Hybrid sc-SWCNT Purification via Polymer Extraction and Adsorption

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Solution Overview

Problem

Current methods for enriching semiconducting single-walled carbon nanotubes (sc-SWCNTs) face limitations in scalability, cost, yield, and device performance, particularly in achieving high purity and yield simultaneously, which is crucial for applications like thin film transistors.

Innovation Solution

A hybrid process involving the use of conjugated polymers for selective dispersion and extraction of sc-SWCNTs followed by an inorganic adsorptive medium to further separate sc-SWCNTs from metallic SWCNTs, optimizing the polymer:SWCNT ratio and processing conditions for high purity and yield.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conjugated polymer extraction is used to enrich sc-SWCNTs, then sc-SWCNT purity can be improved to >99%, but the yield remains limited and scalability is challenging

Engineering Contradiction:
Improvesc-SWCNT purityVSAvoidyield and scalability
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent divides the enrichment process into two distinct stages: (1) conjugated polymer extraction to achieve high purity (>99% sc-SWCNTs), and (2) inorganic adsorptive medium treatment to further separate and concentrate the enriched fraction. This segmentation allows each step to be optimized independently, with the first step focusing on purity and the second on yield and scalability.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent introduces an inorganic adsorptive medium as an intermediary substance that selectively binds to sc-SWCNTs in the enriched dispersion. This intermediary enables further separation and concentration without requiring additional complex polymer chemistry, thereby improving yield and scalability while maintaining high purity.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Manufacturing precision

If density gradient ultracentrifugation is used to separate sc-SWCNTs, then high purity can be achieved, but the method lacks scalability and is costly

Engineering Contradiction:
Improvesc-SWCNT purityVSAvoidscalability and cost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The patent replaces the mechanical and costly density gradient ultracentrifugation system with a chemical extraction approach using conjugated polymers. The polymers selectively interact with sc-SWCNTs through pi-pi stacking and van der Waals forces, enabling separation without complex mechanical equipment, thereby improving scalability and reducing cost while maintaining high purity.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

3Manufacturing precision

If gel chromatography is used to enrich sc-SWCNTs, then high purity can be achieved, but the cost becomes prohibitive

Engineering Contradiction:
Improvesc-SWCNT purityVSAvoidcost
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The patent employs conjugated polymers as disposable, low-cost extraction media that can be easily removed from the final product through simple filtration or precipitation. These polymers are significantly cheaper than gel chromatography materials and can be discarded after a single use, thereby reducing overall process cost while achieving high purity enrichment.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

4Manufacturing precision

If selective polymer extraction is used, then sc-SWCNT purity can be improved, but device performance and yield are limited

Engineering Contradiction:
Improvesc-SWCNT purityVSAvoiddevice performance and yield
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The patent performs preliminary enrichment using conjugated polymer extraction to achieve high purity (>99% sc-SWCNTs) before applying the inorganic adsorptive medium treatment. This preliminary action concentrates the sc-SWCNTs in a purified form, making the subsequent adsorption step more effective and enabling better device performance and higher yield.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent combines two different separation mechanisms: conjugated polymer extraction (based on electronic structure and chirality) and inorganic adsorption (based on surface interactions). This composite approach leverages the strengths of both methods, achieving both high purity and improved device performance with enhanced yield.

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

This hybrid process achieves high sc-SWCNT purity (>99%) and yield (>20%), enabling improved device performance with enhanced mobility and on/off ratios in thin film transistors, while being cost-effective and scalable.

Implementation Method 1

conjugated polymers could selectively disperse semiconducting SWCNTs and lead to enriched semiconducting SWCNT fractions

Methodology Applied
Scientific EffectSelective dispersion:

Implementation Method 2

extracting a mixture of sc-SWCNTs and m-SWCNTs with a conjugated polymer in a non-polar solvent to produce an enriched sc-SWCNT dispersion

Methodology Applied
Scientific EffectExtraction: Liquid-Liquid Extraction

Implementation Method 3

exposing the enriched sc-SWCNT dispersion to an inorganic adsorptive medium in a non-polar solvent, the inorganic adsorptive medium selectively binding the m-SWCNTs

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP3036024B1Process for purifying semiconducting single-walled carbon nanotubes
Publication Date: 2019.05.01 NAT RES COUNCIL OF CANADA
  • EP3036024B1 patent drawingFigure 1
  • EP3036024B1 patent drawingFigure 2
  • EP3036024B1 patent drawingFigure 3

AI summary

A two-step sc-SWCNT enrichment process involves a first step based on selective dispersion and extraction of semiconducting SWCNT using conjugated polymer followed by a second step based on an adsorptive process in which the product of the first step is exposed to an inorganic absorptive medium to selectively bind predominantly metallic SWCNTs such that what remains dispersed in solution is further enriched in semiconducting SWCNTs. The process is easily scalable for large-diameter semi- conducting single-walled carbon nanotube (sc-SWCNT) enrichment with average diameters in a range, for example, of about 0.6 to 2.2 nm. The first step produces an enriched sc-SWCNT dispersion with a moderated sc-purity (98%) at a high yield, or a high purity (99% and up) at a low yield. The second step can not only enhance the purity of the polymer enriched sc-SWCNTs with a moderate purity, but also further promote the highly purified sample to an ultra-pure level. Therefore, this two-step hybrid process provides sc-SWCNT materials with a super high purity, as well as both a high sc-purity (for example greater than 99%) and a high yield (up to about 20% or higher).