A new family of single-atom-thick 2D germanium-based materials with graphene-like atomic arrangement, germanene and functionalized germanene, has attracted intensive attention due to their large bandgap and easily tailored electronic properties. Unlike carbon atoms in graphene, germanium atoms tend to adopt mixed sp2 /sp3 hybridization in germanene, which makes it chemically active on the surface and allows its electronic states to be easily tuned by chemical functionalization. Impressive achievements in terms of the applications in energy storage and catalysis have been reported by using germanene and functionalized germanene. Herein, the fabrication of epitaxial germanene on different metallic substrates and its unique electronic properties are summarized. Then, the preparation strategies and the fundamental properties of hydrogen-functionalized germanene (germanane or GeH) and other ligand-terminated forms of germanene are presented. Finally, the progress of their applications in energy storage and catalysis, including both experimental results and theoretical predictions, is analyzed.

/pdf/recent-progress-on-germanene-and-functionalized-germanene-45bzp1pc8m.pdf

Recent Progress on Germanene and Functionalized Germanene: Preparation, Characterizations, Applications, and Challenges

The sp3-hybridized group 14 graphane analogues are a unique family of 2D materials in which every atom requires a terminal ligand for stability. Consequently, the optical, electronic, and thermal properties of these materials can be manipulated via covalent chemistry. Herein, we review the methodologies for preparing these materials, and compare their functionalization densities to Si/Ge(111) surfaces and other covalently terminated 2D materials. We discuss how the electronic structure, optical properties, and thermal stability of the 2D framework can be broadly tuned with the ligand identity and framework element. We highlight their recent application in electronics, optoelectronics, photocatalysis, and batteries. Overall, these materials are an intriguing regime in materials design in which both surface functionalization and solid-state chemistry can be uniquely exploited to systematically design properties and phenomena.

Covalent functionalization of two-dimensional group 14 graphane analogues

Germanane is a two-dimensional, strongly confined form of germanium. It presents an interesting combination of (i) ease of integration with CMOS technology, (ii) low toxicity, and (iii) electronic confinement which transforms the indirect bandgap of the bulk material into a direct bandgap featuring photoluminescence. However, the optoelectronic properties of this material remain far less investigated than its structural properties. Here, we investigate the photoluminescence and transport properties of arrays of methyl-terminated germanane flakes. The photoluminescence appears to have two contributions, one from the band edge and the other from trap states. The dynamics of the exciton appear to be in the range of 1–100 ns. Conduction in this material appears to be p-type, while the photoconduction time response can be made as short as 100 μs.

https://hal.archives-ouvertes.fr/hal-02267953/document

Optoelectronic properties of methyl-terminated germanane

Arsenic has been predicted to present significantly more diverse 2D phases than other elemental compounds like graphene. While practical applications must be based on finite arsenene samples, like nanoribbons, theory has so far focused on the infinite sheet. Our ab initio simulations show the clear contrast between the properties of arsenene nanoribbons and those of the monolayer, ranging from phase stability to electronic structure. We include nanoribbons derived from the buckled, puckered and square/octagon structures of bulk arsenene. The flexibility afforded by different parent structures, widths and edge passivations leads to a rich variety of semiconducting structures with tunable gaps.

/pdf/tunable-gap-in-stable-arsenene-nanoribbons-opens-the-door-to-eh5dkj85qe.pdf

Tunable gap in stable arsenene nanoribbons opens the door to electronic applications

Germanane, a van der Waals layered material predicted to have a direct band gap and high carrier mobility, is a promising two-dimensional material with applications in optoelectronics. The electronic properties of germanane have been well studied; however, experimentally measured properties are orders of magnitude lower than predicted values, potentially limiting future device applications. The structure of germanane contains an inherent disorder along the c-axis, resulting in a diffuse halo with hexagonal symmetry in the electron diffraction pattern. The origin of this disorder is not well understood, further limiting the device application of germanane. Here, we have used experimental and simulated electron diffraction patterns to show that this diffuse scattering arises from turbostratic disorder present in the germanane structure with rotational disorder as the main contribution. The maximum rotation angle in the examined germanane crystal is limited to three degrees. For larger angles, germanane would become unstable as DFT calculations show. DFT calculations also indicate that small angle rotations cause a change in charge distribution in Ge and H atoms, and thus should affect the electronic properties of germanane considerably. This study explains for the first time the origin of the c-axis disorder in this van der Waals structure and establishes computationally analyzed diffraction patterns as a tool to quantify turbostratic disorder.

Identification of turbostratic twisting in germanane

Germanane (GeH), a hydrogen-terminated layered germanium structure, has recently been synthesized. Here, we employed a four-probe thermal transport measurement method to obtain the basal-plane thermal conductivity of thin exfoliated GeH flakes and correlated the measurement results with the crystal structure. The obtained thermal conductivity increases with increasing temperature, suggesting that extrinsic grain boundary and defect scattering dominate over intrinsic phonon-phonon scattering. Annealing a polycrystalline GeH sample at 195 °C caused it to become amorphous, reducing the room-temperature thermal conductivity from 0.53 ± 0.09 W m−1 K−1, which is close to the value calculated for 16 nm grain size, to 0.29 ± 0.05 W m−1 K−1, which approaches the calculated amorphous limit in the basal plane thermal conductivity.

Gabriella Coloyan

Papers

Basal-plane thermal conductivity of nanocrystalline and amorphized thin germanane