BACKGROUND Materials by design is an appealing idea that is very hard to realize in practice. Combining the best of different ingredients in one ultimate material is a task for which we currently have no general solution. However, we do have some successful examples to draw upon: Composite materials and III-V heterostructures have revolutionized many aspects of our lives. Still, we need a general strategy to solve the problem of mixing and matching crystals with different properties, creating combinations with predetermined attributes and functionalities. ADVANCES Two-dimensional (2D) materials offer a platform that allows creation of heterostructures with a variety of properties. One-atom-thick crystals now comprise a large family of these materials, collectively covering a very broad range of properties. The first material to be included was graphene, a zero-overlap semimetal. The family of 2D crystals has grown to includes metals (e.g., NbSe 2 ), semiconductors (e.g., MoS 2 ), and insulators [e.g., hexagonal boron nitride (hBN)]. Many of these materials are stable at ambient conditions, and we have come up with strategies for handling those that are not. Surprisingly, the properties of such 2D materials are often very different from those of their 3D counterparts. Furthermore, even the study of familiar phenomena (like superconductivity or ferromagnetism) in the 2D case, where there is no long-range order, raises many thought-provoking questions. A plethora of opportunities appear when we start to combine several 2D crystals in one vertical stack. Held together by van der Waals forces (the same forces that hold layered materials together), such heterostructures allow a far greater number of combinations than any traditional growth method. As the family of 2D crystals is expanding day by day, so too is the complexity of the heterostructures that could be created with atomic precision. When stacking different crystals together, the synergetic effects become very important. In the first-order approximation, charge redistribution might occur between the neighboring (and even more distant) crystals in the stack. Neighboring crystals can also induce structural changes in each other. Furthermore, such changes can be controlled by adjusting the relative orientation between the individual elements. Such heterostructures have already led to the observation of numerous exciting physical phenomena. Thus, spectrum reconstruction in graphene interacting with hBN allowed several groups to study the Hofstadter butterfly effect and topological currents in such a system. The possibility of positioning crystals in very close (but controlled) proximity to one another allows for the study of tunneling and drag effects. The use of semiconducting monolayers leads to the creation of optically active heterostructures. The extended range of functionalities of such heterostructures yields a range of possible applications. Now the highest-mobility graphene transistors are achieved by encapsulating graphene with hBN. Photovoltaic and light-emitting devices have been demonstrated by combining optically active semiconducting layers and graphene as transparent electrodes. OUTLOOK Currently, most 2D heterostructures are composed by direct stacking of individual monolayer flakes of different materials. Although this method allows ultimate flexibility, it is slow and cumbersome. Thus, techniques involving transfer of large-area crystals grown by chemical vapor deposition (CVD), direct growth of heterostructures by CVD or physical epitaxy, or one-step growth in solution are being developed. Currently, we are at the same level as we were with graphene 10 years ago: plenty of interesting science and unclear prospects for mass production. Given the fast progress of graphene technology over the past few years, we can expect similar advances in the production of the heterostructures, making the science and applications more achievable.

2D materials and van der Waals heterostructures

Research Development on Sodium-Ion Batteries

Since the discovery of superconductivity above 30 K by Bednorz and M\"uller in the La copper oxide system, the critical temperature has been raised to 90 K in Y${\mathrm{Ba}}_{2}$${\mathrm{Cu}}_{3}$${\mathrm{O}}_{7}$ and to 110 and 125 K in Bi-based and Tl-based copper oxides, respectively. In the two years since this Nobel-prize-winning discovery, a large number of electronic structure calculations have been carried out as a first step in understanding the electronic properties of these materials. In this paper these calculations (mostly of the density-functional type) are gathered and reviewed, and their results are compared with the relevant experimental data. The picture that emerges is one in which the important electronic states are dominated by the copper $d$ and oxygen $p$ orbitals, with strong hybridization between them. Photon, electron, and positron spectroscopies provide important information about the electronic states, and comparison with electronic structure calculations indicates that, while many features can be interpreted in terms of existing calculations, self-energy corrections ("correlations") are important for a more detailed understanding. The antiferromagnetism that occurs in some regions of the phase diagram poses a particularly challenging problem for any detailed theory. The study of structural stability, lattice dynamics, and electron-phonon coupling in the copper oxides is also discussed. Finally, a brief review is given of the attempts so far to identify interaction constants appropriate for a model Hamiltonian treatment of many-body interactions in these materials.

Electronic structure of the high-temperature oxide superconductors

The rapidly expanding field of nonaqueous multivalent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present analysis covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. On the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a...

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges

This review article focuses on the sol-gel preparation of high temperature superconducting oxides wherein different classes of gel technologies were utilized. These involve: 1) the sol-gel route based upon hydrolysis-condensation of metal-alkoxides, 2) the gelation route based upon concentration of aqueous solutions involving metal-chelates, often called as “chelate gel” or “amorphous chelate” route, and 3) the organic polymeric gel route. This paper reviews the current status of these sol-gel processes, and illustrates the underlying chemistry involved in each sol-gel technology. It is demonstrated that the chemical homogeneity of the gel is often disturbed by the differences in the chemistries of the cations. Prior to gelation the starting precursor solution containing various forms of metal-complexes must be chemically modified to overcome this problem. Illustration of a variety of strategies for success in obtaining a homogeneous multicomponent gel with no precipitation is focal point of this review article.

Invited review “sol-gel” preparation of high temperature superconducting oxides

Single crystal sof the 84-K superconductor ${\mathrm{Bi}}_{2.2}{\mathrm{Sr}}_{2}{\mathrm{Ca}}_{0.8}{\mathrm{Cu}}_{2}{\mathrm{O}}_{8+\ensuremath{\delta}}$ were characterized by x-ray diffraction, dc magnetic susceptibility, electrical resistivity, and microwave absorption. The structure has ${[\mathrm{Cu}{\mathrm{O}}_{2}]}_{\ensuremath{\infty}}$ planes separated by calcium atoms, edge-shared bismuth oxide double layers, and an incommensurate superlattice along $b$ with a period of 4.76. The in-plane resistivity above ${T}_{c}$ is linear in $T$, with ${\ensuremath{\rho}}_{\mathrm{RT}}=130$ \ensuremath{\mu}\ensuremath{\Omega} cm. Initial results on Pb substitution yielding ${T}_{c}'\mathrm{s}$ of 107 K are reported.

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

A new family of high-temperature superconductors is described, with the general formula Pb2Sr2ACu3O8+δ. Although they have the planes of CuO5 square pyramids characteristic of the other copper-oxide superconductors, the new compounds belong to a distinct structural series, with wide scope for elemental substitution. Their unusual electronic configuration also gives new insight into the role of charge distribution among the structural building blocks in controlling superconductivity.

Superconductivity near 70 K in a new family of layered copper oxides

SUPERCONDUCTING K3C60 (ref. 1) has been shown2 to have an intercalated face-centred cubic (f.c.c.) structure, and other A3C60 compounds (where A is K, Rb or mixtures of K, Rb and/or Cs) form an isostructural series with superconducting transition temperatures up to 31.3 K (ref. 3). Recently we reported413C NMR studies of KxC60 for x<3, and concluded that the system contained two phases (x = 0 and x = 3) for 0<x<3. Here we report an investigation of AxC60 in the range 3<x<6 and find evidence for an additional phase at x = 4. In contrast to f.c.c. A3C60 (refs 2, 3) and body-centred cubic A6C60 (ref. 5), A4C60 (where A is K, Rb, Cs) has a body-centred tetragonal structure. We show that all of the experimentally observed phases of AxC60 can be predicted solely on the basis of electrostatic considerations. We have found no evidence for superconductivity in A4C60.

Preparation and structure of the alkali-metal fulleride A4C60

THE well-known 90-K superconductor Y2Ba2Cu3O7 ('123') is the first (n = 0) member of a homologous series of compounds with the general formula Y2Ba4Cu6+nO14+n. These compounds combine layers of copper–oxygen pyramids with single and/or double copper–oxygen chains. The n =2 member, Y2Ba2Cu7O8 ('124'), with double Cu–O chains, and the n = 1 ytterbium analogue, Yb2Ba4Cu7O15 ('247'), which mixes single and double chains, were first observed as intergrowths in bulk 123 by electron microscopy1,11. The 124 phase was then synthesized as a majority phase in thin films2,3,12, and its crystal structure was determined4 and found to be in agreement with the model proposed from microscopy. An important advance in the synthesis of bulk materials, the result of extensive pressure–temperature phase equilibria studies, was the isolation of 124 and 247 at oxygen pressures of >200 atm, and detailed determinations of their crystal structures (see, for example, refs 5–9). High-pressure studies have also shown that the 124 phase could be made with many rare-earth elements13. Here we report the synthesis of the 124 phase in pure bulk form by a novel synthetic route in a flowing oxygen stream at 1 atm pressure. This technique allows YBa2Cu4O8 to be synthesized without specialized equipment, will make it generally available for study of its normal and superconducting properties, and will make possible more extensive comparisons with YBa2Cu3O7 and other high-Tc superconductors. Our results suggest that 124 is the thermodynamically stable phase at low temperatures and 1 atm pressure, under oxidizing conditions; the usual inability to synthesize it in these conditions is probably due to the limitations of reaction kinetics.

Synthesis of bulk superconducting YBa2Cu4O8 at one atmosphere oxygen pressure

Crystals of C60 or C70 cocrystallized with n-pentane grow as elongated, ten-sided columns. X-ray diffraction shows ordering of C60 or C70 molecules along the column and a remarkable tenfold symmetry normal to the column. The ratio of the x-ray-diffraction vectors of the two lowest-order diffraction spots is nearly equal to the “golden ratio,” τ. Despite these similarities with decagonal, quasicrystalline order, the diffraction indicates crystalline order with a twinned unit cell.

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P. Marsh

Papers

Structure and physical properties of single crystals of the 84-K superconductor Bi 2.2 Sr 2 Ca 0.8 Cu 2 O 8+δ

Superconductivity near 70 K in a new family of layered copper oxides

Preparation and structure of the alkali-metal fulleride A4C60

Synthesis of bulk superconducting YBa2Cu4O8 at one atmosphere oxygen pressure

Pseudotenfold symmetry in pentane-solvated C60 and C70