Maxx Q. Arguilla

Covalently-controlled properties by design in group IV graphane analogues.

CONSPECTUS: The isolation of graphene has sparked a renaissance in the study of two-dimensional materials. This led to the discovery of new and unique phenomena such as extremely high carrier mobility, thermal conductivity, and mechanical strength not observed in the parent 3D structure. While the emergence of these phenomena has spurred widespread interest in graphene, the paradox between the high-mobility Fermi-Dirac electronic structure and the need for a sizable band gap has challenged its application in traditional semiconductor devices. While graphene is a fascinating and promising material, the limitation of its electronic structure has inspired researchers to explore other 2D materials beyond graphene. In this Account, we summarize our recent work on a new family of two-dimensional materials based on sp(3)-hybridized group IV elements. Ligand-terminated Si, Ge, and Sn graphane analogues are an emerging and unique class of two-dimensional materials that offer the potential to tailor the structure, stability, and properties. Compared with bulk Si and Ge, a direct and larger band gap is apparent in group IV graphane analogues depending on the surface ligand. These materials can be synthesized in gram-scale quantities and in thin films via the topotactic deintercalation of layered Zintl phase precursors. Few layers and single layers can be isolated via manual exfoliation and deintercalation of epitaxially grown Zintl phases on Si/Ge substrates. The presence of a fourth bond on the surface of the layers allows various surface ligand termination with different organic functional groups achieved via conventional soft chemical routes. In these single-atom thick materials, the electronic structure can be systematically controlled by varying the identities of the main group elements and by attaching different surface terminating ligands. In contrast to transition metal dichalcogenides, the weaker interlayer interaction allows the direct band gap single layer properties such as photoluminescence to be readily observable without the need to exfoliate down to single layers. Furthermore, these materials can be resilient to oxidation and thermal degradation, making them attractive candidates for next generation functional materials for electronic devices and beyond. This class of two-dimensional materials not only are promising building blocks for a variety of conventional semiconductor applications but also provide a pioneering platform to systematically and rationally control material properties using covalent chemistry. The stability and tunability of these versatile materials will push this system toward the forefront of two-dimensional research.

NaSn2As2: An Exfoliatable Layered van der Waals Zintl Phase.

The discovery of new families of exfoliatable 2D crystals that have diverse sets of electronic, optical, and spin-orbit coupling properties enables the realization of unique physical phenomena in these few-atom-thick building blocks and in proximity to other materials. Herein, using NaSn2As2 as a model system, we demonstrate that layered Zintl phases having the stoichiometry ATt2Pn2 (A = group 1 or 2 element, Tt = group 14 tetrel element, and Pn = group 15 pnictogen element) and feature networks separated by van der Waals gaps can be readily exfoliated with both mechanical and liquid-phase methods. We identified the symmetries of the Raman-active modes of the bulk crystals via polarized Raman spectroscopy. The bulk and mechanically exfoliated NaSn2As2 samples are resistant toward oxidation, with only the top surface oxidizing in ambient conditions over a couple of days, while the liquid-exfoliated samples oxidize much more quickly in ambient conditions. Employing angle-resolved photoemission spectroscopy, density functional theory, and transport on bulk and exfoliated samples, we show that NaSn2As2 is a highly conducting 2D semimetal, with resistivities on the order of 10-6 Ω·m. Due to peculiarities in the band structure, the dominating p-type carriers at low temperature are nearly compensated by the opening of n-type conduction channels as temperature increases. This work further expands the family of exfoliatable 2D materials to layered van der Waals Zintl phases, opening up opportunities in electronics and spintronics.

Water activated doping and transport in multilayered germanane crystals.

The synthesis of germanane (GeH) has opened the door for covalently functionalizable 2D materials in electronics. Herein, we demonstrate that GeH can be electronically doped by incorporating stoichiometric equivalents of phosphorus dopant atoms into the CaGe2 precursor. The electronic properties of these doped materials show significant atmospheric sensitivity, and we observe a reduction in resistance by up to three orders of magnitude when doped samples are measured in water-containing atmospheres. This variation in resistance is a result of water activation of the phosphorus dopants. Transport measurements in different contact geometries show a significant anisotropy between in-plane and out-of-plane resistances, with a much larger out-of-plane resistance. These measurements along with finite element modeling results predict that the current distribution in top-contacted crystals is restricted to only the topmost, water activated crystal layers. Taken together, these results pave the way for future electronic and optoelectronic applications utilizing group IV graphane analogues.

EuSn2As2: an exfoliatable magnetic layered Zintl–Klemm phase

Despite the immense interest in magnetic, topological, and magnetoelectronic phenomena in isolated layers of 2D materials and their vertically stacked heterostructures, there remains a dearth of 2D magnetic materials that can be readily exfoliated into single layers. Here, we synthesize EuSn2As2, the first exfoliatable, layered magnetic Zintl–Klemm phase that features van der Waals bonding between neighboring layers. In these crystals, Eu2+ 4f7 spins magnetically order at 24 K and are coupled ferromagnetically within each layer and antiferromagnetically, with some potential canting, across adjacent layers. Magnetic ground state DFT calculations and temperature-dependent transport measurements on single crystals together establish that EuSn2As2 is semimetallic. Finally, we show that this material can be thinned down to a few layers having steps corresponding to SnAsEuAsSn layers via micromechanical exfoliation. This work opens up further explorations into the design, synthesis, and layer-dependent magnetic properties of exfoliatable, lanthanide-based magnetic van der Waals Zintl phases.

Optical properties and Raman-active phonon modes of two-dimensional honeycomb Zintl phases

Intermetallic Zintl phases whose structures consist of honeycomb layers of main group elements often serve as useful precursors for two-dimensional group 14 graphane derivatives. Here, we probe how the Raman spectra and band gaps evolve in these precursor intermetallic phases before they transform into their van der Waals counterparts. Through polarization-dependent Raman experiments on seven different group 14 and 15 Zintl phases with different stacking motifs, we show that the in-plane and out-of-plane Raman frequencies mostly depend on the reduced mass and the in-plane bond lengths of the elements constituting the honeycomb framework. From optical absorption measurements, we show that the honeycomb framework comprised of single elements is metallic, but when the framework is comprised of alternating elements in a BN-like fashion, such as in NaSnP, KSnAs and KSnSb, a band gap is opened up ranging from 0.54 eV for KSnSb to 0.95 eV for NaSnP. This study allows for the determination of the structure and stacking motifs for this emerging class of 2D layered metallic and semiconducting materials.

Group-13 and group-15 doping of germanane

Germanane, a hydrogen-terminated graphane analogue of germanium has generated interest as a potential 2D electronic material. However, the incorporation and retention of extrinsic dopant atoms in the lattice, to tune the electronic properties, remains a significant challenge. Here, we show that the group-13 element Ga and the group-15 element As, can be successfully doped into a precursor CaGe2 phase, and remain intact in the lattice after the topotactic deintercalation, using HCl, to form GeH. After deintercalation, a maximum of 1.1% As and 2.3% Ga can be substituted into the germanium lattice. Electronic transport properties of single flakes show that incorporation of dopants leads to a reduction of resistance of more than three orders of magnitude in H2O-containing atmosphere after As doping. After doping with Ga, the reduction is more than six orders of magnitude, but with significant hysteretic behavior, indicative of water-activation of dopants on the surface. Only Ga-doped germanane remains activated under vacuum, and also exhibits minimal hysteretic behavior while the sheet resistance is reduced by more than four orders of magnitude. These Ga- and As-doped germanane materials start to oxidize after one to four days in ambient atmosphere. Overall, this work demonstrates that extrinsic doping with Ga is a viable pathway towards accessing stable electronic behavior in graphane analogues of germanium.