparing a shell layer on the surface of the initial QD cores, where the step of preparing the shell layer on the surface of the initial QD cores is performed in a shell-growth reaction system containing an organic carboxylic acid; mixing the solution system, obtained after the completion of the shell-layer growth reaction, with an organic amine such that the organic amine complexes with the shell of the remaining cationic precursor; or mixing and heating the solution system, obtained after the completion of the shell-layer growth reaction, with an organic phosphine; or mixing and heating the solution system, obtained after the completion of the shell-layer growth reaction, with a mixed solution of an organic amine and an organic phosphine.