Mn4+ Doped Phosphor Synthesis via Segmented Ion Exchange

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Solution Overview

Problem

Existing processes for synthesizing Mn 4+ doped phosphors are not optimized for improved phosphor properties or lower manufacturing costs, which are desirable for achieving efficient warm white light emission.

Innovation Solution

A process involving the contact of Mn 4+ ions with a suspension of aqueous hydrofluoric acid and a complex fluoride compound, followed by the addition of A+ ions, to form Mn 4+ doped phosphors, which can be further treated with a fluorine-containing oxidizing agent to enhance performance.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional synthesis processes are used for Mn 4+ doped phosphors, then manufacturing is simpler, but phosphor properties and luminous efficacy are insufficient

Engineering Contradiction:
Improvephosphor propertiesVSAvoidsynthesis process
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The synthesis process is divided into distinct stages: (1) preparing the complex fluoride compound suspension, (2) adding Mn 4+ ions to dope the phosphor, (3) adding A+ ions to complete the crystal structure, and (4) optional fluorine-containing oxidizing agent treatment. This segmentation allows optimization of each stage independently to achieve superior phosphor properties while maintaining process manageability

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The complex fluoride compound is prepared and suspended in advance before introducing the Mn 4+ ions. This preliminary preparation ensures the host matrix is ready to accept dopant ions in controlled amounts, leading to more uniform doping and improved phosphor consistency and performance

Inventive Principle:
Principle #10Preliminary action

2Use of energy by moving object

If existing synthesis methods are used, then manufacturing cost is lower, but luminous efficacy and quantum efficiency are reduced

Engineering Contradiction:
Improveluminous efficacyVSAvoidmanufacturing process
Core Design Contradiction:
Use of energy by moving objectVSEase of manufacture

Solution Approach 1:

The synthesis process employs specific parameter controls including temperature ranges (room temperature to reflux), controlled addition rates of reagents, and precise stoichiometric ratios of Mn 4+ and A+ ions. These parameter optimizations maximize quantum efficiency (exceeding 85%) and luminous efficacy by ensuring optimal dopant incorporation into the crystal lattice

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The complex fluoride compound acts as an intermediary host matrix that facilitates the incorporation of Mn 4+ ions. This intermediary structure provides a stable framework that enhances energy transfer efficiency from the blue LED excitation source to the red emission, thereby improving overall luminous efficacy

Inventive Principle:
Principle #24Intermediary (Mediator)

3Stability of the object's composition

If simple synthesis processes are used, then manufacturing is easier, but emission spectrum tailoring and color stability are poor

Engineering Contradiction:
Improvecolor stabilityVSAvoidsynthesis process
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The process incorporates controlled feedback through sequential ion addition where the incorporation of Mn 4+ ions is followed by addition of A+ ions to complete the crystal structure. This feedback mechanism ensures proper stoichiometry and dopant distribution, resulting in stable emission characteristics and color consistency

Inventive Principle:
Principle #23Feedback

Solution Approach 2:

The phosphor is synthesized as a composite material combining the complex fluoride host compound with Mn 4+ dopant ions and A+ counter ions. This composite structure allows tailoring of the emission spectrum by adjusting the ratios and types of ions used, while maintaining color stability through the stable crystal lattice of the host material

Inventive Principle:
Principle #40Composite materials

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 results in Mn 4+ doped phosphors with improved properties, such as high quantum efficiency and tailored emission spectra, suitable for producing warm white light with enhanced luminous efficacy and color stability.

Implementation Method 1

contacting a source of Mn 4+ ions with a suspension of aqueous hydrofluoric acid and a complex fluoride compound

Methodology Applied
Scientific EffectIon Exchange: Ion Exchange

Implementation Method 2

the addition of A+ ions, to form Mn 4+ doped phosphors

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 3

treated with a fluorine-containing oxidizing agent to enhance performance

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 4

These materials absorb blue light strongly and efficiently emit between about 610-635 nm with little deep red/NIR emission

Methodology Applied
Scientific EffectPhotoluminescence: Photoluminescence

Data Source

PatentEP4553131A1Red-emitting phosphors, associated processes and devices
Publication Date: 2025.05.14 GE LIGHTING SOLUTIONS LLC
  • EP4553131A1 patent drawingFigure 1~2
  • EP4553131A1 patent drawingFigure 3~4
  • EP4553131A1 patent drawingFigure 5

AI summary

A process for synthesizing a Mn4+ doped phosphor is presented. The process includes contacting a source of Mn4+ ions to a suspension comprising aqueous hydrofluoric acid and a complex fluoride compound of formula (II) in solid form, and then contacting a source of A+ ions to the suspension to form the Mn4+ doped phosphor,         Ax [MFy]     (II) Wherein, A is Li, Na, K, Rb, Cs, or a combination thereof; M is Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, Gd, or a combination thereof; x is the absolute value of the charge of the [MFy] ion; y is 5, 6 or 7.