InP Quantum Dots Narrow FWHM via SILAR Shell Growth

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Solution Overview

Problem

Current methods for manufacturing red-emitting quantum dots, particularly those based on InP, face challenges in achieving a Full Width at Half Maximum (FWHM) of 40 nm or less and a quantum efficiency of 70% or more, which are essential for high color-purity displays and stability.

Innovation Solution

A method involving the preparation of an InX-based quantum dot seed, followed by continuous injection of a Zn(In)X-based cluster to form a core, and subsequent coating with a ZnSe and ZnS shell using the Successive Ion Layer Adsorption and Reaction (SILAR) method, where X comprises phosphorus, arsenic, or antimony, to enhance quantum efficiency and color purity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Object-generated harmful factors

If InP quantum dots are synthesized using general methods, then cadmium-free material is achieved, but manufacturing difficulty increases and mass production becomes difficult

Engineering Contradiction:
Improvecadmium pollutionVSAvoidmanufacturing difficulty
Core Design Contradiction:
Object-generated harmful factorsVSEase of manufacture

Solution Approach 1:

The patent changes the synthesis parameters by introducing a seed-mediated growth method with controlled temperature profiles (nucleation at lower temperature, growth at higher temperature) and specific precursor concentrations to enable mass production of InP quantum dots while maintaining cadmium-free composition

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a seed layer as an intermediary to facilitate the formation of InP quantum dots, allowing controlled nucleation and growth that simplifies mass production while maintaining the desired optical properties and cadmium-free composition

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-generated harmful factors

If InP quantum dots are synthesized by general methods, then cadmium-free material is achieved, but particle size uniformity deteriorates

Engineering Contradiction:
Improvecadmium pollutionVSAvoidparticle size uniformity
Core Design Contradiction:
Object-generated harmful factorsVSManufacturing precision

Solution Approach 1:

The patent performs preliminary nucleation at a lower temperature to form uniform seeds with controlled size distribution, then uses these seeds as templates for controlled growth at higher temperature, ensuring uniform particle size throughout the batch while maintaining cadmium-free composition

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent employs staged temperature parameters - first nucleation at lower temperature (e.g., 200-300°C) to form uniform seeds, then growth at higher temperature (e.g., 300-400°C) to achieve desired size, resulting in uniform particle size distribution for cadmium-free InP quantum dots

Inventive Principle:
Principle #35Parameter changes

3Object-generated harmful factors

If InP quantum dots are synthesized by general methods, then cadmium-free material is achieved, but quantum yield deteriorates

Engineering Contradiction:
Improvecadmium pollutionVSAvoidquantum yield
Core Design Contradiction:
Object-generated harmful factorsVSReliability

Solution Approach 1:

The patent introduces a shell layer as an intermediary to protect the InP quantum dot core, improving quantum yield by reducing surface recombination and enhancing stability while maintaining the cadmium-free composition

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent creates a composite structure with InP core and shell layer (e.g., ZnS or CdSe shell), combining the advantages of cadmium-free core material with the protective and optical properties of the shell, achieving high quantum yield while maintaining environmental compatibility

Inventive Principle:
Principle #40Composite materials

4Reliability

If shell coating is applied to InP quantum dots, then luminescence stability improves, but productivity and manufacturing cost increase

Engineering Contradiction:
Improveluminescence stabilityVSAvoidreaction time
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The patent performs shell coating in a continuous one-step process rather than multiple separate steps, maintaining reaction conditions and preventing interruptions that would extend total reaction time, thereby improving productivity while achieving stable luminescence

Inventive Principle:
Principle #20Continuity of useful action

Solution Approach 2:

The patent optimizes shell coating parameters including temperature, precursor concentration, and injection rate to achieve complete shell formation in reduced time, balancing luminescence stability with manufacturing efficiency

Inventive Principle:
Principle #35Parameter changes

5Reliability

If shell coating is applied to InP quantum dots, then luminescence stability improves, but manufacturing cost increases

Engineering Contradiction:
Improveluminescence stabilityVSAvoidmanufacturing cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent consolidates shell coating into a single continuous step, reducing the number of reagents and process cycles needed, thereby lowering manufacturing cost while maintaining luminescence stability through complete shell formation

Inventive Principle:
Principle #20Continuity of useful action

6Reliability

If shell coating is applied to InP quantum dots, then luminescence stability improves, but coating uniformity deteriorates

Engineering Contradiction:
Improveluminescence stabilityVSAvoidcoating uniformity
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The patent performs preliminary surface treatment and seed formation to create uniform templates before shell growth, ensuring even shell distribution and preventing defects that would compromise luminescence stability

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent optimizes shell coating parameters including temperature profile, precursor concentration, and injection rate to achieve uniform shell thickness and composition throughout the quantum dot batch, ensuring consistent luminescence properties

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 approach results in quantum dots with improved light-emitting efficiency, color purity, and reproducibility across a wide range, achieving a FWHM of 40 nm or less and a quantum yield of 70% or more, while also protecting the core from external environments.

Implementation Method 1

a roomtemperature organometallic compound is rapidly injected to a high-temperature solvent using a precursor to cause nucleation through a pyrolysis reaction

Methodology Applied
Scientific EffectNucleation: Nucleation

Implementation Method 2

cause nucleation through a pyrolysis reaction

Methodology Applied
Scientific EffectPyrolysis: Pyrolysis

Implementation Method 3

adding a selenium compound and a zinc precursor to the mixture to form a first shell to be coated on the InX-based core

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Implementation Method 4

adding a sulfur compound and the zinc precursor to the mixture to form a second shell to be coated on the first shell

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Data Source

PatentEP3760692B1Red-emitting quantum dots having narrow full width at half maximum and emission wavelength for application to high-color-purity display, and preparation method therefor
Publication Date: 2023.03.15 DAEGU GYEONGBUK INSTITUTE OF SCIENCE AND TECHNOLOGY
  • EP3760692B1 patent drawingFigure 1
  • EP3760692B1 patent drawingFigure 2
  • EP3760692B1 patent drawingFigure 3(a)~3(d)

AI summary

Disclosed is a method of manufacturing InP-based nanoparticles for application to high color-purity displays. More particularly, provided is a method of manufacturing quantum dots, the method comprising: preparing a mixture including an InX-based quantum dot seed; continuously injecting a Zn(In)X-based cluster to the mixture to form an InX-based core; adding a selenium compound and a zinc precursor to the mixture to form a first shell to be coated on the InX-based core; and adding a sulfur compound and the zinc precursor to the mixture to from a second shell to be coated on the first shell, wherein the first shell is formed of ZnSe, the second shell is formed of ZnS, and X comprises phosphorus (P), arsenic (As) or antimony (Sb). Further, a technology of synthesizing uniform core quantum dots and a light-emitting layer for a next-generation self-luminous device capable of addressing color purity and stability problems of existing quantum dots are provided.