Core/Shell Quantum Dot Sphericity via Acid Etching

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Solution Overview

Problem

Current methods for producing highly luminescent quantum dots face challenges in achieving spherical morphology and stability, particularly for cadmium-free InP quantum dots, which are prone to degradation and have poor size distribution and crystal facets, limiting their application in LEDs and displays.

Innovation Solution

A method involving acid etching and/or annealing of nanocrystal cores with organic acids, such as lauric acid or trifluoromethanesulfonic acid, followed by heating, to improve the sphericity and surface defects of the cores, resulting in more stable and luminescent core/shell nanostructures like InP/ZnSe/ZnS.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a thick shell coating of several nanometers is deposited on the quantum dot core, then stability against degradation is improved, but the quantum yield decreases due to increased probability of non-radiative recombination at the core-shell interface

Engineering Contradiction:
ImprovestabilityVSAvoidquantum yield
Core Design Contradiction:
ReliabilityVSLoss of energy

Solution Approach 1:

The shell is divided into multiple sub-shells with different compositions and thicknesses. The first sub-shell (e.g., ZnSe) provides initial protection, while the second sub-shell (e.g., ZnS) with higher band gap further suppresses charge transfer. This segmented approach allows achieving both stability and high quantum yield by optimizing each sub-shell's contribution.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

Different regions of the shell have different material compositions tailored to specific functions. The inner sub-shell has composition optimized for lattice matching and initial passivation, while the outer sub-shell has composition optimized for suppressing charge transfer to environmental agents. This local optimization resolves the contradiction between stability and quantum yield.

Inventive Principle:
Principle #3Local quality

2Object-affected harmful factors

If InP quantum dots are used as cadmium-free alternative, then environmental safety is improved, but inherent stability and resistance to photooxidation deteriorate compared to cadmium selenide quantum dots

Engineering Contradiction:
Improveenvironmental safetyVSAvoidstability
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The InP core is combined with shell materials (ZnSe, ZnS) to form a composite core/shell structure. The shell materials provide the stability and photooxidation resistance that InP lacks, while the InP core maintains the cadmium-free, environmentally safe property. This composite approach allows InP quantum dots to achieve both environmental safety and stability.

Inventive Principle:
Principle #40Composite materials

3Reliability

If multiple shells and thick shells are formed to mitigate photoinduced deterioration, then optical stability is improved, but the complexity of shelling engineering increases

Engineering Contradiction:
Improveoptical stabilityVSAvoidshelling engineering complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent extracts the essential protective function from complex multi-shell structures and implements it through a simplified two-sub-shell design. By identifying the key requirements (lattice matching, band gap progression, sufficient thickness), the solution achieves optical stability with reduced engineering complexity compared to elaborate multi-shell approaches.

Inventive Principle:
Principle #2Taking out (Extraction)

4Duration of action of moving object

If quantum dots are exposed to continuous excitation photons, then luminescence function is maintained, but photoinduced deterioration increases over time

Engineering Contradiction:
Improveluminescence durationVSAvoidphotoinduced deterioration
Core Design Contradiction:
Duration of action of moving objectVSReliability

Solution Approach 1:

The core/shell structure provides beforehand cushioning against photoinduced deterioration. The shell layers are designed in advance to suppress charge transfer and protect the core from environmental agents and photooxidation. This protective cushioning allows the quantum dots to maintain luminescence function over extended periods of continuous excitation without significant deterioration.

Inventive Principle:
Principle #11Beforehand cushioning (Prior cushioning)

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 process enhances the sphericity and photoluminescence quantum yield of the nanostructures, achieving up to 99% quantum yield and maintaining high luminescence intensity under continuous exposure, addressing the stability and morphology issues of previous methods.

Implementation Method 1

contacting a nanocrystal core, with an organic acid, wherein the molar ratio of the nanocrystal core to the organic acid is between about 1:1 and about 1:1000

Methodology Applied
Scientific EffectAcid etching:

Implementation Method 2

heating (a) at a temperature between about 50 °C and about 250 °C to provide a nanostructure

Methodology Applied
Scientific EffectThermal annealing: Annealing

Implementation Method 3

highly luminescent nanostructures are particularly desirable for such applications

Methodology Applied
Scientific EffectPhotoluminescence: Photoluminescence

Data Source

PatentEP3458545B1Method to improve the morphology of core/shell quantum dots for highly luminescent nanostructures
Publication Date: 2020.10.21 NANOSYS INC
  • EP3458545B1 patent drawingFigure 1
  • EP3458545B1 patent drawingFigure 2
  • EP3458545B1 patent drawingFigure 3

AI summary

Highly luminescent nanostructures, particularly highly luminescent quantum dots, comprising a nanocrystal core are provided. Also provided are methods of increasing the sphericity of nanostructures comprising subjecting nanocrystal cores to an acid etch step, an annealing step, or a combination of an acid etch step and an annealing step.