Fine-Tuning of Single-Walled Carbon Nanotube Properties for Transparent Conductive Applications

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School of Chemical Technology | Doctoral thesis (article-based) | Defence date: 2023-01-13
Degree programme
67 + app. 115
Aalto University publication series DOCTORAL THESES, 187/2022
Single-walled carbon nanotubes (SWCNTs) are a unique material for next-generation electronics, thanks to their outstanding physical properties. In particular, SWCNT-based transparent conductive films (TCFs) are of great interest for replacing indium-tin-oxide in touch screens, displays, and solar cells with a technology development paradigm shifting to stretchable and wearable devices. However, recent advances in the field of SWCNT thin-film production, particularly material performance and synthesis productivity, are insufficient for pushing SWCNTs into the industry. This fact highlights the relevance of research on the efficient synthesis of SWCNTs with tailored characteristics, which is the main focus of the current thesis. Two different aerosol chemical vapor deposition (CVD) reactors based on carbon monoxide disproportionation and hybrid hydrocarbon pyrolysis were thoroughly investigated and used to tackle the challenge of highly conductive SWCNT film synthesis with desired productivity. The systematic study of the carbon monoxide-based system allowed to associate SWCNT structural properties and optoelectrical performance of their films, providing a direction for further optimization. In particular, low defectiveness, thick nanotube diameter, and high length corresponded to the highest optoelectrical performance of the films. The engineering of gas flows in the reactor was carried out to enhance material performance and synthesis productivity. Thus, the investigation of catalyst injection strategy reinforced with CFD simulations helped to reach a 9-fold enhancement of synthesis yield, preserving SWCNT characteristics. Besides, the residence time adjustment was employed for lengthening the produced SWCNTs. Despite its positive effect on length and film sheet resistance, high residence time resulted in elevated diffusion losses on the reactor walls limiting the process productivity. For post-synthesis enhancement of SWCNT optoelectrical properties, a reversible doping technique based on electrochemical gating of the films was developed. The method was evaluated on the samples produced by the carbon monoxide-based reactor, which exhibited a 13-fold drop in sheet resistance at 90% transmittance down to 53 Ω/□. A more complex and multiparametric hydrocarbon-based synthesis, implementing toluene and ethylene as feedstocks, was employed with a focus on overcoming performance-productivity trade-off. The adjustment of synthesis parameters resulted in sheet resistance (at 90% transmittance) value of 57 Ω/□ and yield of 0.24 cm2·L-1, outperforming previous advances. The multiparametric experimental data was also used in the comparative analysis of machine-learning algorithms and their applicability for predicting SWCNT properties. Among the tested algorithms, artificial neural networks were found to provide the lowest error comparable with experimental inaccuracy, coping well with the prediction of sheet resistance.
Supervising professor
Kallio, Tanja, Associate Prof., Aalto University, Department of Chemistry and Materials Science, Finland
Thesis advisor
Nasibulin, Albert G., Prof., Skolkovo Institute of Science and Technology, Russia
Krasnikov, Dmitry V., Dr., Skolkovo Institute of Science and Technology, Russia
single-walled carbon nanotubes, floating-catalyst chemical vapor deposition, transparent conductive films
  • [Publication 1]: Khabushev Eldar M.; Krasnikov Dmitry V.; Kolodiazhnaia Julia V.; Bubis Anton V.; Nasibulin Albert G. 2020. Structure-dependent performance of single-walled carbon nanotube films in transparent and conductive applications. Elsevier Ltd. Carbon, 161, 712-717. ISSN: 00086223.
    Full text in Acris/Aaltodoc:
    DOI: 10.1016/j.carbon.2020.01.068 View at publisher
  • [Publication 2]: Khabushev Eldar M.; Kolodiazhnaia Julia V.; Krasnikov Dmitry V.; Nasibulin Albert G. 2021. Activation of catalyst particles for single-walled carbon nanotube synthesis. Elsevier B.V. Chemical Engineering Journal, 413, 127475. ISSN: 13858947.
    Full text in Acris/Aaltodoc:
    DOI: 10.1016/j.cej.2020.127475 View at publisher
  • [Publication 3]: Novikov Ilya V.; Khabushev Eldar M.; Krasnikov Dmitry V.; Bubis Anton V.; Goldt Anastasia E.; Shandakov Sergey D.; Nasibulin Albert G. 2021. Residence time effect on single-walled carbon nanotube synthesis in an aerosol CVD reactor. Elsevier B.V. Chemical Engineering Journal, 420, 129869. ISSN: 13858947.
    DOI: 10.1016/j.cej.2021.129869 View at publisher
  • [Publication 4]: Kopylova Daria S.; Satco Daria A.; Khabushev Eldar M.; Bubis Anton V.; Krasnikov Dmitry V.; Kallio Tanja; Nasibulin Albert G. 2020. Electrochemical enhancement of optoelectronic performance of transparent and conducting single-walled carbon nanotube films. Elsevier Ltd. Carbon, 167, 244-248. ISSN: 00086223.
    DOI: 10.1016/j.carbon.2020.05.103 View at publisher
  • [Publication 5]: Khabushev Eldar M.; Krasnikov Dmitry V.; Goldt Anastasia E.; Fedorovskaya Ekaterina O.; Tsapenko Alexey P.; Zhang Qiang; Kauppinen Esko I.; Kallio Tanja; Nasibulin Albert G. 2022. Joint effect of ethylene and toluene on carbon nanotube growth. Elsevier Ltd. Carbon, 189, 474-483. ISSN: 00086223.
    Full text in Acris/Aaltodoc:
    DOI: 10.1016/j.carbon.2021.12.052 View at publisher
  • [Publication 6]: Krasnikov Dmitry V.; Khabushev Eldar M.; Gaev Andrey; Bogdanova Alisa R.; IakovlevVsevolod Ya.; Lantsberg Anna; Kallio Tanja; Albert Nasibulin G. 2022. Machine learning methods for aerosol synthesis of single-walled carbon nanotubes. Elsevier Ltd. Carbon, 202, 76-82. ISSN: 00086223.
    Full text in Acris/Aaltodoc:
    DOI: 10.1016/j.carbon.2022.10.044 View at publisher