Sulfonated Regioregular Polythiophene for Stable Hole Transport

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Solution Overview

Problem

Current technologies face challenges in controlling solubility and electronic energy levels of hole injection and transport layers in organic-based devices like OLEDs and OPVs, particularly with polythiophenes, due to issues such as unstable doping, limited solubility, and lack of structural control, which affect the performance and versatility of these materials.

Innovation Solution

The development of sulfonated water-soluble or water-dispersible regioregular polythiophenes with sulfonate substituents directly bonded to the backbone, allowing for improved solubility, energy level control, and the elimination of separate dopants, enabling the formation of high-quality, thin films with enhanced orthogonal compatibility and processability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional polythiophenes are used for hole injection and transport layers, then the materials can provide basic conductivity, but they suffer from poor solubility, unstable doping, and lack of control over solubility and energy levels

Engineering Contradiction:
Improvestability of doping and solubility controlVSAvoidability to control solubility and energy levels for different applications
Core Design Contradiction:
ReliabilityVSAdaptability or versatility

Solution Approach 1:

The patent applies parameter changes by introducing sulfonate substituents at controlled positions (3-position and 4-position) on the polythiophene backbone. This chemical modification changes the solubility parameters and energy levels (HOMO and LUMO) of the polymer, enabling precise control over processing properties and electronic characteristics. The degree of sulfonation can be varied to achieve different levels of water solubility and conductivity, directly addressing the need for controllable solubility and energy levels.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite material structures by combining polythiophene backbone with sulfonate side groups and various counterions (such as metal cations or organic cations). This composite approach allows the material to exhibit both the conducting properties of polythiophene and the solubility enhancement from sulfonate groups, while the counterion selection further tunes the overall properties. This composite structure enables simultaneous achievement of stability and versatility.

Inventive Principle:
Principle #40Composite materials

2Reliability

If separate dopants are added to polythiophene systems, then conductivity can be enhanced, but the doping becomes unstable and processing complexity increases

Engineering Contradiction:
Improvestability of dopingVSAvoidneed for separate dopants and formulation steps
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent merges the dopant function directly into the polymer structure by incorporating sulfonate groups as integral part of the polythiophene chain. The sulfonate groups serve as both structural elements and dopant sources, eliminating the need for separate dopant addition steps. This self-doping approach ensures stable doping because the dopant is covalently bound to the polymer backbone, preventing leaching or aggregation issues associated with physical mixing of separate dopants.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The sulfonated polythiophene system is self-doping, meaning the polymer itself provides the dopant function through its sulfonate groups. This self-service capability eliminates the need for external dopant management, simplifying formulation and processing while ensuring stable, reproducible doping levels. The polymer automatically regulates its own conductivity through the inherent sulfonate groups.

Inventive Principle:
Principle #25Self-service

3Reliability

If thick films are used to ensure adequate hole transport, then film quality can be maintained, but the device performance and efficiency are reduced due to excessive thickness

Engineering Contradiction:
Improvefilm qualityVSAvoiddevice efficiency and performance
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The sulfonate substitution changes the physical parameters of the polythiophene, dramatically improving water solubility and enabling the formation of uniform, pin-hole-free thin films through solution processing. The enhanced solubility allows for better film formation at lower concentrations and thinner thicknesses, while the sulfonate groups also improve wetting and adhesion properties, ensuring high film quality even at reduced thickness.

Inventive Principle:
Principle #35Parameter changes

4Manufacturing precision

If regioregular polythiophenes are synthesized, then structural control and purity are improved, but the solubility and processability remain limited

Engineering Contradiction:
Improvestructural control and regioregularityVSAvoidsolubility and processability
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The introduction of sulfonate substituents changes the solubility parameters of regioregular polythiophenes without affecting their structural regularity. The sulfonate groups are added as side chains that do not disrupt the head-to-tail coupling pattern of the regioregular backbone, maintaining crystallinity and structural order while dramatically improving solubility in water and aqueous solutions. This allows regioregular polymers to be processed from water-based solvents.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The sulfonate groups act as intermediary elements that mediate between the structurally rigid regioregular polythiophene backbone and the processing environment. These water-soluble side groups serve as a bridge, allowing the otherwise insoluble regioregular polymer to be dissolved and processed from aqueous solutions while maintaining the structural integrity and regioregularity of the backbone.

Inventive Principle:
Principle #24Intermediary (Mediator)

Data Source

PatentEP2537874B1Sulfonation of conducting polymers and OLED, photovoltaic, and ESD devices
Publication Date: 2021.05.19 NISSAN CHEM CORP
  • EP2537874B1 patent drawingFigure 1
  • EP2537874B1 patent drawingFigure 2
  • EP2537874B1 patent drawingFigure 3

AI summary

Conducting polymer systems for hole injection or transport layer applications including a composition comprising: a water soluble or water dispersible regioregular polythiophene comprising (i) at least one organic substituent, and (ii) at least one sulfonate substituent comprising sulfonate sulfur bonding directly to the polythiophene backbone. The polythiophene can be water soluble, water dispersible, or water swellable. They can be self-doped. The organic substituent can be an alkoxy substituent, or an alkyl substituent. OLED, PLED, SMOLED, PV, and ESD applications can be used.