Single-layer Materials

In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials derived from single elements generally carry the -ene suffix in their names, e.g. graphene. Single-layer materials that are compounds of two or more elements have -ane or -ide suffixes. 2D materials can generally be categorized as either 2D allotropes of various elements or as compounds (consisting of two or more covalently bonding elements).

It is predicted that there are hundreds of stable single-layer materials. The atomic structure and calculated basic properties of these and many other potentially synthesisable single-layer materials, can be found in computational databases. 2D materials can be produced using mainly two approaches: top-down exfoliation and bottom-up synthesis. The exfoliation methods include sonication, mechanical, hydrothermal, electrochemical, laser-assisted, and microwave-assisted exfoliation.

Single element materials

C: graphene and graphyne

;Graphene

Graphene is a crystalline allotrope of carbon in the form of a nearly transparent (to visible light) one atom thick sheet. It is hundreds of times stronger than most steels by weight. It has the highest known thermal and electrical conductivity, displaying current densities 1,000,000 times that of copper. It was first produced in 2004.

Andre Geim and Konstantin Novoselov won the 2010 Nobel Prize in Physics "for groundbreaking experiments regarding the two-dimensional material graphene". They first produced it by lifting graphene flakes from bulk graphite with adhesive tape and then transferring them onto a silicon wafer.

;Graphyne
Graphyne is another 2-dimensional carbon allotrope whose structure is similar to graphene's. It can be seen as a lattice of benzene rings connected by acetylene bonds. Depending on the content of the acetylene groups, graphyne can be considered a mixed hybridization, spⁿ, where 1 < n < 2, compared to graphene (pure sp²) and diamond (pure sp³).

First-principle calculations using phonon dispersion curves and ab-initio finite temperature, quantum mechanical molecular dynamics simulations showed graphyne and its boron nitride analogues to be stable.

The existence of graphyne was conjectured before 1960. It has not yet been synthesized. However, graphdiyne (graphyne with diacetylene groups) was synthesized on copper substrates. Recently, it has been claimed to be a competitor for graphene due to the potential of direction-dependent Dirac cones.

B: borophene

Borophene is a crystalline atomic monolayer of boron and is also known as ''boron sheet''.
First predicted by theory in the mid-1990s in a freestanding state, and then demonstrated as distinct monoatomic layers on substrates by Zhang et al.,
different borophene structures were experimentally confirmed in 2015.

Ge: germanene

Germanene is a two-dimensional allotrope of germanium with a buckled honeycomb structure.
Experimentally synthesized germanene exhibits a honeycomb structure.
This honeycomb structure consists of two hexagonal sub-lattices that are vertically displaced by 0.2 A from each other.

Si: silicene

Silicene is a two-dimensional allotrope of silicon, with a hexagonal honeycomb structure similar to that of graphene. Its growth is scaffolded by a pervasive Si/Ag(111) surface alloy beneath the two-dimensional layer.

Sn: stanene

Stanene is a predicted topological insulator that may display dissipationless currents at its edges near room temperature. It is composed of tin atoms arranged in a single layer, in a manner similar to graphene. Its buckled structure leads to high reactivity against common air pollutants such as NO_x and CO_x and it is able to trap and dissociate them at low temperature.
A structure determination of stanene using low energy electron diffraction has shown ultra-flat stanene on a Cu(111) surface.

Pb: plumbene

Plumbene is a two-dimensional allotrope of lead, with a hexagonal honeycomb structure similar to that of graphene.

P: phosphorene

Phosphorene is a 2-dimensional, crystalline allotrope of phosphorus. Its mono-atomic hexagonal structure makes it conceptually similar to graphene. However, phosphorene has substantially different electronic properties; in particular it possesses a nonzero band gap while displaying high electron mobility. This property potentially makes it a better semiconductor than graphene.
The synthesis of phosphorene mainly consists of micromechanical cleavage or liquid phase exfoliation methods. The former has a low yield while the latter produce free standing nanosheets in solvent and not on the solid support. The bottom-up approaches like chemical vapor deposition (CVD) are still blank because of its high reactivity. Therefore, in the current scenario, the most effective method for large area fabrication of thin films of phosphorene consists of wet assembly techniques like Langmuir-Blodgett involving the assembly followed by deposition of nanosheets on solid supports.

Sb: antimonene

Antimonene is a two-dimensional allotrope of antimony, with its atoms arranged in a buckled honeycomb lattice. Theoretical calculations predicted that antimonene would be a stable semiconductor in ambient conditions with suitable performance for (opto)electronics. Antimonene was first isolated in 2016 by micromechanical exfoliation and it was found to be very stable under ambient conditions. Its properties make it also a good candidate for biomedical and energy applications.

In a study made in 2018, antimonene modified screen-printed electrodes (SPE's) were subjected to a galvanostatic charge/discharge test using a two-electrode approach to characterize their supercapacitive properties. The best configuration observed, which contained 36 nanograms of antimonene in the SPE, showed a specific capacitance of 1578 F g⁻¹ at a current of 14 A g⁻¹. Over 10,000 of these galvanostatic cycles, the capacitance retention values drop to 65% initially after the first 800 cycles, but then remain between 65% and 63% for the remaining 9,200 cycles. The 36 ng antimonene/SPE system also showed an energy density of 20 mW h kg⁻¹ and a power density of 4.8 kW kg⁻¹. These supercapacitive properties indicate that antimonene is a promising electrode material for supercapacitor systems. A more recent study, concerning antimonene modified SPEs shows the inherent ability of antimonene layers to form electrochemically passivated layers to facilite electroanalytical measurements in oxygenated environments, in which the presence of dissolved oxygens normally hinders the analytical procedure. The same study also depicts the in-situ production of antimonene oxide/PEDOT:PSS nanocomposites as electrocatalytic platforms for the determination of nitroaromatic compounds.

Bi: bismuthene

Bismuthene, the two-dimensional (2D) allotrope of bismuth, was predicted to be a topological insulator. It was predicted that bismuthene retains its topological phase when grown on silicon carbide in 2015. The prediction was successfully realized and synthesized in 2016. At first glance the system is similar to graphene, as the Bi atoms arrange in a honeycomb lattice. However the bandgap is as large as 800mV due to the large spin–orbit interaction (coupling) of the Bi atoms and their interaction with the substrate. Thus, room-temperature applications of the quantum spin Hall effect come into reach. It has been reported to be the largest nontrivial bandgap 2D topological insulator in its natural state. Top-down exfoliation of bismuthene has been reported in various instances with recent works promoting the implementation of bismuthene in the field of electrochemical sensing. Emdadul et al. predicted the mechanical strength and phonon thermal conductivity of monolayer β-bismuthene through atomic-scale analysis. The obtained room temperature (300K) fracture strength is ~4.21 N/m along the armchair direction and ~4.22 N/m along the zigzag direction. At 300 K, its Young's moduli are reported to be ~26.1 N/m and ~25.5 N/m, respectively, along the armchair and zigzag directions. In addition, their predicted phonon thermal conductivity of ~1.3 W/m∙K at 300 K is considerably lower than other analogous 2D honeycombs, making it a promising material for thermoelectric operations.

Metals

Single and double atom layers of platinum in a two-dimensional film geometry has been demonstrated. These atomically thin platinum films are epitaxially grown on graphene which imposes a compressive strain that modifies the surface chemistry of the platinum, while also allowing charge transfer through the graphene. Single atom layers of palladium with the thickness down to 2.6 Å, and rhodium with the thickness of less than 4 Å have also been synthesized and characterized with atomic force microscopy and transmission electron microscopy.

2D alloys

Two-dimensional alloys (or surface alloys) are a single atomic layer of alloy that is incommensurate with the underlying substrate. One example is the 2D ordered alloys of Pb with Sn and with Bi. Surface alloys have been found to scaffold two-dimensional layers, as in the case of silicene.

2D supracrystals

The supracrystals of 2D materials have been proposed and theoretically simulated. These monolayer crystals are built of supra atomic periodic structures where atoms in the nodes of the lattice are replaced by symmetric complexes. For example, in the hexagonal structure of graphene patterns of 4 or 6 carbon atoms would be arranged hexagonally instead of single atoms, as the repeating node in the unit cell.

Compounds

*Boron nitride nanosheet

* Titanate nanosheet
* Borocarbonitrides
*MXenes
* 2D silica
* Niobium bromide and Niobium chloride