First virtual Bilateral Conference on Functional Materials (BiC-FM)

[3] S.S. Fedotov et al Journal of Power Sources 480, 228840 (2020)

[4] S.S. Fedotov et al Journal of Materials Chemistry A, 6, 14420 (2018)

Dip-coating as efficient technique for single-walled carbon nanotube doping

Anastasia E. Goldt1, Orysia T. Zaremba1, Eldar M. Khabushev1,2, Stepan A. Romanov1,

Albert G. Nasibulin1,2

1Skolkovo Institute of Science and Technology, 3 Nobel Street, Moscow, 121205, Russia

2Aalto University School of Chemical Engineering, Kemistintie 1, 02015, Espoo, Finland

[e-mail]

Single-walled carbon nanotube (SWCNT) based transparent and conductive films (TCFs) are one of the most prospective materials for novel flexible and stretchable electronic devices. Development of reproducible and scalable doping procedure is the key step towards the widespread implementation of SWCNT TCFs.

We propose and thoroughly investigate a novel approach for SWCNTs doping utilizing traditional dip-coating technique with gold (III) chloride solution as a dopant. Adjusting of the process conditions (dopant concentration and withdrawal speed) allows effectively govern SWCNT film doping degree and define the optimal conditions for fabrication of high-performance nanotube films. It leads to achievement of sheet resistance value of 36 Ohm/sq. at the 90 % transmittance the middle of visible spectral range by increasing a work function value from 4.8 (for pristine SWCNTs) to 6.0 eV.

This method allows easy fine-tuning of SWCNT films optoelectronic parameters and achieve a sheet resistance value of 36 Ohm/sq. at the 90 % transmittance in the middle of visible spectral range by increasing a work function value from 4.8 (for pristine SWCNTs) to 6.0 eV

In addition, the fabrication of uniform, highly conductive and transparent SWCNT films opens a space for the development of a robust continuous roll-to-roll process by immersing roller modules into a dopant solution.

Acknowledgement.The authors acknowledge the Russian Science Foundation (project No. 17-19-01787).

Dielectric properties of intercalated graphite fluoride compounds with bromine and acetonitrile

Grebenkina M.A.1,2, Chekhova G.N.1, Pinakov D.V.1, Gusel'nikov A.V.1, Bulusheva L.G.1,2, Okotrub A.V.1,2

1 – Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Russia

2 – Novosibirsk State University, Novosibirsk, Russia

[e-mail]

Fluorinated graphite intercalated compounds (FGICs) consist of a layered matrix formed by graphene layers with attached fluorine atoms and guest molecules, which are embedded in the interlayer space [1]. The study of the dielectric properties of FGICs will provide information of the intercalated molecules’ arrangement in the interlayer space and the effect of intercalated molecules and the matrix’s composition on the dielectric permittivity of the material.

In this research we investigated the temperature and the frequency dependences of the dielectric permittivity of FGICs with matrixes’ compositions C2F1,05, C2F0,85, C2F0,60 and inserted bromine (Br2) or acetonitrile (CH3CN). The temperature was varied from 180 to 25 °C, the frequency – from 1 Hz to 7 MHz. It was indicated that low-fluorinated graphite intercalated with bromine has extremely high dielectric permittivity. The effect is associated with the formation of Br2- and Br3- ions which lead to an increase in the dielectric response and the appearance of an ion-relaxation mechanism of polarization. In highly fluorinated samples, interaction between Br2 molecules are similar to that of a liquid. Moreover, it was demonstrated that the freezing of the movement of acetonitrile CH3CN molecules in the interplanar space of graphite fluorides occurs at temperatures below -100 °C what causes a decrease of the dielectric permittivity of FGIGs.

Acknowledgement.This work was supported by the Russian Foundation for Basic Research, grant 18-29-19073.

References:

[1] G.N. Chekhova, D.V. Pinakov, Yu.V. Shubin, V.P. Fadeeva, V.D. Tikhova, A.V. Okotrub, L.G. BulushevaJ. Fluor. Chem. Elsevier B.V., 232, 109482 (2020).

Fine tuning of single-walled carbon nanotube properties for transparent and conductive applications

Khabushev E.M.1,2, Krasnikov D.V.1, Tsapenko A.P.1,2, Zaremba O.T.1, Kolodyaznaya Y.V.1, Goldt A.E.1, and Nasibulin A.G.1,2

1 – Skolkovo Institute of Science and Technology, Moscow, Russia

2 – Aalto University, Espoo, Finland

[e-mail]

Single-walled carbon nanotubes (SWCNTs) are still a material attracting a significant attention of the scientific community: current technological advances are focused on their implementation in novel optoelectronic devices [1]. Currently, aerosol CVD is a well-established technique to produce SWCNTs of high quality, possessing excellent scalability and material purity. Nevertheless, precise control over output parameters is still not achieved that hampers SWNCT widespread implementation.

In this work SWCNT synthesis by aerosol CVD based on the Boudouard reaction utilizing ferrocene as catalyst precursor. We inspected the influence of synthesis conditions (temperature, carbon dioxide and ferrocene partial pressure) on SWCNT parameters utilizing the four-probe technique, Raman and optical spectroscopy and electron microscopy. Finely tuning synthesis parameters, we obtained SWCNTs with a mean diameter varying in the range from 1 to 2 nm and Raman quality factor IG/ID up to 500. Analyzing the obtained results, we prove a high Raman peak ratio (IG/ID), length, and diameter of the nanotubes to decrease the equivalent sheet resistance of the nanotube-based film [2]. Temperature kinetic measurements revealed the change in the nanotube growth mechanism at the temperature coinciding with the phase transition between α-Fe and γ-Fe catalyst phases, which highlighted a significant difference in the conductive properties of films producing at different synthesis temperatures.

As a result of equivalent sheet resistance optimization, we obtained pristine films with R90=250 Ω/. Moreover, this value dropped down to 39 Ω/ after HAuCl4 doping providing

Acknowledgement.This work was supported by Russian Foundation for Basis Research grant 18-29-20032

References:

[1] J. Du, S. Pei, L. Ma, H.M. Cheng, Advanced Materials, 26, 1958–1991, (2014).

[2] E.M. Khabushev, D. V. Krasnikov, J. V. Kolodiazhnaia, A. V. Bubis, A.G. Nasibulin, Carbon, 161, 712–717, (2020).

[3] E.M. Khabushev, D. V. Krasnikov, O.T. Zaremba, A.P. Tsapenko, A.E. Goldt, A.G. Nasibulin, Journal of Physical Chemistry Letters 10, 6962–6966, (2019).

Holey single-walled carbon nanotubes for ultra-fast bolometers

Daria S. Kopylova1*, Fedor S. Fedorov1, Alena А. Alekseeva1, Zakhar I. Popov2, Pavel B. Sorokin2, Anton S. Anisimov3, and Albert G. Nasibulin1,4

1Skolkovo Institute of Science and Technology, Nobel str. 3, Moscow, 121205, Russia

2National University of Science and Technology MISIS, Leninskiy prospect, 4, Moscow, 119049, Russia

3Canatu Ltd. Konalankuja 5, 00390, Helsinki, Finland

4Aalto University, Department of Applied Physics, 00076, Aalto, Finland

[e-mail]

The development of new materials for sensitive and fast broadband photodetectors remains actual problem in the fields of IR vision and spectroscopy. Carbon nanotubes have already been demonstrated as a promising material for bolometers [1]. However, the sensitivity enhancement of such bolometers while maintaining the speed of operation is still a great challenge. Here, we present a new material, holey carbon nanotube network, designed to improve the temperature coefficient of resistance (TCR), the key parameter that determine the sensitivity of bolometers [2]. Fine treatment with low frequency oxygen plasma allows to control the conductive properties of the material. The temperature coefficient of resistance of our films is much higher than reported values for pristine carbon nanotubes in wide temperature range up to 3 % K-1 in absolute value at liquid nitrogen temperature which is much higher than reported values for carbon nanotubes and comparable with vanadium oxides. The bolometer prototypes made of free-standing plasma treated SWCNT films possess high sensitivity in wide IR range (3-50 µm), smooth spectral characteristics of IR absorption, ultrafast (3 ms) response time and relatively low noise level comparing to similar devices made of carbon nanotubes.

Acknowledgement. The reported study was funded by RFBR, project number 20-03-00804.

Fig.1 The plasma treatment effect on TCR of SWCNT films and bolometers response (a) TCR of pristine SWCNT films and the ones treated in oxygen plasma at different exposure time, inset: temperature dependence of film sheet resistance. (b) Spectral characteristics of bolometric samples made of 100 nm thick free-standing SWCNT film, pristine and oxygen plasma treated with different time of treatment.

A simple and reliable approach to fabricate arrays of single-walled carbon nanotube network field-effect transistor for advanced characterization

Grigoriy B. Livshits1, Alena A. Alekseeva1, Anton V. Bubis1, Dmitry V. Krasnikov1, Albert G. Nasibulin1,2

1Skolkovo University of Science and Technology, Moscow, Russia

2Aalto University School of Chemical Engineering, Espoo, Finland

[e-mail]

Nowadays, flexible electronics demands new materials for integrated circuits of high flexibility and stretchability[1]. Single-walled carbon nanotubes (SWCNTs) are one of the most promising materials for utilization in the flexible integrated circuits owing to the outstanding electrical and mechanical properties[2]. Field-effect transistors (FETs) with on/off ratio of 108 and 100 cm2/(V∙s) have already been reported on SWCNT films purified from metallic nanotubes[3] as well as on pristine films[4]. However, implementation of developed technologies in industry seeks advances in both the fabrication technology and deeper understanding of interplay between SWCNT film properties.

Here we present a technology for SWCNT film-based FETs that can be used as a versatile tool for examination of intrinsic properties of the films. The method relies on a simple capillary transfer technique of as-synthesized SWCNT film from a nitrocellulose filter. The method is simple, scalable, and does not require tedious and contaminating procedure of filter dissolution. We have fabricated a series of SWCNT FET arrays to demonstrate the advanced quality and uniformity of the transfer. The relation of FET parameters (such as opened and closed state resistance, on/off ratio etc.) can be easily brought to light via the procedure proposed. We have investigated the relations in the vast range of on/off ratio (10–106) and on-state resistance (104 – 108 Ω) on SWCNT film FETs with channel lengths in range of 60-350 μm. Moreover, this framework can provide access for more fundamental quantities such as SWCNT film density[5], metallic to semiconducting nanotube ratio, doping level etc[6].

Acknowledgement.The authors acknowledge the Russian Science Foundation (project No. 17-19-01787).

References:

[1] Q. Huang and Y. Zhu, “Printing Conductive Nanomaterials for Flexible and Stretchable Electronics: A Review of Materials, Processes, and Applications,” Adv. Mater. Technol., vol. 4, no. 5, pp. 1-41, 2019, doi: 10.1002/admt.201800546.

[2] D. Jariwala, V. K. Sangwan, L. J. Lauhon, T. J. Marks, and M. C. Hersam, “Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing,” Chem. Soc. Rev., vol. 42, no. 7, pp. 2824–2860, 2013, doi: 10.1039/c2cs35335k.

[3] W. Talsma et al., “Remarkably Stable, High-Quality Semiconducting Single-Walled Carbon Nanotube Inks for Highly Reproducible Field-Effect Transistors,” Adv. Electron. Mater., vol. 5, no. 8, 2019, doi: 10.1002/aelm.201900288.

[4] D. M. Sun et al., “Flexible high-performance carbon nanotube integrated circuits,” Nat. Nanotechnol., vol. 6, no. 3, pp. 156–161, 2011, doi: 10.1038/nnano.2011.1.

[5] A. Kaskela, K. Mustonen, P. Laiho, Y. Ohno, and E. I. Kauppinen, “Toward the Limits of Uniformity of Mixed Metallicity SWCNT TFT Arrays with Spark-Synthesized and Surface-Density-Controlled Nanotube Networks,” ACS Appl. Mater. Interfaces, vol. 7, no. 51, pp. 28134-28141, 2015, doi: 10.1021/acsami.5b10439.

[6] N. Wei et al., “Fast and Ultraclean Approach for Measuring the Transport Properties of Carbon Nanotubes,” Adv. Funct. Mater., vol. 1907150, pp. 1–9, 2019, doi: 10.1002/adfm.201907150.

Investigation of sensory properties of CNT in relation to acetone vapors

Zaporotskova I.V.1, Vilkeeva D.E.1, Elbakyan L.S.1, Dryuchkov E.S.1.

1 – Volgograd State University, Volgograd, Russia

[e-mail]

Modern methods of diagnostics various diseases, despite their constant improvement, retain the need for fast and inexpensive screening technologies. One of the promising directions in this area is the analysis of exhaled air. Metabolic disorders typical of diabetes mellitus are due to increased acetone content in exhaled air, moreover, selective detection of acetone in breath is very important for diagnosing diseases in a non-invasive way. However, to date, inexpensive portable gas sensors for breath analysis have not been developed. This article provides a theoretical study of the possibility of reacting acetone, a common volatile organic compound (VOC) in human respiration, with carbon nanotubes modified with functional groups – carboxyl and amine. From studies conducted earlier [1,2], it is known, that carbon nanotubes, boundary-modified with carboxyl (COOH) and amine (NH2) groups, form stable chemical complexes. In this paper, we used these sensor models to detect acetone vapor. Calculations of tubulens "zig-zag" (6.0) type were made within the framework of the molecular cluster model using the DFT calculation method. It was found that in both cases a stable chemical interaction is formed. Modified carbon nanotubes can be chemical and biological sensors that make it possible to fix micro amounts of substance. Specified functionalization will ensure high accuracy and selectivity of acetone detection in a complex mixture of gases, vapors and other volatile organic compounds present in exhaled air. Taking into account these features of functioning, it is worth noting the importance of creating a device with a sensor based on modified CNTs for contactless diagnosis of diabetes mellitus.

Acknowledgement.The research was carried out with the financial support of the RFBR and The administration of the Volgograd region in the framework of the scientific project no.19-43-340005 r_a.

References:

[1] I.V. Zaporotskova, N.P. Polikarpova, A.V. Shkodin, D.I. Polikarpov, D.E. Vil’keeva, About boundary modification of nanotube systems by carboxile group, Nanoscience & nanotechnology, 2013, pp. 52–53.

[2] N.P. Boroznina, I.V. Zaporotskova, S.V. Boroznin, E.S. Dryuchkov, Chemosensors, 7 (2019) 1–7.

New ultrathin medical coating of pvp-based medical biliary stents with addition of carbon nanotubes

Zvonareva D.A.1, An E.E. 1, Zaporotskova I.V.1

1 – Volgograd State University, Volgograd, Russia

[e-mail]

We propose as a drug coating a coating based on a known polymer of polyvinylpyrrolidone (PVP) with an injected drug doxorubicin and carbon nanotubes (CNTs), known for their unique sorption and mechanical properties [1–3].

As a result of the experiment, it was found that the most stable is a 60 % PVP solution. After the solution was infused, we divided it into three equal volumes, to which CNTs were added in quantities necessary to create concentrations of 0.1; 0.05; 0.01 wt% CNT. After application and complete drying, the thickness of the created coating averaged 0.02 mm. Then the drug-coated biliary stents were immersed in a saline solution – sodium chloride, which mimicked the internal environment of the human body. [4]

As a result of the study, it was found that the carbon nanotubes present in the coating have a positive effect on the durability and retention of the drug coating on the surface of the biliary stent. The optimal concentration is the concentration of 0.1 wt% nanotubes based on the solution weight.

Acknowledgement.The reported research was funded by Russian Foundation for Basic Research and the government of Volgograd region, grant № 19-43-340005 r_a.

References:

[1] M.T. Byrne, Adv. Mater., 22, pp. 1672–1688 (2010)

[2] L. A. Chernozatonsky, P.B.Sorokin, Carbon nanotubes: from fundamental research to nanotechnology, pp. 154–174 (2007)

[3] Buehler V. Kollidon, Polyvinylpyrrolidone for Pharmaceutical Industry, pp. 287 (1996)

[4] A.G. Beburishvili, I.V. Zaporotskova, E. G. Spiridonov, V.V. Mandrikov, R.A. Shinkarev, Bulletin of VolGMU, 2, 50, pp. 124–130 (2014)