Organic Semiconductor Doping Using Protic Ionic Liquids

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Solution Overview

Problem

Existing methods for p-doping organic semiconductors, particularly triphenylamine-based hole transport materials, face challenges with low hole mobilities and poor long-term stability due to in-situ doping approaches, which result in variability and incorporation of impurities that hinder device performance.

Innovation Solution

Chemical doping of organic semiconductors using protic ionic liquids, specifically bis(trifluoromethanesulfonyl)imide (H-TFSI), to achieve high conductivities and improved atmospheric stability without the need for extraneous additives, separating the effects of p-doping from ionic additives on charge generation and collection.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If in-situ doping approaches are used to dope organic semiconductors, then doping efficiency may be improved, but device stability and performance consistency deteriorate due to variability and incorporation of impurities

Engineering Contradiction:
Improvedoping efficiencyVSAvoiddevice stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent applies preliminary action by pre-synthesizing the doped organic semiconductor material before device fabrication. The doping process is performed in advance during material synthesis, allowing thorough mixing and reaction completion before the material is processed into devices. This eliminates variability introduced by in-situ doping during device manufacturing, as the doping state is already established and stable in the material itself.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent extracts the doping process from the device fabrication process. Instead of performing doping in-situ during device manufacturing, the doping is separated and performed as a standalone material synthesis step. This extraction allows for optimized doping conditions and thorough mixing without constraints from device structure requirements, while preventing impurity incorporation into the final device architecture.

Inventive Principle:
Principle #2Taking out (Extraction)

2Adaptability or versatility

If triphenylamine-based hole transport materials are used, then wide bandgaps and tunable HOMO levels are achieved, but hole mobilities remain low

Engineering Contradiction:
Improvebandgap and HOMO level tunabilityVSAvoidhole mobility
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent applies parameter changes by systematically varying the doping level of the triphenylamine-based hole transport material. By controlling the amount of dopant (e.g., iodine, bromine) incorporated during synthesis, the electrical conductivity and hole mobility are enhanced while preserving the inherent advantages of wide bandgap and tunable HOMO levels. The doping introduces charge carriers that improve conductivity without fundamentally altering the molecular structure and optoelectronic properties of the triphenylamine core.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite materials by combining triphenylamine-based hole transport materials with electron-accepting dopants such as iodine or bromine. This composite approach leverages the beneficial properties of both components: the triphenylamine provides wide bandgap and tunable HOMO levels, while the dopant introduces mobile charge carriers that enhance hole mobility and conductivity. The resulting doped material exhibits superior overall performance compared to the undoped parent compound.

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 use of H-TFSI as a protic ionic liquid enables effective p-doping of organic semiconductors, enhancing conductivity and long-term stability, and eliminating the need for additional additives, thereby improving the performance and reliability of semiconductor devices.

Implementation Method 1

chemical doping introduces impurities into the organic semiconductors which increase the density of mobile charge carriers and thus conductivity

Methodology Applied
Scientific EffectChemical doping: Oxidation

Implementation Method 2

One of the first described mechanisms was the protonic acid (H +

Methodology Applied
Scientific EffectProtonic acid doping mechanism: Oxidation

Data Source

PatentEP3005434B1Organic semiconductor doping process
Publication Date: 2019.03.20 OXFORD UNIVERSITY INNOVATION LTD
  • EP3005434B1 patent drawingFigure 1(a)~2
  • EP3005434B1 patent drawingFigure 3~4
  • EP3005434B1 patent drawingFigure 5(a)~6

AI summary

The present invention relates to the doping of organic semiconductors and processes for producing layers of p-doped organic semiconductors. Disclosed is a process for p-doping organic semiconductors comprising treating the organic semiconductor with an oxidised salt of the organic semiconductor. A process for producing a layer of a p-doped organic semiconductor comprising producing a p-doped organic semiconductor by treating the organic semiconductor with an oxidised salt of the organic semiconductor; disposing a composition comprising a solvent and the p-doped organic semiconductor on a substrate; and removing the solvent is also described. Also disclosed is a process for producing a layer of a p-doped organic semiconductor comprising: disposing a composition comprising a solvent, the organic semiconductor and a protic ionic liquid on a substrate; and removing the solvent. A process for producing a semiconductor device comprising a process for doping an organic semiconductor according to the invention is also described. Finally, a high purity p-dopant composition is described.