We report free-standing atomic crystals that are strictly 2D and can be viewed as individual atomic planes pulled out of bulk crystals or as unrolled single-wall nanotubes. By using micromechanical cleavage, we have prepared and studied a variety of 2D crystals including single layers of boron nitride, graphite, several dichalcogenides, and complex oxides. These atomically thin sheets (essentially gigantic 2D molecules unprotected from the immediate environment) are stable under ambient conditions, exhibit high crystal quality, and are continuous on a macroscopic scale.

/pdf/two-dimensional-atomic-crystals-57l57mf7h5.pdf

Two-dimensional atomic crystals

Dimensionality plays a critical role in determining the properties of materials due to, for example, the different ways that electrons interact in three-dimensional, twodimensional (2D), and one-dimensional (1D) structures.1-5 The study of dimensionality has a long history in chemistry and physics, although this has been primarily with the prefix “quasi” added to the description of materials; that is, quasi-1D solids, including square-planar platinum chain and metal trichalcogenide compounds,2,6 and quasi2D layered solids, such as metal dichalcogenides and copper oxide superconductors.3-5,7,8 The anisotropy inherent in quasi-1D and -2D systems is central to the unique properties and phases that these materials exhibit, although the small but finite interactions between 1D chains or 2D layers in bulk materials have made it difficult to address the interesting properties expected for the pure low-dimensional systems. Are pure low-dimensional systems interesting and worth pursuing? We believe that the answer to this question is an unqualified yes from the standpoints of both fundamental science and technology. One needs to look no further than past studies of the 2D electron gas in semiconductor heterostructures, which have produced remarkably rich and often unexpected results,9,10 and electron tunneling through 0D quantum dots, which have led to the concepts of the artificial atom and the creation of single electron transistors.11-15 In these cases, lowdimensional systems were realized by creating discrete 2D and 0D nanostructures. 1D nanostructures, such as nanowires and nanotubes, are expected to be at least as interesting and important as 2D and 0D systems.16,17 1D systems are the smallest dimension structures that can be used for efficient transport of electrons and optical excitations, and are thus expected to be critical to the function and integration of nanoscale devices. However, little is known about the nature of, for example, localization that could preclude transport through 1D systems. In addition, 1D systems should exhibit density of states singularities, can have energetically discrete molecularlike states extending over large linear distances, and may show more exotic phenomena, such as the spin-charge separation predicted for a Luttinger liquid.1,2 There are also many applications where 1D nanostructures could be exploited, including nanoelectronics, superstrong and tough composites, functional nanostructured materials, and novel probe microscopy tips.16-29 To address these fascinating fundamental scientific issues and potential applications requires answers to two questions at the heart of condensed matter chemistry and physics research: (1) How can atoms or other building blocks be rationally assembled into structures with nanometer-sized diameters but much longer lengths? (2) What are the intrinsic properties of these quantum wires and how do these properties depend, for example, on diameter and structure? Below we describe investigations from our laboratory directed toward these two general questions. The organization of this Account is as follows. In section II, we discuss the development of a general approach to the rational synthesis of crystalline nanowires of arbitrary composition. In section III, we outline key challenges to probing the intrinsic properties of 1D systems and illustrate solutions to these challenges with measurements of the atomic structure and electronic properties of carbon nanotubes. Last, we discuss future directions and challenges in section IV.

http://cmliris.harvard.edu/assets/AccChemRes_32_435.pdf

Chemistry and Physics in One Dimension: Synthesis and Properties of Nanowires and Nanotubes

The successful synthesis of pure boron nitride (BN) nanotubes is reported here. Multi-walled tubes with inner diameters on the order of 1 to 3 nanometers and with lengths up to 200 nanometers were produced in a carbon-free plasma discharge between a BN-packed tungsten rod and a cooled copper electrode. Electron energy-loss spectroscopy on individual tubes yielded B:N ratios of approximately 1, which is consistent with theoretical predictions of stable BN tube structures.

https://science.sciencemag.org/content/sci/269/5226/966.full.pdf

Boron Nitride Nanotubes

Preface Acknowledgements Notation Part I. Overview and Background Topics: 1. Introduction 2. Overview 3. Theoretical background 4. Periodic solids and electron bands 5. Uniform electron gas and simple metals Part II. Density Functional Theory: 6. Density functional theory: foundations 7. The Kohn-Sham ansatz 8. Functionals for exchange and correlation 9. Solving the Kohn-Sham equations Part III. Important Preliminaries on Atoms: 10. Electronic structure of atoms 11. Pseudopotentials Part IV. Determination of Electronic Structure, The Three Basic Methods: 12. Plane waves and grids: basics 13. Plane waves and grids: full calculations 14. Localized orbitals: tight binding 15. Localized orbitals: full calculations 16. Augmented functions: APW, KKR, MTO 17. Augmented functions: linear methods Part V. Predicting Properties of Matter from Electronic Structure - Recent Developments: 18. Quantum molecular dynamics (QMD) 19. Response functions: photons, magnons ... 20. Excitation spectra and optical properties 21. Wannier functions 22. Polarization, localization and Berry's phases 23. Locality and linear scaling O (N) methods 24. Where to find more Appendixes References Index.

Electronic Structure: Basic Theory and Practical Methods

Hexagonal boron nitride (h-BN), a layered material similar to graphite, is a promising dielectric. Monolayer h-BN, so-called "white graphene", has been isolated from bulk BN and could be useful as a complementary two-dimensional dielectric substrate for graphene electronics. Here we report the large area synthesis of h-BN films consisting of two to five atomic layers, using chemical vapor deposition. These atomic films show a large optical energy band gap of 5.5 eV and are highly transparent over a broad wavelength range. The mechanical properties of the h-BN films, measured by nanoindentation, show 2D elastic modulus in the range of 200-500 N/m, which is corroborated by corresponding theoretical calculations.

Large Scale Growth and Characterization of Atomic Hexagonal Boron Nitride Layers

We report the successful synthesis of B{sub {ital x}}C{sub {ital y}}N{sub {ital z}} nanotubes. Arc-discharge methods were used to produce stable nanotubule structures identified by high-resolution transmission-electron microscopy. Local electron-energy-loss spectroscopy of {ital K}-edge absorptions for B, C, and N atoms was used to determine the atomic compositions of individual tubules. Tubes of stoichiometry BC{sub 2}N and BC{sub 3} have been observed, in agreement with theoretical predictions.

Synthesis of B x C y N z nanotubules

The sharp resistive transitions in superconducting single crystals of natural abundance and 99% ${}^{13}\mathrm{C}$-enriched ${\mathrm{Rb}}_{3}{\mathrm{C}}_{60}$ reveal the carbon isotope effect with unprecedented accuracy. The measured isotope exponent ${\ensuremath{\alpha}}_{\mathrm{C}}\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0.21\ifmmode\pm\else\textpm\fi{}0.012$ is outside the error bars of all previous reported values. Our precise value for ${\ensuremath{\alpha}}_{\mathrm{C}}$, combined with ${T}_{c}$, ${\ensuremath{\alpha}}_{\mathrm{Rb}}$, and an ab initio calculation of the frequency distribution of the electron-phonon coupling, allows a fully constrained determination of the coupling strength $\ensuremath{\lambda}{\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0.9}_{\ensuremath{-}0.1}^{+0.15}$ and the Coulomb repulsion ${\ensuremath{\mu}}^{*}{\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0.22}_{\ensuremath{-}0.02}^{+0.03}$. These new measurements reveal a phonon-mediated superconductor with moderate coupling to a wide range of phonons centered near $\ensuremath{\sim}1400\mathrm{K}$.

http://research.physics.berkeley.edu/zettl/pdf/227.PRL.83-Fuhrer.pdf

K. Cherrey

Papers

Boron Nitride Nanotubes

Synthesis of B x C y N z nanotubules

Carbon isotope effect in single-crystal rb3c60