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

Low cost lasers as suitable instrument for graphene oxide thin film modification

Komarov I.A.¹, Struchkov N.S.², Danilova E.A.¹, Denisenko E.I.¹, Pretyagin V.G.¹

1 – Bauman Moscow State Technical University, Moscow, Russia

2 – National Research University of Electronic Technology

ikomarov@emtc.ru

Our work is related to the processing of graphene oxide films for large variety of applications including formation of bio- and chemical sensor transducer, coatings with different drugs for faster healing, transparent conductive coatings etc. One of the most important goals for sensing and drug transfer is to control number and type of functional groups remaining on the graphene oxide surface. This goal can be achieved by different approaches including UV [1] and laser irradiation [2]. But in our opinion laser irradiation is more perspective due to the possibility of maskless direct patterning of the graphene oxide film.

In this work we used two types of low-cost lasers: near IR (1060 nm) and blue (445 nm) to modify graphene oxide film. We successfully showed possibility of graphene oxide reduction with both types of lasers, but blue laser showed better uniformity of reduced graphene oxide film parameters including film morphology, resistance (from 4 to 12 kOhm) and Raman intensity ratios. Usage of near IR laser leads to large nonuniformity of resistance with relatively high values (from tenth of kOhm to MOhm). We also showed presence of carboxyl functional groups in reduced graphene oxide areas that is suitable for biosensor, drug transfer and implants applications.

The presented work was financially supported by the Russian Foundation for Basic Research (Project No. 18-29-19172).

References:

[1] Rabchinskii M.K. et al. Fullerenes Nanotubes and Carbon Nanostructures, 28, 3, 221–225 (2020)

[2] Zhang Y-L, Guo L, Xia H, Chen Q‐D, Feng J and Sun H‐B. Adv. Optical Mater., 2, 10–28 (2014).

Eco-Friendly Photocatalysts for Degradation of Dyes

Lau. G.E¹, Che Azurahanim, C.A. ^1,2, *, Wan Amir N.W.A ³, Suvik. A⁴ and Alvin. L.T.Z.⁵

1 – Universiti Putra Malaysia, Serdang 43400 UPM, Selangor, Malaysia.

2 – Institute of Advanced Technology (ITMA)

eenlau313@gmail.com

In the current era of globalization, synthetic dyes are one of the key factors of water pollution. Photocatalysis constitutes a promising technology for the treatment of wastewater, especially to those containing hard-to-remove organic compounds. Zinc oxide nanoparticles (ZnONPs) play a vital role as a photocatalyst material. This research highlights the synthesized ZnONPs with roselle flower and oil palm leaf extract. The extracts and sodium hydroxide (NaOH) act as reducing agents during the synthesis process. Synthesis without the addition of plant extract is used as blank control for the experiment. Structural and optical studies of the three variants of ZnONPs were performed. High purity of ZnONPs with element Zn and O was obtained. The size of the three variants of ZnONPs was from 10–15 nm and found in agglomerated spherical shape. Large band gap, 3.2 eV was obtained by UV–Vis and high thermal stability was proven by TGA. Oxygen vacancies that assist in the degradation phenomenon were found in ZnONPs. Five percent of ZnONPs with the presence of 10 W UV light could effectively degrade 10 ppm MO in 5 h and MB in 3 h. Besides, high antioxidant properties and low toxicity demonstrated the ability of ZnONPs to be used as photocatalysts. In conclusion, ZnONPs can be further developed for pharmaceutical and industrial use.

Acknowledgement.This research received no external funding.

Preparation of carbon nanotube fibers by folding the randomly oriented SWCNT films

Lomakin M.V.¹, Vershinina A.I.¹, Zhilyaeva M.A.², Rybakov M.S.¹, Kosobutsky A.V.¹, Shandakov S.D.¹

1 – Kemerovo State University, Kemerovo, Russia

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

maximius13@yandex.ru

The growing demand for wearable electronics requires flexible and stretchable conductive materials. Compared to ordinary conducting materials, single-walled carbon nanotubes (SWCNTs) are extremely lightweight and demonstrate a higher ability to prevent corrosion and oxidation. CNTs are usually used in the form of fibers, arrays or films [1]. In this work, we investigated the preparation of CNT fibers from the randomly oriented SWCNT films using a recently developed wet pulling technique [2]. Crucial phenomena in the wet pulling process are a folding of a solvent soaked SWCNT film due to the liquid surface tension and fiber densification during the solvent evaporation. It is shown that application of the wet pulling technique to randomly oriented SWCNT films results in low-density fibers with large number of the folds on their surface. Depending on the solvent nature (ethanol, acetone, dimethyl sulfoxide, and tetrahydrofuran), the fiber density varies in the range of 0.03-0.09 g/cm³. By applying a twisting process, the density might be increased up to 0.19 g/cm³. The specific strength is found to be only weakly dependent on the sample fabrication conditions. The obtained tenacity values of 0.60-0.78 N/tex are close to the published data for fibers directly spun from a CVD reactor using the bath-spinning or rotating-anchor spinning methods. The specific strength of the manufactured fibers is relatively high thus indicating a good interconnection of the CNT bundles. As a result of tensile tests conducted in this work, it is established that the fiber treated in the solutions of HAuCl₄ in ethanol had the highest value of a total absorbed energy up to fracture (127 J/g at 23 % strain).

Acknowledgement.This work was supported by the Russian Foundation for Basic Research (project no. 18-29-19169).

References:

[1] A.G. Nasibulin, A. Kaskela, K. Mustonen, et al., ACS Nano, 5, 3214 (2011).

[2] M.A. Zhilyaeva, E.V. Shulga, S.D. Shandakov, et al., Carbon, 150, 69 (2019).

Helicity sensitive plasmonic teraherts interferometer

Matyushkin Y.^1,2,3,4, Danilov S.², Moskotin M.^1,3, Belosevich V.^1,3, Kaurova N.³, Rybin M.^1,5, Obraztsova E.D.^1,5, Fedorov G.^1,3, Gorbenko I.^6,7, Kachorovskii V.^6,8, Ganichev S.D.^2,8

1 – Moscow Institute of Physics and Technology National Research University, Dolgoprudny, Russia

2 – Terahertz Center, University of Regensburg, Regensburg, Germany

3 – Physics Department, Moscow State Pedagogical University, Moscow, Russia

4 – National Research University Higher School of Economics, Moscow, Russia

5 – Prokhorov General Physics Institute, RAS, Moscow, Russia

6 – Ioffe Institute, St. Petersburg, Russia

7 – ITMO University, St. Petersburg, Russia

8 – CENTERA Laboratories, Institute of High Pressure Physics, PAS, Warsaw, Poland

ya.matyushkin@gmail.com

Plasmonic interferometry is a rapidly growing area of research with a huge potential for applications in the terahertz frequency range [1–3]. Here we present our recent work in which we explore a plasmonic interferometer based on a graphene field effect transistor connected to specially designed antennas. As a key result, we observe helicity- and phasesensitive conversion of circularly-polarized radiation into dc photovoltage caused by the plasmon-interference mechanism: two plasma waves, excited at the source and drain part of the transistor interfere inside the channel. The helicity sensitive phase shift between these waves is achieved by using an asymmetric antenna configuration. The dc signal changes sign with inversion of the helicity. A suggested plasmonic interferometer is capable of measuring the phase difference between two arbitrary phase-shifted optical signals. The observed effect opens a wide avenue for phasesensitive probing of plasma wave excitations in two-dimensional materials.

Fig.1. Device configuration. (a) Optical image. (b) Structure cross-section showing relative location of the source, drain and top gate electrodes.

Acknowledgement.This work was supported by the Russian Foundation for Basic Research, grant 18-29-20116.

References:

[1] Ali, J., Pornsuwancharoen, N., Youplao, P., Aziz, M. S., Chiangga, S., Jaglan, J.,… & Yupapin, P. Results in physics, 8, 438 (2018)

[2] Graydon, O. Nat. Photonics 6, 139 (2012)

[3] Bandurin, D.A., Svintsov, D., Gayduchenko, I. et al. Nat. Commun 9, 5392 (2018)

Dependence of frequency-capacitance curves for the «Air – Langmuir Monolayer – Water» system on the colloid solution amount spread out the water surface

Mironyuk V.N.¹, Begletsova N.N.¹, Chumakov A.S.¹, Smirnova A.I.², Usol’tseva N.V.², Glukhovskoy E.G.¹

1 – Saratov State University, Saratov, Russia

2 – Nanomaterials Research Institute, Ivanovo State University, Ivanovo, Russia

 

glukhovskoy@gmail.com

Obtaining additional information on frequency-dependent processes occurring in Langmuir monolayers is an urgent task, especially in cases where methods for measuring surface tension may not provide complete information. Such situation often arises when a monolayer of complex composition is formed on the water surface. For example, it can be a monolayer of nanoparticles in an organic matrix [1, 2], a mixture of amphiphilic and non-amphiphilic molecules [3], etc.

This work we present the frequency-capacitance characteristics of a flat capacitor, where the «Air – Langmuir Monolayer – Water» (A-LM-W) system was used as the dielectric. A monolayer was formed in a Langmuir bath KN 2002 from the solution of potassium polytitanate (PPT) nanoparticles with arachidic acid (ArA) in chloroform (C = 10^-3 M). A highly sensitive Agilent B1500A analyzer was used to register the frequency-capacitive characteristics. C-f dependences were recorded in the frequency range of 1 kHz – 5 MHz. The condenser consisted of two 20x20 mm copper plates – one at the bottom of the bath and the other above the monolayer.

When 20, 30, 40 l of colloid solutions of PPT and ArA were spread out the water surface, the frequency-capacitance curves for the A-LM-W system were obtained in semi-logarithmic coordinates. The maximal capacity level decrease of 20 % compared with the initial values (pure water) was detected for 40 l solution amount.

Acknowledgement.This work was supported by the RFBR, grant 19-03-00763a.

References:

[1] A.S. Chumakov, A.J.K. Al-Alwani, I.A. Gorbachev, A.V. Ermakov, A.A. Kletsov, E.G. Glukhovskoy, A.V. Kazak, N.V. Usol’tseva, S.N. Shtykov, BioNanoScience, 7, 666 (2017)

[2] Al-Alwani A.J.K., Kosolapova K.I., Chumakov A.S., Lukyanova V.O., Gorbachev I.A., Kazak А.V., Smirnova А.I., Shtykov S.N., Usol’tseva N.V., Glukhovskoy E.G., BioNanoScience, 8, 1081 (2018)

[3] Shinkarenko O.A., Safonov R.A., Kolesnikova A.S., Al-Alwani A.J.K., Pozharov M.V., Glukhovskoy E.G., Applied Surface Science, 424, 177 (2017)

Pulse switchable fiber laser based on ionic liquid gated carbon nanotube saturable absorber

Mkrtchyan A. A.¹, Gladush Yu. G.¹, Kopylova D. S.¹, Khabushev E.¹, Nasibulin A. G.¹

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

Aram.mkrtchyan@skoltech.ru

Saturable absorber (SA) based pulse generation in a fibre laser cavity is conditional on modulation characteristics determined by the nonlinear material and implementation geometry of the SA. Commonly, these parameters can be controlled during the satuable absorber fabrication. For instance, modulation depth of a single-wall carbon nanotube saturable absorber (SWCNT-SA) transferred on a D-shape fiber is governed by its thickness and length [1]. Here we demonstrate switching of pulse lasing regimes in an all-PM fibre laser using electrochemically gated in-line SWCNT-SA. SWCNT-based electrochemical cell prepared from high quality aerosol synthesized SWCNTs collected on the cellulose filter directly from the reactor zone. SWCNTs were dry-transferred on a polarization maintaining D-shape fiber, then covered by ionic liquid and implemented it into the fiber laser (Fig. 1a). By applying the voltage on the SWCNT-SA we were able to switch the laser operation between the ultrashort mode-lock and microsecond Q-switch regimes [2]. A transmittance-voltage dependent map with pulse lasing regime regions is shown in Fig. 1b. In Fig. 1c shown the optical spectra of these regimes. Thus, pulse regime switching in the fibre lasers with the ionic liquid gated SWCNT-SA was established.

Figure 1. (a) Scheme of the fiber laser with a gated SWCNT-SA; (b) SWCNT-SA sample linear transmittance depending on the voltage. Colour corresponds to the generation regime depending on the voltage; (c) Optical spectra measured both in Mode-lock and Q-switch regimes

Acknowledgement.The reported study was funded by RFBR, project number 20-32-90233.

References:

[1] A. A. Mkrtchyan, Yu. G. Gladush, D. Galiakhmetova, V. Yakovlev, V. T. Ahtyamov, and A. G. Nasibulin, Opt. Mater. Express 9, 1551, (2019)

[2] Yu. Gladush, A. A. Mkrtchyan, D. S. Kopylova, A. Ivanenko, B. Nyushkov, S. Kobtsev, A. Kokhanovskiy, A. Khegai, M. Melkumov, M. Burdanova, M. Staniforth, J. Lloyd-Hughes, and A. G. Nasibulin, Nano Lett. 19, 9, 5836–5843 (2019)

Copper (2+) ions decrease conductivity of melanin in both bulk and film forms

Gerbenko A.K.^1,3, Savinov M.², Zhukov S.S.³, Mostert A.B.⁴, Motovilov K.A.³

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

2 – Institute of Physics AC CR, Prague, Czech Republic

3 – Moscow Institute of Physics and Technology, Dolgoprudny, Russia

4 – Department of Chemistry, Swansea University, Wales, UK

k.a.motovilov@gmail.com

Melanin, the most widespread pigment among living systems [1], has emerged as promising material for bioelectronic devices and interfaces due to its ability to form device-grade thin films, sufficient conductivity and biocompatibility [2–4]. The nature of melanin conductivity is still a matter of controversies, however, in synthetic melanin the protonic origin of the hydration dependent contribution to conductivity obviously dominates.

Enhancement and linearization of melanin conductivity with respect to hydration level should assist in further development of melanin-based applications. One of the discussed approaches is doping of melanin with metal ions to substitute protons in corresponding protonogenic groups and to stabilize semiquinone-anion monomers which are thought to be responsible for hydration dependent increase of protonic conductivity.

In current study we demonstrated that doping of hydrated melanin with copper 2+ ions leads to complex dose-dependent response. Low concentrations of dopant (3.81 mg/g) slightly increase complex conductivity of bulk melanin. Growth of dopant concentration (29,14 mg/g) breaks the tendency and strongly decrease conductivity of melanin both in bulk and film forms. However, it was shown earlier that greater copper concentration also pushes melanin to change its organization towards formation of more ordered and prolonged structures [5], leading to the observed increase of the dispersionless frequency area for σ`.

Being a porous material melanin demonstrates colossal values of ε` up to 10<sup>8</sup> and even higher at frequencies below 0.01 Hz. We show that higher concentration of copper 2+ ions leads to more smooth dependence of ε` on frequency.

In the framework of study we offer a model to explain the observed phenomena based on peculiarities of Cu²⁺ ion interactions with the functional groups of melanin monomers and water molecules in coordination sphere.

Acknowledgement.This work was supported by the Russian Science Foundation, grant 19-73-10154.

References:

[1] L.D’Alba and M.D.Shawkey, Physiological Reviews, 99, 1 (2018)

[2] M.Sheliakina, A.B.Mostert and P.Meredith, Materials Horizons, 5, 256 (2018)

[3] U.Divakar, P.E.Schwenn and P.Meredith, Advanced Materials, 20, 3539 (2008)

[4] S.P.Whelan et al, 2d Materials, 7, 024008 (2020)

[5] J.M.Gallas et al, Biophysical Journal, 77, 1135 (1999)

Toxin detection through graphene Dirac point shift tracking

Nekrasov N.P.¹, Emelianov A.V.^1,2, Bobrinetskiy I.I.^1,3 (12 pt)

1 – National Research University of Electronic Technology, Moscow, Zelenograd, Russia

2 – Р.N. Lebedev Physical Institute of the Russian Academy of Sciences, Moscow, Russia

3 – Biosenes Institute, Novi-Sad, Serbia

8141147@gmail.com

To accurately track the response of specific aptamer to the presence of the toxin, measuring the liquid transfer characteristics of graphene transistor can be performed. This method is possible using sensor development based on a solution-gated ions-sensitive field-effect transistor (ISFET) with a graphene channel [1]. Graphene is supremely sensitive to its surroundings, enabling to see chemically induced reaction between specific aptamer and toxin [2]. Owing to the ~1-nm-thick electric double layer, ionic liquids enable low-voltage operation of the ISFET. Specific aptamers, that reacts with specific micotoxin were assembled to graphene through 1-pyrenebutyric acid N-hydroxysuccinimide (PBASE) layer Sensor demonstrates high sensitivity for toxin concentration form 1 pM to 100 nM showing ~10 mV shift of Dirac point per one decade of concentration change.

a

b

Figure 1. (a) transfer current-voltage characteristics for aflatoxin-M1 detection, (b) Dirac point change according to toxin concentration

Acknowledgement.This work was supported by the Russian Science Foundation, grant 19-19-00401.

References:

[1] Inaba, A. Yoo, G., Takei Y., Matsumoto K. and Shimoyama I., IEEE, 969–972 (2013)

[2] Cruz-Aguado J. A. and Penner G., Journal of agricultural and food chemistry, 56(22) (2008)

Green Synthesis Approach to Produce Luminescent Nanoparticles from Agricultural Waste and their potential biomedical application

Ashreen Norman ^1,2, Che Azurahanim Che Abdullah ^1,2, Ahmad Kamil bin Hj Mohd Jaaffar³

1- Institute of Bioscience, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

2- Biophysics Lab, Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

3- Lembaga Koko Malaysia, Tingkat 5–7, Wisma SEDCO, Lorong Plaza Wawasan, Off Coastal

Highway, Beg Berkunci 211, 88999, Kota Kinabalu, Sabah, Malaysia

ashreeeen@gmail.com

Malaysia has a large agricultural potential that can support economic activity. Rubber, palm oil, and cocoa are major agricultural export in Malaysia. Polyphenols are naturally occurring antioxidants found in foods like fruits and vegetables. They have been linked to numerous health benefits. Luminescent nanoparticles (LNPs) has attracted a great attention of researchers in the current era due to their unique properties. Though, the top-down synthesis of LNPs has always been one of the most preferred method to obtain CDs in significant yields. The LNPs used in this process could be obtained by a green approach such as the one-step hydrothermal method. The top- down synthesis method of LNPs has side effects such as toxicity which are still a major concern before it can be used as pharmaceutical excipients or drug delivery transporter. Owing to that, herein we proposed green LNPs from agricultural waste for bio-applications. The synthesis, structural and optical properties, as well as photoluminescence mechanisms of prepared nanoparticles are reviewed. Green technology opens new windows as there are readily available, renewable, economic and environmental-friendly in nature.

References:

[1] Liu, W., Diao, H., Chang, H., Wang, H., Li, T., & Wei, W. (2017). Green synthesis of carbon dots from rose-heart radish and application for Fe3+ detection and cell imaging. Sensors and Actuators B: Chemical, 241, 190–198.

Residence time as a tool for optimization of aerosol CVD synthesis of single-walled carbon nanotubes

Novikov I.V.¹, Khabushev E.M.^1,2 Krasnikov D.V.¹, Bubis A.V.¹, Goldt A.E.¹, Nasibulin A.G.^1,2

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

2 – Aalto University School of Chemical Engineering, Espoo, Finland

ilya.novikov@skoltech.ru

Aerosol chemical vapor deposition (CVD) is one of the most promising methods for synthesis of single-walled carbon nanotubes (SWCNTs) as it provides stabilization of the fine catalyst nanoparticles by extreme dilution solving the problem of non-reversible agglomeration of SWCNTs. Moreover, being a one-stage and a liquid-free process for SWCNT film production, this approach results in a number of advanced SWCNT-based optoelectronic applications [1]. Yet, unable to immobilize aerosol nanoparticles, aerosol CVD is limited towards conventional methods for catalyst evolution studies. In this investigation, we vary residence time via total flowrate control and consider its effect on SWCNT growth maintaining all the processes preceding nanotube growth: catalyst formation and nanotube nucleation (by means of fixing feeding rate and catalyst precursor concentration). The latter has been proved by unchanged SWCNT diameter distribution assessed via UV-vis-NIR spectroscopy. Furthermore, optoelectronic performance of the SWCNT films collected dependence on the residence time has been studied as well.

We have demonstrated intuitive relation as the SWCNT bundles lengthen with residence time (by scanning electron microscopy (SEM) observations). SWCNT quality, bundling degree and yield dependence on the residence time have investigated as well (using Raman spectroscopy, transmission electron microscopy (TEM), differential mobility analysis (DMA)). Having revealed yield decrease with residence time, we then have found a drop in the aerosol phase concentration, which is attributed to crucial deposition losses. Nevertheless, such a tendency leads to even more pronounced increase in equivalent sheet resistance conductivity (compared to expected effect caused exclusively by SWCNT lengthening), which is likely caused by decrease in catalyst particles and shorter nanotubes.

Acknowledgement.This work was supported by Russian Science Foundation project No. 20-73-10256.

References:

[1] Q. Zhang, N. Wei, P. Laiho, E.I. Kauppinen, Top. Curr. Chem. 375, 1-30 (2017).