Pyridine-Based TADF Emitters for OLED Stability

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Solution Overview

Problem

Current organic light-emitting diode (OLED) materials face issues with long-term stability, thermal stability, chemical stability against water and oxygen, limited emission colors, non-evaporability, and insufficient efficiency at high current densities or luminances, particularly with thermally activated delayed fluorescence (TADF) materials, which also have high production costs and unsuitable energy levels.

Innovation Solution

Development of organic molecules with specific structures, such as those described by formulas 1 and 3b, incorporating a divalent linking group that separates the conjugated systems of electron-donating and electron-accepting parts, enhancing the localization of frontier orbitals and increasing the overlap integral between HOMO and LUMO for improved luminescence and decay times.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Use of energy by moving object

If TADF materials are used in OLEDs, then all excitons can be converted into light (theoretical 100% efficiency), but the materials suffer from insufficient long-term stability, thermal stability, and chemical stability

Engineering Contradiction:
Improveexciton conversion efficiencyVSAvoidlong-term stability and thermal stability
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The patent employs composite molecular structures combining electron-donating units (carbazole, triphenylamine) with electron-accepting units (pyridine, pyrimidine, triazine) linked through specific linking groups. This composite approach creates TADF emitters with both high exciton conversion efficiency and improved stability, as the synergistic interaction between donor and acceptor units optimizes both photophysical properties and material robustness

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent introduces specific structural modifications at localized positions within the molecule, such as fluorine substitution at positions 2 and 6 of the pyridine ring, and specific substitution patterns on the electron-donating units. These localized modifications enhance stability without compromising the overall TADF mechanism and exciton conversion efficiency

Inventive Principle:
Principle #3Local quality

2Use of energy by moving object

If TADF materials are used to achieve high efficiency, then all excitons can be converted into light, but the materials have insufficient efficiency at high current densities or high luminances

Engineering Contradiction:
Improveexciton conversion efficiencyVSAvoidefficiency at high current densities
Core Design Contradiction:
Use of energy by moving objectVSReliability

Solution Approach 1:

The patent systematically adjusts key molecular parameters including the energy gap between S1 and T1 states (ΔEST), HOMO-LUMO energy levels, and molecular geometry through varying the electron-donating and electron-accepting units. These parameter optimizations ensure efficient TADF at both low and high current densities by maintaining appropriate energy levels for exciton management under different operating conditions

Inventive Principle:
Principle #35Parameter changes

3Adaptability or versatility

If previous TADF materials are used, then some emission colors are available, but not all major emission colors are available and syntheses are expensive

Engineering Contradiction:
Improveemission color availabilityVSAvoidsynthesis cost
Core Design Contradiction:
Adaptability or versatilityVSEase of manufacture

Solution Approach 1:

The patent develops a universal molecular platform based on the pyridine/pyrimidine/triazine core with variable electron-donating units that can be systematically modified to achieve different emission colors across the visible spectrum. This modular approach allows tuning of emission wavelengths while using common synthetic building blocks, thereby reducing synthesis costs and enabling access to all major emission colors

Inventive Principle:
Principle #6Universality (Multi-functionality)

Solution Approach 2:

The patent divides the TADF emitter into distinct functional segments: a core electron-accepting unit (pyridine/pyrimidine/triazine), electron-donating units (carbazole, triphenylamine derivatives), and linking groups. This segmentation allows independent optimization of each module for cost-effective synthesis while maintaining overall TADF performance and enabling color tuning through combinatorial assembly of these segments

Inventive Principle:
Principle #1Segmentation

4Use of energy by moving object

If TADF materials are used, then theoretically all excitons can be converted into light, but the materials have insufficient chemical stability with respect to water and oxygen

Engineering Contradiction:
Improveexciton conversion efficiencyVSAvoidchemical stability against water and oxygen
Core Design Contradiction:
Use of energy by moving objectVSObject-affected harmful factors

Solution Approach 1:

The patent extracts and addresses the specific vulnerability of TADF materials to water and oxygen by incorporating structural features that enhance chemical stability, such as fluorine substitution and aromatic ring systems with high electron density delocalization. These extracted stability-enhancing motifs are integrated into the TADF emitter structure without compromising the exciton conversion mechanism

Inventive Principle:
Principle #2Taking out (Extraction)

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

These organic molecules achieve high luminescence quantum yields and short decay times, overcoming the limitations of previous TADF materials by allowing efficient emission and thermal activated delayed fluorescence, while maintaining solubility and polymerizability without altering electronic properties.

Implementation Method 1

A new generation of OLEDs is based on the use of delayed fluorescence (TADF: thermally activated delayed fluorescence or singlet harvesting). Here, for example, Cu(I) complexes can be used, which can thermally reset triplet exitons into a singlet state due to a small energy gap between the lowest triplet state T1 and the overlying singlet state S1 (ΔE(S1-T1)).

Methodology Applied
Scientific EffectThermally activated delayed fluorescence (TADF):

Implementation Method 2

In this layer, negative charge carriers (electrons) and positive charge carriers (holes) meet, which recombine to form so-called excitons (=excited states). The energy contained in the excitons can be emitted by the corresponding emitters in the form of light, in which case one speaks of electroluminescence.

Methodology Applied
Scientific EffectElectroluminescence: Electroluminescence

Data Source

PatentEP3247771B1Pyridines and derivatives thereof as components for use in optoelectronic components
Publication Date: 2020.06.10 CYNORA
  • EP3247771B1 patent drawingFigure 1
  • EP3247771B1 patent drawingFigure 2
  • EP3247771B1 patent drawing

AI summary

The invention relates to organic molecules, having a structure of formula 1 and to the use thereof in optoelectronic components, wherein: X represents SO2, CO or a C–C-single bond; m represents 0 or 1; n represents 1, 2 or 3; r represents 0 or 1; s represents 0 or 1; LG is a divalent linker group, selected from: (II); or LG is an element–element-single bond.