Single-layer metal dichalcogenides are two-dimensional semiconductors that present strong potential for electronic and sensing applications complementary to that of graphene.

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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

Fabrication techniques developed for graphene research allow the disassembly of many layered crystals (so-called van der Waals materials) into individual atomic planes and their reassembly into designer heterostructures, which reveal new properties and phenomena. Andre Geim and Irina Grigorieva offer a forward-looking review of the potential of layering two-dimensional materials into novel heterostructures held together by weak van der Waals interactions. Dozens of these one-atom- or one-molecule-thick crystals are known. Graphene has already been well studied but others, such as monolayers of hexagonal boron nitride, MoS2, WSe2, graphane, fluorographene, mica and silicene are attracting increasing interest. There are many other monolayers yet to be examined of course, and the possibility of combining graphene with other crystals adds even further options, offering exciting new opportunities for scientific exploration and technological innovation. Research on graphene and other two-dimensional atomic crystals is intense and is likely to remain one of the leading topics in condensed matter physics and materials science for many years. Looking beyond this field, isolated atomic planes can also be reassembled into designer heterostructures made layer by layer in a precisely chosen sequence. The first, already remarkably complex, such heterostructures (often referred to as ‘van der Waals’) have recently been fabricated and investigated, revealing unusual properties and new phenomena. Here we review this emerging research area and identify possible future directions. With steady improvement in fabrication techniques and using graphene’s springboard, van der Waals heterostructures should develop into a large field of their own.

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Van der Waals heterostructures

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Excitonic solar cells1—including organic, hybrid organic–inorganic and dye-sensitized cells (DSCs)—are promising devices for inexpensive, large-scale solar energy conversion. The DSC is currently the most efficient2 and stable3 excitonic photocell. Central to this device is a thick nanoparticle film that provides a large surface area for the adsorption of light-harvesting molecules. However, nanoparticle DSCs rely on trap-limited diffusion for electron transport, a slow mechanism that can limit device efficiency, especially at longer wavelengths. Here we introduce a version of the dye-sensitized cell in which the traditional nanoparticle film is replaced by a dense array of oriented, crystalline ZnO nanowires. The nanowire anode is synthesized by mild aqueous chemistry and features a surface area up to one-fifth as large as a nanoparticle cell. The direct electrical pathways provided by the nanowires ensure the rapid collection of carriers generated throughout the device, and a full Sun efficiency of 1.5% is demonstrated, limited primarily by the surface area of the nanowire array.

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Nanowire dye-sensitized solar cells

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

Probing Peptide Amphiphile Self-Assembly in Blood Serum

The recent discovery that specific materials can simultaneously exhibit n-type conduction and p-type conduction along different directions of the single crystal has the potential to impact a broad ...

The Chemical Design Principles for Axis-Dependent Conduction Polarity.

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.

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Group-13 and group-15 doping of germanane.

There has been an expanding library of materials in which the framework connectivity of prevalent solid-state crystal structure types is terminated with ligands along specific axes to produce robust, crystalline, single- and few-atom/polyhedral thick fragments. The abrupt termination of the ionic/covalent inorganic framework along a particular direction, gives these materials fundamentally different electronic, optical, thermal, and magnetic properties, which can be manipulated via the design of the organic component. These new materials often exhibit advantageous electronic and optoelectronic behavior, making them viable platforms for applications ranging from light emitting phosphors, to thin film field effect transistors, to photovoltaics. This Perspective highlights our current understanding and future opportunities in the synthesis, properties, and applications of these atomic-scale derivatives of solid-state materials.

Joshua E. Goldberger

Papers

Probing Peptide Amphiphile Self-Assembly in Blood Serum

The Chemical Design Principles for Axis-Dependent Conduction Polarity.

Group-13 and group-15 doping of germanane.

Atomic-Scale Derivatives of Solid-State Materials

All-optical switching of magnetization in atomically thin CrI3