Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...

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Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

Graphene-Like Two-Dimensional Materials

A new phototransistor based on the mechanically exfoliated single-layer MoS2 nanosheet is fabricated, and its light-induced electric properties are investigated in detail. Photocurrent generated from the phototransistor is solely determined by the illuminated optical power at a constant drain or gate voltage. The switching behavior of photocurrent generation and annihilation can be completely finished within ca. 50 ms, and it shows good stability. Especially, the single-layer MoS2 phototransistor exhibits a better photoresponsivity as compared with the graphene-based device. The unique characteristics of incident-light control, prompt photoswitching, and good photoresponsivity from the MoS2 phototransistor pave an avenue to develop the single-layer semiconducting materials for multifunctional optoelectronic device applications in the future.

Single-Layer MoS2 Phototransistors

By using ab initio calculations, we predict that a vertical electric field is able to open a band gap in semimetallic single-layer buckled silicene and germanene. The sizes of the band gap in both silicene and germanene increase linearly with the electric field strength. Ab initio quantum transport simulation of a dual-gated silicene field effect transistor confirms that the vertical electric field opens a transport gap, and a significant switching effect by an applied gate voltage is also observed. Therefore, biased single-layer silicene and germanene can work effectively at room temperature as field effect transistors.

Tunable Bandgap in Silicene and Germanene

Recent development in 2D materials beyond graphene

Silicon nanomaterials are encouraging candidates for application to photonic, electronic, or biosensing devices, due to their size-quantization effects. Two-dimensional silicon nanosheets could help to realize a widespread quantum field, because of their nanoscale thickness and microscale area. However, there has been no example of a successful synthesis of two-dimensional silicon nanomaterials with large lateral size and oxygen-free surfaces. Here we report that oxygen-free silicon nanosheets covered with organic groups can be obtained by exfoliation of layered polysilane as a result of reaction with n-decylamine and dissolution in an organic solvent. The amine residues are covalently bound to the Si(111) planes. It is estimated that there is ca. 0.7 mol of residue per mole of Si atoms in the reaction product. The amine-modified layered polysilane can dissolve in chloroform and exfoliate into nanosheets that are 1-2 microm wide in the lateral direction and with thicknesses on the order of nanometers. The nanosheets have very flat and smooth surfaces due to dense coverage of n-decylamine, and they are easily self-assembled in a concentrated state to form a regularly stacked structure. The nanosheets could be useful as building blocks to create various composite materials.

Silicon nanosheets and their self-assembled regular stacking structure.

Silicon nanomaterials and nanostructures exhibit different properties from those of bulk silicon materials based on quantum confinement effects. They are expected to lead to the development of new applications of silicon, in addition to wide use in semiconductor devices. Aside from industrial interest, intriguing issues of academic interest still remain with respect to the origins of their characteristic properties. Zero- and one-dimensional crystalline silicon nanomaterials have been synthesized, to date, by using many methods and there has been rapid progress in size control and modification procedures. However, there have been only a few examples of silicon nanomaterials with atomic-order thickness akin to carbon nanomaterials, such as two-dimensional silicon nanosheets. Moreover, mass production of silicon nanomaterials with relatively low cost is not easily achievable, due to the typically severe conditions required for fabrication, such as high temperature and ultralow pressure. Recently, we have developed a soft synthetic method for silicon nanosheets with chemical surface modification in a solution process. This review provides methods for the synthesis and modification of silicon nanosheets and other silicon nanomaterials with examples of their potential applications.

Synthesis and modification of silicon nanosheets and other silicon nanomaterials.

The synthesis of silicon nanosheets for fabricating electronic devices, without using conventional vacuum processes and vapor deposition, is challenging and is anticipated to receive significant attention for a wide range of applications. Here, we report the synthesis of oxygen-free, phenyl-modified organosilicon nanosheets with atomic thickness. In organic solvents, a consequence of this new silicon structure is its uniform dispersion and the possibility of exfoliation into unilamellar nanosheets. Light-induced photocurrent in [Si6H4Ph2] was observed, leading to the possibility of various organosilicon nonamaterials with useful properties.

Synthesis and Optical Properties of Monolayer Organosilicon Nanosheets

Alkyl-modified crystalline silicon nanosheets 2 were synthesized and maintained the crystal structure of a Si(111) plane, in which the dangling silicon bond is stabilized by capping with the alkyl group. 2 was characterized using UV-vis, Fourier transform-infrared, and X-ray photoelectron spectroscopies; X-ray diffraction; and X-ray absorption near edge structure analysis. A model structure is proposed that has a periodicity through the nanosheet surface.

Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane (Si6H6).

We have characterized the electron transport properties of n-decylamine-functionalized Si nanosheets (NSs) using atomic force microscopy with a conductive cantilever under vacuum conditions at room temperature. Electrons are transported from the cantilever to the substrate through Si NSs. The Si NSs exhibit nonresonant tunneling; the transport mechanisms are based on direct tunneling at low bias voltages and Fowler–Nordheim tunneling at high bias voltages.

Sugiyama Yusuke

Papers

Silicon nanosheets and their self-assembled regular stacking structure.

Synthesis and modification of silicon nanosheets and other silicon nanomaterials.

Synthesis and Optical Properties of Monolayer Organosilicon Nanosheets

Preparation of alkyl-modified silicon nanosheets by hydrosilylation of layered polysilane (Si6H6).

Electron transport properties of Si nanosheets: Transition from direct tunneling to Fowler-Nordheim tunneling