skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solution-phase p-type doping of highly enriched semiconducting single-walled carbon nanotubes for thermoelectric thin films

Journal Article · · Applied Physics Letters
DOI:https://doi.org/10.1063/5.0055837· OSTI ID:1812330

Single-walled carbon nanotubes (SWCNTs) are attractive materials for next-generation energy-harvesting technologies, including thermoelectric generators, due to their tunable opto-electronic properties and high charge carrier mobilities. Controlling the Fermi level within these unique 1D nanomaterials is often afforded by charge transfer interactions between SWCNTs and electron or hole accepting species. Conventional methods to dope SWCNT networks typically involve the diffusion of molecular redox dopant species into solid-state thin films, but solution-phase doping could potentially provide routes and/or benefits for charge carrier transport, scalability, and stability. Here, we develop a methodology for solution-phase doping of polymer-wrapped, highly enriched semiconducting SWCNTs using a p-type charge transfer dopant, F4TCNQ. This allows doped SWCNT inks to be cast into thin films without the need for additional post-deposition doping treatments. We demonstrate that the introduction of the dopant at varying stages of the SWCNT dispersion process impacts the ultimate thermoelectric performance and observe that the dopant alters the polymer selectivity for semiconducting vs metallic SWCNTs. In contrast to dense semiconducting polymer films, where solution-phase doping typically leads to disrupted morphologies and poorer TE performance than solid-state doping, thin films of solution-doped s-SWCNTs perform similarly to their solid-state doped counterparts. Interestingly, our results also suggest that solution-phase F4TCNQ doping leads to fully ionized and dimerized F4TCNQ anions in solid-state films that are not observed in films doped with F4TCNQ after deposition. Our results provide a framework for the application of solution-phase doping to a broad array of high-performance SWCNT-based thermoelectric materials and devices that may require high-throughput deposition techniques.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1812330
Alternate ID(s):
OSTI ID: 1807725
Report Number(s):
NREL/JA-5K00-79957; MainId:40164; UUID:0bb2caf8-3b27-4ff2-b280-535a6387bffb; MainAdminID:48417; TRN: US2213229
Journal Information:
Applied Physics Letters, Vol. 119, Issue 2; ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (43)

Spontaneous Dissolution of a Single-Wall Carbon Nanotube Salt journal January 2005
Carbon-Nanotube-Based Thermoelectric Materials and Devices journal January 2018
Spectroscopy of Ground- and Excited-State Charge Carriers in Single-Wall Carbon Nanotubes book January 2019
Morphology control strategies for solution-processed organic semiconductor thin films journal January 2014
Polymer-Free Carbon Nanotube Thermoelectrics with Improved Charge Carrier Transport and Power Factor journal November 2016
Solution Dimerization of the Tetracyanoquinodimethane Ion Radical journal November 1965
Organic thermoelectric materials for energy harvesting and temperature control journal August 2016
Stretchable fabric generates electric power from woven thermoelectric fibers journal January 2020
Large n- and p-type thermoelectric power factors from doped semiconducting single-walled carbon nanotube thin films journal January 2017
Customizing the Polarity of Single‐Walled Carbon‐Nanotube Field‐Effect Transistors Using Solution‐Based Additives journal November 2019
Semiconducting Single-Walled Carbon Nanotubes in Solar Energy Harvesting journal June 2017
Flexible and Robust Thermoelectric Generators Based on All-Carbon Nanotube Yarn without Metal Electrodes journal July 2017
The difference between metallic and insulating salts of tetracyanoquinodimethone (TCNQ): how to design an organic metal journal March 1979
Optical measurement of doping efficiency in poly(3-hexylthiophene) solutions and thin films journal February 2015
Simple Salt-Coordinated n-Type Nanocarbon Materials Stable in Air journal April 2016
Evaporation vs Solution Sequential Doping of Conjugated Polymers: F 4 TCNQ Doping of Micrometer-Thick P3HT Films for Thermoelectrics journal August 2019
True solutions of single-walled carbon nanotubes for assembly into macroscopic materials journal November 2009
Improvement of thermoelectric performance of single-wall carbon nanotubes by heavy doping: Effect of one-dimensional band multiplicity journal November 2016
Optical absorption spectroscopy of single-wall carbon nanotubes doped with a TCNQ derivative journal April 2003
Giant Seebeck coefficient in semiconducting single-wall carbon nanotube film journal January 2014
Overcoming Film Quality Issues for Conjugated Polymers Doped with F 4 TCNQ by Solution Sequential Processing: Hall Effect, Structural, and Optical Measurements journal November 2015
n-Type Transparent Conducting Films of Small Molecule and Polymer Amine Doped Single-Walled Carbon Nanotubes journal March 2011
A practical field guide to thermoelectrics: Fundamentals, synthesis, and characterization journal June 2018
Dopant-Modulated Conjugated Polymer Enrichment of Semiconducting SWCNTs journal March 2018
Solving the Thermoelectric Trade-Off Problem with Metallic Carbon Nanotubes journal September 2019
Macroscopically aligned carbon nanotubes for flexible and high-temperature electronics, optoelectronics, and thermoelectrics journal December 2019
Tailored semiconducting carbon nanotube networks with enhanced thermoelectric properties journal April 2016
Morphology controls the thermoelectric power factor of a doped semiconducting polymer journal June 2017
High-Performance, Wearable Thermoelectric Generator Based on a Highly Aligned Carbon Nanotube Sheet journal December 2019
Balancing the electrical conductivity and Seebeck coefficient by controlled interfacial doping towards high performance benzothienobenzothiophene-based organic thermoelectric materials journal January 2019
Diameter dependence of thermoelectric power of semiconducting carbon nanotubes journal October 2015
Polar Side Chains Enhance Processability, Electrical Conductivity, and Thermal Stability of a Molecularly p-Doped Polythiophene journal April 2017
Thermoelectric composites of poly(3-hexylthiophene) and carbon nanotubes with a large power factor journal January 2013
Origin of poor doping efficiency in solution processed organic semiconductors journal January 2018
Solvent Effects on Polymer Sorting of Carbon Nanotubes with Applications in Printed Electronics journal August 2014
Organic Thermoelectrics: Materials Preparation, Performance Optimization, and Device Integration journal January 2019
Thickness-dependent thermoelectric power factor of polymer-functionalized semiconducting carbon nanotube thin films journal August 2018
A Solution-Doped Polymer Semiconductor:Insulator Blend for Thermoelectrics journal September 2016
Varying the ionic functionalities of conjugated polyelectrolytes leads to both p- and n-type carbon nanotube composites for flexible thermoelectrics journal January 2015
Supramolecular Functionalization for Improving Thermoelectric Properties of Single-Walled Carbon Nanotubes–Small Organic Molecule Hybrids journal November 2020
High-Yield Dispersions of Large-Diameter Semiconducting Single-Walled Carbon Nanotubes with Tunable Narrow Chirality Distributions journal February 2013
Systematic Conversion of Single Walled Carbon Nanotubes into n-type Thermoelectric Materials by Molecular Dopants journal November 2013
Intrinsic and Extrinsically Limited Thermoelectric Transport within Semiconducting Single‐Walled Carbon Nanotube Networks journal February 2019