{"id":39036,"date":"2019-10-31T22:27:30","date_gmt":"2019-10-31T19:27:30","guid":{"rendered":"https:\/\/prohoster.info\/blog\/dvumernyj-duet-sozdanie-borofen-grafenovyh-geterostruktur\/"},"modified":"2019-10-31T22:27:30","modified_gmt":"2019-10-31T19:27:30","slug":"dvumernyj-duet-sozdanie-borofen-grafenovyh-geterostruktur","status":"publish","type":"post","link":"https:\/\/prohoster.info\/en\/blog\/news\/dvumernyj-duet-sozdanie-borofen-grafenovyh-geterostruktur","title":{"rendered":"Two-Dimensional Duo: Creating Borophen-Graphene Heterostructures","gt_translate_keys":[{"key":"rendered","format":"text"}]},"content":{"rendered":"

\"Two-Dimensional
\n
\n\"Mutation is the key to unlocking the mystery of evolution. The path from simple organisms to the dominant biological species spans millennia. But every few hundred thousand years, evolution takes a dramatic leap forward\" (Charles Xavier, X-Men, 2000). If we set aside all the science fiction elements present in comics and films, Professor X's words hold true. The development of anything progresses uniformly for the most part, but sometimes there are leaps that have a tremendous impact on the entire process. This applies not only to the evolution of species but also to the evolution of technologies, primarily driven by humans, their research, and inventions. Today we will introduce you to a study that, according to its authors, represents a true evolutionary leap in nanotechnology. How researchers from Northwestern University (USA) succeeded in creating a new two-dimensional heterostructure, why graphene and borophen were chosen as the foundation, and what properties such a system may possess? This will be explained by the research group's report. Let's go.<\/a><\/noindex><\/p>\n

The foundation of the research<\/h3>\n

\nThe term \"graphene\" has been heard many times \u2014 it is a two-dimensional modification of carbon, consisting of a single layer of carbon atoms that is one atom thick. However, \"borophen\" is encountered very rarely. This term refers to a two-dimensional crystal composed exclusively of boron (B) atoms. The possibility of borophen's existence was first predicted back in the mid-90s, but in practice, this structure was only successfully obtained by 2015. <\/p>\n

The atomic structure of borophen consists of triangular and hexagonal elements and is a result of the interaction between two-center and multi-center in-plane bonds, which is characteristic of elements with an electron deficiency, to which boron belongs.<\/p>\n

*<\/b>Two-center and multi-center bonds refer to chemical bonds \u2014 interactions between atoms that characterize the stability of a molecule or crystal as a unified structure. For example, a two-center two-electron bond occurs when 2 atoms share 2 electrons, while a two-center three-electron bond involves 2 atoms and 3 electrons, and so on.<\/p><\/blockquote>\n

From a physical standpoint, borophene may be more durable and flexible compared to graphene. It is also believed that borophene structures could serve as effective additives for batteries, as borophene possesses high specific capacity and unique properties of electronic conductivity and ion transport. However, this is currently just a theory.<\/p>\n

Being a trivalent element*<\/i>, boron has at least 10 allotropes*<\/i>. In its two-dimensional form, such polymorphism*<\/i> is also observed. <\/p>\n

A trivalent element*<\/b> is capable of forming three covalent bonds, with a valence of three. <\/p><\/blockquote>\n

Allotropy*<\/b> is when a single chemical element can be represented in the form of two or more distinct substances. For example, carbon exists as diamond, graphene, graphite, carbon nanotubes, etc.<\/p><\/blockquote>\n

Polymorphism*<\/b> is the ability of a substance to exist in different crystalline structures (polymorphic modifications). For simple substances, this term is synonymous with allotropy. <\/p><\/blockquote>\n

Given such extensive polymorphism, the suggestion arises that borophene could be an excellent candidate for creating new two-dimensional heterostructures, as various boron bonding configurations should relax the requirements for lattice matching. Unfortunately, this issue has previously been studied only at a theoretical level due to the complexities of synthesis.<\/p>\n

For conventional 2D materials derived from bulk layered crystals, vertical heterostructures can be realized using mechanical stacking. On the other hand, two-dimensional lateral heterostructures are based on bottom-up synthesis. Atomically precise lateral heterostructures hold great potential in addressing issues related to controlling the functional capabilities of heterojunctions, yet due to covalent bonding, imperfect lattice matching often results in broad and disordered interfaces. Consequently, while there is potential, there are also challenges in its realization.<\/p>\n

In this work, researchers managed to integrate borophene and graphene into a single two-dimensional heterostructure. Despite the mismatch in the crystallographic lattices and symmetry between borophene and graphene, the sequential deposition of carbon and boron on an Ag(111) substrate in ultra-high vacuum (UHV) results in nearly atomically precise lateral hetero-interfaces with predicted lattice alignments, as well as vertical hetero-interfaces. <\/p>\n

Preparation for the study<\/h3>\n

\nBefore studying the heterostructure, it needed to be fabricated. The growth of graphene and borophene was carried out in an ultra-high vacuum chamber at a pressure of 1\u00d710^-10 millibar.<\/p>\n

The single crystal substrate Ag(111) was cleaned through repeated cycles of Ar+ sputtering (1 x 10^-5 millibar, energy 800 eV, for 30 minutes) and thermal annealing (550 \u00b0C, for 45 minutes) to obtain an atomically clean and flat surface of Ag(111).<\/p>\n

Graphene was grown by electron beam evaporation of pure (99.997%) graphite rods with a diameter of 2.0 mm onto a substrate of Ag(111) heated to 750 \u00b0C at a filament current of ~ 1.6 A and accelerating voltage of ~ 2 kV, resulting in an emission current of ~ 70 mA and a carbon flux of ~ 40 nA. The pressure in the chamber was 1 x 10^-9 millibar.<\/p>\n

Borophene was grown by electron beam evaporation of pure (99.9999%) boron rods onto a sub-monolayer graphene on Ag(111) heated to 400-500 \u00b0C. The filament current was ~ 1.5 A, and the accelerating voltage was 1.75 kV, resulting in an emission current of ~ 34 mA and a boron flux of ~ 10 nA. During the growth of borophene, the pressure in the chamber was approximately 2 x 10^-10 millibar.<\/p>\n

Research Results<\/h3>\n

\n\"Two-Dimensional
\nImage No. 1<\/i><\/p>\n

In the image 1A<\/b> shown STM*<\/i> image of the grown graphene, where graphene domains are best visualized using the map dI<\/i>\/dV<\/i> (1B<\/b>), where I<\/i> and V<\/i> \u2014 tunnel current and sample bias, and d<\/i> \u2014 density. <\/p>\n

STM*<\/b> \u2014 scanning tunneling microscope.<\/p><\/blockquote>\n

dI<\/i>\/dV<\/i> Sample maps allowed seeing a higher local density of states in graphene compared to the Ag(111) substrate. Consistent with previous studies, the surface state of Ag(111) has a stepped characteristic, shifted towards positive energies on dI<\/i>\/dV<\/i> the graphene spectrum (1C<\/b>), which explains the higher local density of states in graphene at 1B<\/b> 0.3 eV.<\/p>\n

In the image 1D<\/b> we can see the structure of monolayer graphene, where the honeycomb lattice is clearly visible and moir\u00e9 superstructure*<\/i>.<\/p>\n

Superstructure* <\/b> \u2014 a feature of the crystalline structure of a compound that repeats at certain intervals, thereby creating a new structure with a different periodicity. <\/p>\n

Moire*<\/b> \u2014 the overlapping of two periodic mesh patterns on top of each other.<\/p><\/blockquote>\n

At lower temperatures, growth leads to the formation of dendritic and defective graphene domains. Due to weak interactions between graphene and the underlying substrate, the rotational alignment of graphene relative to the underlying Ag (111) is not unique.<\/p>\n

After boron deposition, scanning tunneling microscopy (1E<\/b>) showed the presence of borophenic and graphene domains. Areas within graphene were also observed, later identified as graphene intercalated with boron (marked in the image Gr\/B<\/b>). This area also clearly shows linear elements oriented in three directions and separated by an angle of 120\u00b0 (yellow arrows).<\/p>\n

\"Two-Dimensional
\nImage #2<\/i><\/p>\n

The images at 2A<\/b>, as well as 1E<\/b>, confirm the appearance of localized dark depressions in graphene after boron deposition.<\/p>\n

To better examine these formations and understand their origin, another image of the same area was taken using the cart |dlnI<\/i>\/dz| (2\u0412), \u0433\u0434\u0435 I<\/i> \u2014 tunneling current, d<\/i> \u2014 density, and z<\/i> \u2014 the probe-sample separation (the gap between the microscope tip and the sample). Using this method allows for images with high spatial resolution. CO or H2 can also be applied to the microscope tip for this purpose. <\/p>\n

Image 2C<\/b> is an image obtained using STM, with the tip covered with CO. Comparing the images A<\/b>, In<\/b> and C<\/b> shows that all atomic elements are defined as three adjacent bright hexagons oriented in two nonequivalent directions (red and yellow triangles in the images). <\/p>\n

Enlarged images of this area (2D<\/b>) confirm that these elements align with boron's doping impurities, occupying two sublattices of graphene, as indicated by the overlapping structures.<\/p>\n

The CO coating on the microscope tip made it possible to reveal the geometric structure of the borophene sheet (2E<\/b>), which would not have been possible if the tip were standard (metallic) without a CO coating.<\/p>\n

\"Two-Dimensional
\nImage #3<\/i><\/p>\n

The formation of lateral heterointerfaces between borophenes and graphene (3A<\/b>) should occur when borophene grows next to graphene domains that already contain boron. <\/p>\n

Scientists remind us that lateral heterointerfaces based on graphene-hBN (graphene + boron nitride) have lattice coherence, while heterojunctions based on transition metal dichalcogenides exhibit symmetry coherence. In the case of graphene\/borophene, the situation is somewhat different\u2014they have minimal structural similarity in terms of lattice constants or crystalline symmetry. However, despite this, the lateral heterointerface of graphene\/borophene shows nearly perfect atomic coherence, with boron row (B-row) directions aligned with the zigzag (ZZ) directions of graphene (3A<\/b>). In 3B<\/b> an enlarged image of the ZZ region of the heterointerface is shown (interfacial elements corresponding to boron-carbon covalent bonds are marked by blue lines).<\/p>\n

Since borophene growth occurs at lower temperatures compared to graphene, the edges of the graphene domain are unlikely to have high mobility during the formation of the heterointerface with borophene. Consequently, the nearly atomically precise heterointerface is likely a result of different configurations and characteristics of boron multicenter bonds. Scanning tunneling spectroscopy (3C<\/b>) and differential tunneling conductivity (3D<\/b>) spectra show that electronic transfer from graphene to borophene occurs over a distance of ~ 5 \u00c5 without visible interface states.<\/p>\n

In the image 3E<\/b> Three scanning tunneling spectroscopy spectra are shown, taken along three dotted lines on the 3D, confirming that this short electronic transfer is insensitive to local interfacial structures and comparable to that at the borophene-silver boundaries. <\/p>\n

\"Two-Dimensional
\nImage No. 4<\/i><\/p>\n

Graphene intercalation*<\/i> has also been widely studied before; however, the transformation of intercalants into true 2D sheets is relatively rare.<\/p>\n

Intercalation*<\/b> is the reversible inclusion of a molecule or group of molecules between other molecules or groups of molecules.<\/p><\/blockquote>\n

The small atomic radius of boron and the weak interaction between graphene and Ag (111) suggest the possibility of boron intercalation with graphene. The image shows 4A<\/b> evidence not only of boron intercalation but also of the formation of vertical borophene-graphene heterostructures, particularly triangular domains surrounded by graphene. The honeycomb lattice observed on this triangular domain confirms the presence of graphene. However, this graphene exhibits a lower local density of states at -50 meV compared to the surrounding graphene (4B<\/b>). Compared to graphene directly on Ag (111), the absence of signs of high local density of states in the spectrum dI<\/i>\/dV<\/i> (4C<\/b>(blue curve), corresponding to the surface state of Ag (111), is the first evidence of boron intercalation.<\/p>\n

As expected for partial intercalation, the graphene lattice remains continuous across the lateral interface between the graphene and the triangular area (4D<\/b> \u2014 corresponds to the rectangular area on 4A<\/b>, marked with a red dotted line). A scan using the AFM tip also confirmed the presence of substitutive boron impurities (4E<\/b> \u2014 corresponds to the rectangular area on 4A<\/b>, marked with a yellow dotted line).<\/p>\n

During the analysis, uncoated AFM tips were also used. In this case, signs of one-dimensional linear elements with a periodicity of 5 \u00c5 were found in the intercalated graphene domains (4F<\/b> and 4G<\/b>). These one-dimensional structures resemble rows of boron in the borophene model. In addition to the set of points corresponding to graphene, the Fourier transform of the image at 4G<\/b> displays a pair of orthogonal points corresponding to a rectangular lattice of 3 \u00c5 x 5 \u00c5 (4N<\/b>), which aligns well with the borophene model. Additionally, the observed triple orientation of the lattice of linear elements (1E<\/b>) is consistent with the same predominant structure observed for borophene sheets.<\/p>\n

All these observations convincingly indicate boron intercalation with graphene near the edges of Ag, which subsequently leads to the formation of vertical borophene-graphene heterostructures that could be primarily realized by increasing the initial coverage of graphene.<\/p>\n

4I<\/b> is a schematic representation of a vertical heterostructure on 4H<\/b>, where the direction of the boron row (pink arrow) is closely aligned with the zigzag direction of graphene (black arrow), thus forming a rotationally proportionate vertical heterostructure.<\/p>\n

For a more detailed understanding of the nuances of the research, I recommend checking out the the scientists' report<\/a><\/noindex> and additional materials<\/a><\/noindex> related to it.<\/p>\n

Epilogue<\/h3>\n

\nThis research has shown that borophenes are quite capable of forming lateral and vertical heterostructures with graphene. Such systems could be utilized in the development of new types of two-dimensional elements used in nanotechnology, flexible and wearable electronics, as well as in new types of semiconductors.<\/p>\n

The researchers themselves believe that their development could be a significant leap forward for electronics-related technologies. However, it is currently difficult to say for sure whether their words will prove prophetic. There is still much to explore, understand, and invent before those science fiction ideas that fill the minds of scientists become a full-fledged reality.<\/p>\n

Thank you for your attention, stay curious, and have a great work week, everyone. \ud83d\ude42<\/p>\n

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\n
Source: habr.com<\/a><\/p>","protected":false,"gt_translate_keys":[{"key":"rendered","format":"html"}]},"excerpt":{"rendered":"

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