Formation of linear carbon chains in a combined field of an arc discharge and laser radiation

Abstract

We present a method of synthesis of sp-carbon allotropes or carbynes. Linear chains of carbon atoms are obtained from graphite placed in a joint field of laser plasma and arc discharge. The combined action of laser and arc discharge allows to create conditions for the formation of a variety of carbon allotropes, whose structural composition is governed by the interplay of external fields. The method may be employed in the mass production of sp- and sp²- hybridized carbon for the needs of possible applications in micro and nanoelectronics, biosensing.

Full text

Vol.:(0123456789)
Optical and Quantum Electronics (2023) 55:830
https://doi.org/10.1007/s11082-023-05007-0
1 3
Formation oflinear carbon chains inacombined field
ofanarc discharge andlaser radiation
A.Osipov1· S.Kutrovskaya1,2· V.Samyshkin1· A.Abramov1· N.Khalimov1·
S.P.Essaka1· A.Kucherik1
Received: 23 January 2023 / Accepted: 23 May 2023
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023
Abstract
We present a method of synthesis of sp-carbon allotropes or carbynes. Linear chains of
carbon atoms are obtained from graphite placed in a joint field of laser plasma and arc
discharge. The combined action of laser and arc discharge allows to create conditions for
the formation of a variety of carbon allotropes, whose structural composition is governed
by the interplay of external fields. The method may be employed in the mass production of
sp- and sp2- hybridized carbon for the needs of possible applications in micro and nano-
electronics, biosensing.
Keywords sp-hybridized carbon· Laser action· Closed-loop flow cell· Arc discharge
1 Introduction
Carbon is one of the widespread materials having multiple allotropic forms. Carbon-based
nanostructures include nanotubes, fullerenes, onion-structures, linear chains of carbon etc.
The variety of nanostructured forms of carbon opens an opportunity to tailor electronic and
optical properties of carbon-based devices for a variety of perspective applications (Bianco
2018). However, the mass production of nanostructured carbon for industrial applications
would require technologies of controllable synthesis large volumes of specific carbon allo-
tropes characterised by a high stability.
Currently, several carbon synthesis and fabrication methods that are used on the indus-
trial scale. These include the thermal decomposition of graphite in an arc discharge, chemi-
cal deposition of carbon from the gas phase using a catalyst (Bianco 2018; Robertson
1991) physical deposition of carbon from the gas phase. Methods of laser evaporation and
cold destruction of graphite (Fursey etal. 2009) are generally used in research laboratories
* A. Osipov
osipov@vlsu.ru
* A. Kucherik
kucherik@vlsu.ru
1 1D-Lab, Vladimir State University, Gor’kogo Street 87, Vladimir600000, Russia
2 Abrikosov Center forTheoretical Physics, Moscow Institute forPhysics andTechnology,
Institutskii Pereulok 9/7, Dolgoprudny141701, Russia
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

A.Osipov et al.
1 3
830 Page 2 of 7
rather than for industrial production. This is because, first, their output represents a rela-
tively small amount of high quality nanostructures (characterised by a low number of
defects, strong repeatability of the structure). Typically, to achieve a high quality output
one needs to employ more sophisticated, expensive and time-consuming methods. A way
to optimize the fabrication technology of specific carbon allotropes may involve combina-
tion of several methods of synthesis in one single technological process.
However, up to now, no effective hybrid (combined) technology for sp-carbon produc-
tion in sufficient quantities, at least for laboratory studies, has been developed, to the best
of our knowledge. A significant limitation to the effective synthesis of linear carbon chains
comes from the need to create a very specific combination of pressure and temperature in
order to ensure the dominant realization of the sp-hybridized phase of carbon (Lukin and
Gülseren 2021). Based on our previous studies, in this work we present a hybrid scheme for
mass production of sp-carbon. The method is based on thermal decomposition of graphite
in an arc discharge combined with simultaneous plasma retention due to the action of an
intense laser radiation in the course of the accumulation of the resulting material in an
open-type flow cell.
2 Results
The closed-loop flow cell (see Fig.1.) has been designed in order to enable simultaneous
or consecutive realization of two fabrication methods: thermal decomposition of graphite
precursor sticks in an arc discharge and fragmentation of graphite under NIR laser pulse
action. An arc discharge makes it possible to obtain different carbon allotropes (Fomin
and Brazhkin 2020), while an additional laser action, on one hand, preserves the discharge
plasma providing more efficient carbon decomposition, and, on the other hand, creates
conditions for a predominant formation of linear carbon chains (Taguchi 2015). We have
built an experimental setup schematically shown in Fig.1. It enables passing the flow of
Fig. 1 The schematic of an experimental setup allowing for a combined action of the arc discharge and the
laser beam on the graphite target in a closed loop configuration
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Formation oflinear carbon chains inacombined field ofanarc…
1 3
Page 3 of 7 830
a colloidal solution in a direction perpendicular to both the laser beam and the arc dis-
charge. The buffer liquid was a distilled water as in work (Kucherik etal. 2019). Carbon
microparticles turning up in the water only during the process of arc discharge realizing.
The carbon concentration measuring (without additional laser radiation) showed the aver-
age value about 1mkg/1 ml. The dielectric closed-loop flow cell has been manufactured
in order to prevent the charge concentration on its surface. The laminar flow of a colloidal
solution passes the point of a combined action of the discharge arch and the laser beam.
This ensures that all the sublimation products of graphite decomposition appear in a liq-
uid phase only in the open-zone flow cell. The resulting dispersive phase is circulated in
a closed-loop flow cell. To stabilize especially linear carbon form in liquid we have pre-
pared the colloidal solution based on distilled water and spherical gold nanoparticles. Gold
nanoparticles are capable of efficiently catalysing the growth of carbon by pulling the end
carbon atoms into the crystal lattice of metal nanoparticles (NPs). Here, gold anchors stabi-
lize the sp-carbon allotrope by preventing its vibration induced decomposition into shorter
components, folding and bending.
3 Methods
We employed pyrolytic graphite sticks of purity 99.99% as electrodes to generate an arc
discharge. The voltage of 100kV between 2 electrodes located at the distance of 7mm has
been applied using a DC source “Coulomb 715d”. In this case, the current value was of
1.5A.
To fulfil a specific set of conditions required for the formation of sp-carbon we have
used nanosecond laser pulses generated by an Ytterbium (Yb) fiber laser having the central
wavelength of 1064nm, the pulse duration of 100ns, the repetition rate of 20kHz and the
average power of 20W. The laser spot size at the point of a combined action of the dis-
charge arc and the laser beam was about 100mμ.
In the experiments, we have employed the arc discharge and the laser irradiation either
separately or simultaneously and studied their impact on the synthesis of carbon allotropes.
We have also tuned the composition of the target fluid. Here we have relied upon the results
of our previous studies that have proven an ability of spherical gold nanoparticles (
∅=
20nm Au NPs) to stabilize sp-carbon chains (Kutrovskaya etal. 2020, 2021) in a distilled
water solution circulating in a closed-loop flow cell. The best results for selective synthesis
of sp-carbon chains have been obtained in the regime of simultaneous action of the arc dis-
charge and the laser field on a water solution of carbon containing Au NPs.
It is important to note that the solution of carbon with Au NPs becomes transparent and
colourless after the combined action of the arc discharge and laser irradiation (see Fig.2a).
This is indicative of the sp-carbon formation (Tschannen etal. 2022). In contrast, separate
action of the arc discharge and laser irradiation results in a formation of dark carbon solu-
tions rich by sp2-carbon allotropes (Serafini etal. 2022).
3.1 Raman andTEM characterization ofcarbon allotropes
To reveal the morphology and structural features of carbon allotropes resulting from the
synthesis procedures described above, the Raman spectroscopy and the transmission elec-
tron microscopy have been used. The Raman spectra of the solutions have been measured
using the excitation laser light of the wavelength of 532nm and the power of 20mW. The
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

A.Osipov et al.
1 3
830 Page 4 of 7
spectra have been collected in a confocal microscope configuration with 100× magnifi-
cation. The collection time has been 10s, each spectrum is a result of averaging over 7
measurements.
The presence of sp–sp2 carbon allotropes can be easily identified by Raman spectros-
copy. The initial sample of graphite stick precursor is composed of fragments of nonpla-
nar graphene characterised by the sp2-hybridization. For this reason, it manifests itself in
the Raman spectra by two peaks at 1580 and 2580 cm−1 that are typical Raman replicas
for the hexagon carbon lattice (see the Appendix). In Fig.3 the Raman bands are inter-
preted in agreement with the earlier works (Nanomaterials 2021; Kutrovskaya etal. 2020).
The weak band around 1100 cm−1 is caused by the presence of single electron C–C mode
vibrations. The Raman spectra of sp2-carbon allotropes show characteristic features in the
1200–1800 cm−1 region, in general. The peak near 1427 cm−1 correlates to the trans-pol-
yacetylenes (TPA). It is important to note that traces of 1575 cm−1 and 1808 cm−1 are
completely washed out in the case of a solution formed by a combined action of the arc
Fig. 2 Colloidal systems of different compositions realized within the setup that we employed. Left to right:
a the mixed system after the combined action of an arc discharge and laser irradiation, b the carbon system
affected by only electric arc discharge, c the carbon system after the combined action of an arc discharge
and laser irradiation, d the initial water solution containing gold nanoparticles
Fig. 3 a Raman spectra of the solutions prepared in different regimes: the mixed system after a combined
action of an arc discharge and laser irradiation (black curve); the carbon system prepared using only an
electric arc action (red curve); the purely carbon solution (no NPs) after a combined action of an arc dis-
charge and laser irradiation (blue curve). b shows the high resolution transmission electron microscopy (HR
TEM) images of a sample produced by drop off—deposition of a solution containing sp-carbon and Au NPs
on a solid substrate. Here dark points correspond to the Au NPs. These images reveal the bunch arrange-
ment of linear carbon chains confined between Au NPs. (Color figure online)
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Formation oflinear carbon chains inacombined field ofanarc…
1 3
Page 5 of 7 830
discharge and laser irradiation in the presence of Au NPs (see the black curve of Fig.3a).
This spectrum only shows a strong band about 2171 cm−1 characteristic of linear carbon
(Tschannen etal. 2022; Yang 2022). This proves that sp-carbon phase dominates in this
sample. The peak near 2350 cm−1 correlates to the multiphonon scattering (Zavidovskii
etal. 2020), which may shift the signal away from the main line by a quantity equal to pho-
ton energy.
4 Discussion
Let us now briefly discuss the applicability of the developed method for mass production
of sp-carbon. The key role here is played by the circulation of a carbon fluid enriched with
Au NPs on a closed loop. It enable one to achieve the desired ratio of sp-carbon to gra-
phene and other carbon allotropes. The mass ratio of sp-carbon to other fractions may be
controlled by the Raman spectroscopy. As the black curve in Fig.3a shows, the enrichment
of a fluid by sp-carbon can achieve over 95%, in which case the Raman peaks associated
with sp2-carbon are barely visible and the spectrum is dominated by resonances character-
istic of polyyne chains. Once the fluid placed in the closed loop is sufficiently enriched in
sp-carbon, it can be deposited on a substrate as Fig.3b shows. The new target fluid would
be placed in the circuit instead, and the procedure would be repeated. Each cycle includ-
ing loading of the fluid, its enrichment in sp-carbon and substrate deposition takes about
30 min, currently, that enables one to realise 40–50 cycles of synthesis of sp-carbon in
24h. This is a significant step forward compared to the previously employed techniques
such as the growth of carbon chains inside double-wall carbon nanotubes. Note also that
the laser ablation in liquid phase technique that allowed us to obtain record-long straight
carbon chains requires a rather exotic target: shunghit polycrystals. In contrast, the pre-
sent approach operates with a carbon fluid that can be easily prepared from graphite and
distilled water. In order to further optimise the method and shorten the cycle of synthesis,
we paid a special attention to the optimization of the intensity of laser irradiation and the
strength of electric field of the arc discharge. The concentration and size of Au NPs are two
more parameters of the optimization. We cautiously believe that the duration of the cycle
of synthesis of sp-carbon can be reduced to 10min in a near future.
5 Conclusions
In conclusion, we have developed an experimental setup based on a combined effect of
an electric arc discharge and laser irradiation on a fluid containing carbon and Au NPs.
By optimization of the setup we have found a regime allowing for predominant synthesis
of sp- or sp2 -carbon nanostructures. The combined effect of an electric arc discharge and
laser field offers a powerful tool for the synthesis of sp-carbon in liquid media, as con-
firmed by our Raman spectroscopy data. It is important to note that the presence of stabi-
lizing metal nanoparticles is strongly essential stabilization of linear carbon formation. We
have successfully deposited the synthesised polyyne chains on a gold platinum grid. High
resolution TEM images confirm formations of a multitude of linear carbon chains attached
to gold nanoparticles.
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

A.Osipov et al.
1 3
830 Page 6 of 7
Appendix
See Fig.4.
Author contributions AO contributed to the laser ablation experiments and writing manuscript; SK has
written the manuscript; VS has realized TEM experiments; AA contributed to the laser ablation experi-
ments; NK the experimental setup creation; SPE has performed light scattering experiments; AK has con-
ceived the work and contributed to the interpretation of the results.
Funding A.O. acknowledges the support from Ministry of Science and Higher Education of the Russian
Federation within the state assignment in the field of scientific activity (theme FZUN-2020-0013, state
assignment of VlSU). The work of S.K. was supported by Moscow Institute of Physics and Technology
under the Priority 2030 Strategic Academic Leadership Program. The study was also carried out using
the equipment of the interregional multispecialty and interdisciplinary center for the collective usage of
promising and competitive technologies in the areas of development and application in industry/mechanical
engineering of domestic achievements in the field of nanotechnology (Agreement No. 075-15-2021-692 of
August 5, 2021).
Data availability Any used datasets can be accessed via the e-mail request to the corresponding author.
Declarations
Conflict of interest The authors have no competing interests that might be perceived to influence the results
and/or discussion reported in this paper/
Ethical approval The ethical issues, including plagiarism, informed consent, is conduct, data fabrication and/
or falsification, double publication and/or submission, and redundancy, have been completely observed by
the authors.
Fig. 4 Raman spectra of initial
graphite stick precursor contains
two pronounced peak at 1580
and 2680 cm−1 that is typical
feature for sp2 carbon matter
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

Formation oflinear carbon chains inacombined field ofanarc…
1 3
Page 7 of 7 830
References
Bianco, A.: A carbon science perspective in 2018: Current achievements and future challenges. Carbon
132, 785–801 (2018)
Fomin, Y.D., Brazhkin, V.V.: Comparative study of melting of graphite and graphene. Carbon 157, 767–778
(2020)
Fursey, G.N., Petrick, V.I., Novikov, D.V.: Low-threshold field electron emission from carbon nanoclusters
formed upon cold destruction of graphite. Tech Phys. 54, 1048–1051 (2009). https:// doi. org/ 10. 1134/
S1063 78420 90702 02
Guowei Yang, Synthesis, properties, and applications of carbyne nanocrystals, Materials Science and Engi-
neering: R: Reports, 151, 10062, (2022). https:// doi. org/ 10. 1016/j. mser. 2022. 100692
Kucherik, A. O., Osipov, A. V., Arakelian, S. M. [et al.] The laser-assisted synthesis of linear carbon chains
stabilized by noble metal particle/J Phys: Conference Series. 1164(1), (2019). https:// doi. org/ 10. 1088/
1742- 6596/ 1164/1/ 012006
Kutrovskaya, S., Samyshkin, V., Lelekova, A., Povolotskiy, A., Osipov, A., Arakelian, S., Kucherik, A.:
Field-Induced assembly of sp-sp2 carbon sponges. Nanomaterials, 11(3), 1–8 (2021). https:// doi. org/
10. 3390/ nano1 10307 63
Kutrovskaya, S., Osipov, A., Baryshev, S., Zasedatelev, A., Samyshkin, V., Demirchyan, S., Pulci, O., Gras-
sano, D., Gontrani, L., Hartmann, R.R., Portnoi, M.E.: Excitonic fine structure in emission of linear
carbon chains. Nano Lett. 20, 6502–6509 (2020)
Lukin, A., Gülseren, O.: Tuning the spatially controlled growth, structural self-organizing and cluster-
assembling of the carbyne-enriched nano-matrix during ion-assisted pulse-plasma deposition. FDMP.
18(6), 1763–1779 (2022). https:// doi. org/ 10. 32604/ fdmp. 2022. 022016
Robertson, J.: Hard Amorphous (diamond-like) carbons. Prog. Solid. St. Chem. 21, 199–333 (1991)
Serafini, P., Milani, A., Tommasini, M., Castiglioni, C., Proserpio, D.M., Bottani, C.E., Casari, C.S.: Vibra-
tional properties of graphdiynes as 2D carbon materials beyond graphene. Phys. Chem. Chem. Phys.
24, 10524–10536 (2022)
Taguchi, Y., etal.: Polyyne formation by graphite laser ablation in argon and propane mixed gases. Carbon
94, 124–128 (2015)
Tschannen, C.D., Frimmer, M., Vasconcelos, T.L., Shi, L., Pichler, T., Novotny, L.: Tip-enhanced stokes–
anti-stokes scattering from carbyne. Nano Lett. 22(8), 3260–3265 (2022)
Zavidovskii, I.A., Streletskii, O.A., Nishchak, O.Y., etal.: Resistivity of thin carbon films with different sp-
bonds fractions. Tech. Phys. 65, 139–144 (2020)
Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published maps and
institutional affiliations.
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under
a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted
manuscript version of this article is solely governed by the terms of such publishing agreement and applicable
law.
Content courtesy of Springer Nature, terms of use apply. Rights reserved.

1.
2.
3.
4.
5.
6.
Terms and Conditions
Springer Nature journal content, brought to you courtesy of Springer Nature Customer Service Center
GmbH (“Springer Nature”).
Springer Nature supports a reasonable amount of sharing of research papers by authors, subscribers
and authorised users (“Users”), for small-scale personal, non-commercial use provided that all
copyright, trade and service marks and other proprietary notices are maintained. By accessing,
sharing, receiving or otherwise using the Springer Nature journal content you agree to these terms of
use (“Terms”). For these purposes, Springer Nature considers academic use (by researchers and
students) to be non-commercial.
These Terms are supplementary and will apply in addition to any applicable website terms and
conditions, a relevant site licence or a personal subscription. These Terms will prevail over any
conflict or ambiguity with regards to the relevant terms, a site licence or a personal subscription (to
the extent of the conflict or ambiguity only). For Creative Commons-licensed articles, the terms of
the Creative Commons license used will apply.
We collect and use personal data to provide access to the Springer Nature journal content. We may
also use these personal data internally within ResearchGate and Springer Nature and as agreed share
it, in an anonymised way, for purposes of tracking, analysis and reporting. We will not otherwise
disclose your personal data outside the ResearchGate or the Springer Nature group of companies
unless we have your permission as detailed in the Privacy Policy.
While Users may use the Springer Nature journal content for small scale, personal non-commercial
use, it is important to note that Users may not:
use such content for the purpose of providing other users with access on a regular or large scale
basis or as a means to circumvent access control;
use such content where to do so would be considered a criminal or statutory offence in any
jurisdiction, or gives rise to civil liability, or is otherwise unlawful;
falsely or misleadingly imply or suggest endorsement, approval , sponsorship, or association
unless explicitly agreed to by Springer Nature in writing;
use bots or other automated methods to access the content or redirect messages
override any security feature or exclusionary protocol; or
share the content in order to create substitute for Springer Nature products or services or a
systematic database of Springer Nature journal content.
In line with the restriction against commercial use, Springer Nature does not permit the creation of a
product or service that creates revenue, royalties, rent or income from our content or its inclusion as
part of a paid for service or for other commercial gain. Springer Nature journal content cannot be
used for inter-library loans and librarians may not upload Springer Nature journal content on a large
scale into their, or any other, institutional repository.
These terms of use are reviewed regularly and may be amended at any time. Springer Nature is not
obligated to publish any information or content on this website and may remove it or features or
functionality at our sole discretion, at any time with or without notice. Springer Nature may revoke
this licence to you at any time and remove access to any copies of the Springer Nature journal content
which have been saved.
To the fullest extent permitted by law, Springer Nature makes no warranties, representations or
guarantees to Users, either express or implied with respect to the Springer nature journal content and
all parties disclaim and waive any implied warranties or warranties imposed by law, including
merchantability or fitness for any particular purpose.
Please note that these rights do not automatically extend to content, data or other material published
by Springer Nature that may be licensed from third parties.
If you would like to use or distribute our Springer Nature journal content to a wider audience or on a
regular basis or in any other manner not expressly permitted by these Terms, please contact Springer
Nature at
onlineservice@springernature.com