Justification of the feasibility of executing the application (Обоснование целесообразности выполнения заявки на английском языке)

1. Introduction
1.1. Graphene
Graphene is the thinnest known material in the world with a one-atom-thick sheet of sp2-bonded carbon atoms arranged in a hexagonal honey comb crystal lattice [1]. Geim and Novoselov reported the isolation of graphene from graphite using a mechanical exfoliation technique for the first time in 2004 [2]. Graphene has a very interesting and distinct electronic properties. Its carrier density can be easily tuned by applying a gate voltage (i.e. electric field) [2-4]. As predicted by theory about graphene's low-energy excitations, electronic transport and ARPES measurements on graphene devices revealed that graphene’s charge carriers act like massless, chiral, Dirac Fermions [5, 6]. In the presence of the magnetic field, Dirac fermions, unlike ordinary electrons, display new physical phenomena [7] such as the anomalous integer quantum Hall effect (IQHE) [5, 6]. Another remarkable thing about graphene is that it has facilitated the observation of various phenomena, including atomic collapse [8, 9] and Hofstadter's butterfly energy spectrum [10, 11], which were previously challenging to detect in other condensed matter systems experimentally [12]. Due to its favorable electronic, spintronic, thermal, and mechanical characteristics, as well as its straightforward and cost-effective fabrication techniques, graphene has become widely favored, resulting in an abundance of research exploring both theoretical and experimental aspects of its distinct properties and potential applications [12-14].

1.2. Graphene fabrication techniques
Various techniques have been created for producing graphene up to this point. There are two main classes into which these methods can be grouped [15]:
1.2.1. Top-down methods
1.2.1.1. Mechanical exfoliation of graphene from graphite
In 2004, Geim and Novoselov reported the first isolation of graphene single layer using mechanical exfoliation by repeatedly cleaving graphite with an adhesive tape and placing the tape on a SiO2/Si substrate [2]. This method produces ultra-clean single-crystal monolayer graphene, which later can be transferred on a substrate such as SiO2/Si. Although the quality of graphene is excellent in mechanical exfoliation, this method has a couple of disadvantages. Since it is unpredictable and lacks consistent outcomes, repetition is necessary until single layers are successfully attained. As a result, the mechanical exfoliation requires a lot of labour. In addition, this method cannot produce large-area graphene sheets [15].
1.2.1.2. Reduction of graphene oxide to graphene
Reduction of graphene oxide can be carried out using various methods, such as chemical reduction with reducing agents (including hydrazine, sodium borohydride, or ascorbic acid), thermal reduction, and electrochemical reduction [16]. This reduction can be implemented to produce monolayer graphene [15]. Compared to mechanical exfoliation, the self-assembly of reduced graphene oxide (rGO) offers a potential way to produce transparent films on a large scale and at a lower cost. However, introducing a large number of defects and adsorption of functional groups are disadvantages of this method [15].
1.2.2. Bottom–up methods
1.2.2.1. Chemical vapour deposition (CVD)
CVD is a commonly employed technique in material processing where thin films, in this case graphene, are created on a heated substrate through a chemical reaction involving gaseous precursor substances [17]. CVD growth of graphene on catalytic metals, such as Cu and Ni, can produce large-scale defect-free graphene [15]. However, the CVD graphene is polycrystalline and may contain metal and polymer residues [18].
1.2.2.2. Epitaxial growth
Epitaxial growth of high-quality graphene on silicon carbide and ruthenium substrates at elevated temperatures in an ultra-high vacuum setting can yield high-quality graphene sheets the same size as the substrate. Nonetheless, the resulting graphene exhibits some interaction with the substrate, posing challenges for creating electrically isolated monolayer graphene [15].

1.3. The effect of adatoms on graphene
An adatom is an adsorbed atom on a crystal surface (in our case, graphene). There is the unique possibility of altering the electronic behaviour of graphene by depositing adatoms [19, 20]. Adatom can have effects such as inducing negative or positive charge carriers in graphene [19-23], lowering its mobility [21-23], introducing long-range Coulomb scattering [19-24], short-range scattering [24], and opening a band gap [12, 25-27]. Among adatom impacts on graphene, enhancing spin-orbit coupling by heavy metal adatoms to the point the graphene may become a quantum spin Hall insulator [28, 29], or experience a quantum anomalous Hall effect [30] is particularly intriguing [23].


2. Review on literatures: Altering the spin structure in graphene by adatom deposition
Control of the spin structure in graphene, i.e. spin splitting of its electronic states and a topologically nontrivial band gap at the Dirac point, is one of the most important problems in materials science today, which needs to be solved for the use of graphene in spintronics, especially for the implementation of dissipative-free transport. It is known that strong spin-orbit interaction is a necessary condition for observing effects such as the quantum spin Hall effect (QSHE) [31], quantum anomalous Hall effect (QAHE) [32, 33], etc. The second factor influencing the spin structure is the exchange interaction in graphene. In this regard, special attention is drawn to theoretical and experimental studies of possible magnetic order in two-dimensional carbon systems, such as superatomic graphene [34], twisted bilayer graphene [35], triangulene [36], nanographenes [37], etc. The experimentally unrealized Haldane model based on a graphene lattice with a nonuniform magnetic field distribution on the atomic scale [38] remains relevant and attractive since it predicts QAHE in a hexagonal two-dimensional lattice.
It is known that heavy metal adatoms on the surface can lead to enhanced spin-orbit interactions in graphene, which is confirmed by the observation of the spin Hall effect in graphene [39]. Moreover, magnetic metal adatoms at certain adsorption sites can enhance intrinsic spin-orbit interaction and QSH phase in graphene [40]. On the other hand, magnetization in graphene can appear upon contact with non-magnetic atoms, for example, when hydrogen atoms are adsorbed onto the graphene surface [41, 42] or when a second layer of graphene is positioned at a slight angle to the first one, in the so-called twisted graphene [35]. In this regard, it is extremely important to study the electronic structure of graphene to separate the contributions of spin-orbit and exchange interactions in graphene.
It should be noted that while the induction of dominant Kane-Mele spin-orbit coupling (SOC) in graphene by the deposition of indium (In) [28], thallium (Tl) [28], Osmium (Os) and iridium (Ir) [29, 30] is theoretically predicted, this effect was not observed in transport and ARPES experiments [23-24, 43-44]. Although it was suggested that this inconsistency between theory and these experiments probably occurred due to a lack of reliable interaction between the graphene surface and adatom in the transport measurements [21] or masking a possible gap opening by the disorder broadening in the ARPES experiment [24], this demonstrates the difficulty of realizing enhancement of SOC by adatoms in graphene experiments [22].
In the case of copper (Cu) adatoms, it is theoretically predicted that 1% coverage of copper (Cu) adatoms on graphene will induce both Kane-Mele and Bychkov-Rashba spin-orbit coupling [46] or at least one of them [47, 48]. While there is a report of non-local measurement (i.e. sending current through two contacts and measuring the non-local voltage at two other contacts at some distance from the current pads) that interprets the non-local signal as the confirmation of the presence of spin-orbit interaction in CVD graphene with copper residue and also in copper-decorated graphene [49], that non-local signal may have a valley or temperature origin and not necessarily spin [50, 51]. Furthermore, copper can cause magnetism and the exchange interaction in graphene [46-48]. As a result, a more controlled and comprehensive experiment that separates different factors by combining transport techniques such as weak localization with ARPES, STM/AFM, LEED, and XPS experiments measurements is necessary to investigate spin-orbit coupling in copper-doped graphene.


3. Plan and goals of the Project (expected results)
Iranian partner (Dr. Ali Khademi) is working on 2D materials, including graphene and quantum transport. He specifically worked on the effect of adatoms on graphene’s transport and electronic properties. He built a custom-made experimental setup, enabling us to evaporate different metal adatoms on graphene samples while they are at cryogenic temperatures and ultra-high vacuum (UHV) conditions, apply variable perpendicular magnetic fields between -100 and 100 mT, and perform transport measurements.
Russian partner (Dr. Artem G. Rybkin) is studying the electronic and spin structure of low-dimensional systems based on graphene, topological insulators, thin layers of metals and other systems with strong spin-orbit and exchange interactions in the Laboratory of Electronic and Spin Structure of Nanosystems at St. Petersburg State University. His research team has extensive and successful experience in studying the electronic and spin structure of the Dirac cone of electronic states of graphene and topological insulators and its modification under magnetic doping or contact with heavy metals.
Employing the expertise of Russian and Iranian partners, the project is dedicated to the search for new promising structures based on graphene and d-metals for the implementation of spin Hall effect and Rashba-Edelstein effect in spintronic devices.
Within the framework of the project, systems consisting of graphene and copper adatoms on a SiC(0001) substrate and SiO2/Si substrate will be synthesized and studied by experimental methods. It is planned to study the features of their electronic and crystal structure and transport properties to analyze the possibility of using the synthesized systems to realize quantum effects.

The following experimental results are planned:
- Transport and magneto-transport measurements, including weak localization measurements on pristine and copper-doped graphene, will be performed in a custom-made setup designed by the Iranian partner (Dr. Ali Khademi). These results will be used to obtain data about magneto-conductivity, change of charge carrier density by copper adatoms, and scattering rates such as dephasing and intervalley rates.
- The presence of copper adatoms on graphene will be confirmed by methods such as time-of-flight secondary ion mass spectrometry (ToF-SIMS) or X-ray photoelectron spectroscopy (XPS) after performing transport measurements by the Iranian partner.
- The core levels spectra of graphene and adatoms will be measured using the XPS method by the Russian partner (Dr. Artem Rybkin).
- The ARPES intensity maps will be measured in the GK direction of the graphene Brillouin zone by the Russian partner.
- The spin splitting of graphene electronic states will be investigated in the region of the Dirac cone by the Russian partner.
- At each synthesis step, the crystal structure of the system surface will be characterized using the LEED method by the Russian partner.
- For the final systems, surface images will be measured using STM/AFM and SEM methods by the Russian partner.
- The results on the electronic and crystalline surface structure of the synthesized systems obtained by magneto-transport, XPS, ARPES, LEED, and STM/AFM methods will be analyzed by both Russian and Iranian partners.

The results obtained from the project will be used in research and educational activities and will be included in the graduate qualification works of undergraduate and postgraduate students.


4. The purpose of the project (methods and approaches)
Control of the spin structure in graphene, i.e. spin splitting of its electronic states and a topologically nontrivial band gap at the Dirac point, is one of the most important problems in materials science today, which needs to be solved for the use of graphene in spintronics, especially for the implementation of dissipative-free transport. It is known that strong spin-orbit interaction is a necessary condition for observing effects such as the quantum spin Hall effect (QSHE) [31], quantum anomalous Hall effect (QAHE) [32, 33], etc. The second factor influencing the spin structure is the exchange interaction in graphene. In this regard, special attention is drawn to theoretical and experimental studies of possible magnetic order in two-dimensional carbon systems, such as superatomic graphene [34], twisted bilayer graphene [35], triangulene [36], nanographenes [37], etc. The experimentally unrealized Haldane model based on a graphene lattice with a nonuniform magnetic field distribution on the atomic scale [38] remains relevant and attractive since it predicts QAHE in a hexagonal two-dimensional lattice.
It is known that heavy metal adatoms on the surface can lead to enhanced spin-orbit interactions in graphene, which is confirmed by the observation of the spin Hall effect in graphene [39]. Moreover, magnetic metal adatoms at certain adsorption sites can enhance intrinsic spin-orbit interaction and QSH phase in graphene [40]. On the other hand, magnetization in graphene can appear upon contact with non-magnetic atoms, for example, when hydrogen atoms are adsorbed onto the graphene surface [41, 42] or when a second layer of graphene is positioned at a slight angle to the first one, in the so-called twisted graphene [35]. In this regard, it is extremely important to study the electronic structure of graphene to separate the contributions of spin-orbit and exchange interactions in graphene.
It should be noted that while the induction of dominant Kane-Mele spin-orbit coupling (SOC) in graphene by the deposition of indium (In) [28], thallium (Tl) [28], Osmium (Os) and iridium (Ir) [29, 30] is theoretically predicted, this effect was not observed in transport and ARPES experiments [23-24, 43-44]. Although it was suggested that this inconsistency between theory and these experiments probably occurred due to a lack of reliable interaction between the graphene surface and adatom in the transport measurements [21] or masking a possible gap opening by the disorder broadening in the ARPES experiment [24], this demonstrates the difficulty of realizing enhancement of SOC by adatoms in graphene experiments [22].
In the case of copper (Cu) adatoms, it is theoretically predicted that 1% coverage of copper (Cu) adatoms on graphene will induce both Kane-Mele and Bychkov-Rashba spin-orbit coupling [46] or at least one of them [47, 48]. While there is a report of non-local measurement (i.e. sending current through two contacts and measuring the non-local voltage at two other contacts at some distance from the current pads) that interprets the non-local signal as the confirmation of the presence of spin-orbit interaction in CVD graphene with copper residue and also in copper-decorated graphene [49], that non-local signal may have a valley or temperature origin and not necessarily spin [50, 51]. Furthermore, copper can cause magnetism and the exchange interaction in graphene [46-48]. As a result, a more controlled and comprehensive experiment that separates different factors by combining transport techniques such as weak localization with ARPES, STM/AFM, LEED, and XPS measurements is necessary to investigate spin-orbit coupling in copper-doped graphene.
As part of this work, we plan to study the change in the transport properties of graphene during the adsorption of copper atoms; the results of studies of the electronic structure of graphene will be taken into account when analyzing the data. The unique characteristic of this project is that we will employ different experimental techniques, including transport measurements, ARPES, STM/AFM, LEED, and XPS. As a result, the acquired data will present a comprehensive picture of the effect of copper adatoms on graphene. We hope these results will help relate ARPES, STM and transport experiments that have, until now, offered disconnected pictures of adatom-doped graphene.
Experimental studies of graphene electronic structure will be carried out using a whole range of the most modern methods and approaches: magneto-transport measurements including weak localization measurements, angle- and spin-resolved photoelectron spectroscopy, X-ray photoelectron spectroscopy, low-energy electron diffraction, scanning probe microscopy, and scanning electron microscopy. For this purpose, it is planned to use the resources of the St. Petersburg State University Research Park and the Sharif University of Technology.
1) Transport and magneto-transport measurements, including weak localization measurements on pristine and copper-doped graphene, will be performed in a custom-made setup designed by the Iranian partner (Dr. Ali Khademi). A rather unique experimental setup was built, enabling us to evaporate different metal adatoms on graphene samples while they are at cryogenic temperatures and ultra-high vacuum (UHV) conditions, apply variable perpendicular magnetic field between -100 and 100 mT, and perform transport measurements. This setup can be used to obtain data about magneto-conductivity, mobility, change of charge carrier density by adatoms, and scattering rates such as dephasing and intervalley rates.
2) The presence of copper adatoms on graphene will be confirmed by methods such as time-of-flight secondary ion mass spectrometry (ToF-SIMS) or X-ray photoelectron spectroscopy (XPS) after performing transport measurements by the Iranian partner
3) The main part of the Russian partner's experimental research on the project is planned to be carried out in situ using the equipment of the resource center "Physical Methods of Surface Investigation" and the interdisciplinary resource center "Nanotechnologies" of the St. Petersburg State University Research Park. The following equipment will be used for this:
2-1) The unique scientific setup "Nanolab" (Nanolab), in which the measurements will be carried out, is equipped with a hemispherical energy analyzer Scienta R4000 with an energy resolution of about 1 meV and a 6-axis cryo-manipulator for measuring ARPES maps in k-space at liquid helium temperatures. Nanolab is equipped with two Mott detectors for measuring spin polarization in three directions, as well as an Omicron VT AFM XA 50/500 scanning probe microscope for studying surface structure with atomic resolution in a wide temperature range.
2-2) Univer-M research platform, consisting of ultra-high vacuum chamber with hemispherical energy analyzer VG Scienta R4000 with microchannel detector, a 5-axis motorized manipulator with liquid nitrogen cooling, narrowband high-intensity ultraviolet radiation source VUV 5k with a monochromator and retractable capillary, X-ray source with double Al/Mg anode.
4) Scanning electron microscopy studies to study the surface microstructure of the synthesized systems will be carried out at the interdisciplinary resource center "Nanotechnologies" of the St. Petersburg State University Research Park using Zeiss Supra and Zeiss Auriga scanning electron microscopes.


Research Ethics
In terms of accuracy and copyright rules, all rights are reserved. Both sides in through mutual agreement check the results and have contribution on data.


5. Information on envisaged synergies between SPbU and SUT
During the implementation of this project, the potential of the scientific group of Dr. A. Rybkin on the ARPES, STM/AFM, LEED, and XPS experiments in low-dimensional systems based on graphene, topological insulators, thin layers of metals and other systems with strong spin-orbit and exchange interactions and the background in Dr. A. Khademi's lab to study transport properties of two-dimensional materials including adatom-decorated graphene, provide a worthy benchmark to trigger high-quality research. This project can pave the way to combining, coordinating, and relating transport measurement with ARPES, STM/AFM, LEED, and XPS experiments (that have until now offered disconnected pictures) in different materials and electronic mesoscopic systems and have a significant impact on our understanding of these systems. As a result of this project, in addition to publishing one or more prestigious research papers in international scientific journals, knowledge transfer, synergic collaborations, and cooperation can be boosted between Russian-Iranian researchers during this project and future joint projects.


6. Project partners planned sources of follow-up funding for joint projects:
1 .Grants of the Russian Science Foundation in the priority area of RSF activities “Basic Scientific Research and Exploratory Scientific Research, Conducted by International Research Teams” (in cooperation with the Iran National Science Foundation - INSF)
https://www.rscf.ru/upload/iblock/d97/ohc0zqub1dkr60ryz8usmurr4ukdp0fz.pdf
https://rscf.ru/news/found/otkryt-pervyy-konkurs-rnf-sovmestno-s-natsionalnym-nauchnym-fondom-irana-insf/
2. Grants of the Ministry of Education and Science of the Russian Federation in the field of science in the form of subsidies from the federal budget to ensure the conduct of scientific research by Russian scientific organizations and (or) educational organizations of higher education together with organizations of the BRICS countries in the framework of ensuring the implementation of the program of bilateral and multilateral scientific and technological cooperation.
https://minobrnauki.gov.ru/documents/?ELEMENT_ID=74132
https://minobrnauki.gov.ru/grants/grants/?ELEMENT_ID=53387
3. Other competitions and grants for financing of scientific research within the framework of international cooperation between Russia and Iran, as well as BRICS countries.
https://minobrnauki.gov.ru/press-center/news/mezhdunarodnoe-sotrudnichestvo/79833/?sphrase_id=8139048


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