Andrew Davies

Irreversible network transformation in a dynamic porous host catalyzed by sulfur dioxide.

Porous NOTT-202a shows exceptionally high uptake of SO2, 13.6 mmol g(-1) (87.0 wt %) at 268 K and 1.0 bar, representing the highest value reported to date for a framework material. NOTT-202a undergoes a distinct irreversible framework phase transition upon SO2 uptake at 268-283 K to give NOTT-202b which has enhanced stability due to the formation of strong π···π interactions between interpenetrated networks.

Strain-Engineered Graphene Grown on Hexagonal Boron Nitride by Molecular Beam Epitaxy

Graphene grown by high temperature molecular beam epitaxy on hexagonal boron nitride (hBN) forms continuous domains with dimensions of order 20 μm, and exhibits moiré patterns with large periodicities, up to ~30 nm, indicating that the layers are highly strained. Topological defects in the moiré patterns are observed and attributed to the relaxation of graphene islands which nucleate at different sites and subsequently coalesce. In addition, cracks are formed leading to strain relaxation, highly anisotropic strain fields, and abrupt boundaries between regions with different moiré periods. These cracks can also be formed by modification of the layers with a local probe resulting in the contraction and physical displacement of graphene layers. The Raman spectra of regions with a large moiré period reveal split and shifted G and 2D peaks confirming the presence of strain. Our work demonstrates a new approach to the growth of epitaxial graphene and a means of generating and modifying strain in graphene.

Hexagonal Boron Nitride Tunnel Barriers Grown on Graphite by High Temperature Molecular Beam Epitaxy

We demonstrate direct epitaxial growth of high-quality hexagonal boron nitride (hBN) layers on graphite using high-temperature plasma-assisted molecular beam epitaxy. Atomic force microscopy reveals mono- and few-layer island growth, while conducting atomic force microscopy shows that the grown hBN has a resistance which increases exponentially with the number of layers, and has electrical properties comparable to exfoliated hBN. X-ray photoelectron spectroscopy, Raman microscopy and spectroscopic ellipsometry measurements on hBN confirm the formation of sp2-bonded hBN and a band gap of 5.9 ± 0.1 eV with no chemical intermixing with graphite. We also observe hexagonal moiré patterns with a period of 15 nm, consistent with the alignment of the hBN lattice and the graphite substrate.We demonstrate direct epitaxial growth of high-quality hexagonal boron nitride (hBN) layers on graphite using high-temperature plasma-assisted molecular beam epitaxy. Atomic force microscopy reveals mono- and few-layer island growth, while conducting atomic force microscopy shows that the grown hBN has a resistance which increases exponentially with the number of layers, and has electrical properties comparable to exfoliated hBN. X-ray photoelectron spectroscopy, Raman microscopy and spectroscopic ellipsometry measurements on hBN confirm the formation of sp2-bonded hBN and a band gap of 5.9 ± 0.1 eV with no chemical intermixing with graphite. We also observe hexagonal moiré patterns with a period of 15 nm, consistent with the alignment of the hBN lattice and the graphite substrate.

High temperature MBE of graphene on sapphire and hexagonal boron nitride flakes on sapphire

The discovery of graphene and its remarkable electronic properties has provided scientists with a revolutionary material system for electronics and optoelectronics. Here, the authors investigate molecular beam epitaxy (MBE) as a growth method for graphene layers. The standard dual chamber GENxplor has been specially modified by Veeco to achieve growth temperatures of up to 1850 °C in ultrahigh vacuum conditions and is capable of growth on substrates of up to 3 in. in diameter. To calibrate the growth temperatures, the authors have formed graphene on the Si-face of SiC by heating wafers to temperatures up to 1400 °C and above. To demonstrate the scalability, the authors have formed graphene on SiC substrates with sizes ranging from 10 × 10 mm2 up to 3-in. in diameter. The authors have used a carbon sublimation source to grow graphene on sapphire at substrate temperatures between 1000 and 1650 °C (thermocouple temperatures). The quality of the graphene layers is significantly improved by growing on hexagona...

Reversible adsorption of nitrogen dioxide within a robust porous metal–organic framework

Nitrogen dioxide (NO2) is a major air pollutant causing significant environmental1,2 and health problems3,4. We report reversible adsorption of NO2 in a robust metal–organic framework. Under ambient conditions, MFM-300(Al) exhibits a reversible NO2 isotherm uptake of 14.1 mmol g−1, and, more importantly, exceptional selective removal of low-concentration NO2 (5,000 to <1 ppm) from gas mixtures. Complementary experiments reveal five types of supramolecular interaction that cooperatively bind both NO2 and N2O4 molecules within MFM-300(Al). We find that the in situ equilibrium 2NO2 ↔ N2O4 within the pores is pressure-independent, whereas ex situ this equilibrium is an exemplary pressure-dependent first-order process. The coexistence of helical monomer–dimer chains of NO2 in MFM-300(Al) could provide a foundation for the fundamental understanding of the chemical properties of guest molecules within porous hosts. This work may pave the way for the development of future capture and conversion technologies.High and reversible nitrogen dioxide (NO2) uptake, and low-concentration NO2 removal from gas mixtures, is observed in a metal–organic framework. The NO2 is bound within the pores by cooperative supramolecular interactions.

An atomic carbon source for high temperature molecular beam epitaxy of graphene

We report the use of a novel atomic carbon source for the molecular beam epitaxy (MBE) of graphene layers on hBN flakes and on sapphire wafers at substrate growth temperatures of ~1400 °C. The source produces a flux of predominantly atomic carbon, which diffuses through the walls of a Joule-heated tantalum tube filled with graphite powder. We demonstrate deposition of carbon on sapphire with carbon deposition rates up to 12 nm/h. Atomic force microscopy measurements reveal the formation of hexagonal moiré patterns when graphene monolayers are grown on hBN flakes. The Raman spectra of the graphene layers grown on hBN and sapphire with the sublimation carbon source and the atomic carbon source are similar, whilst the nature of the carbon aggregates is different - graphitic with the sublimation carbon source and amorphous with the atomic carbon source. At MBE growth temperatures we observe etching of the sapphire wafer surface by the flux from the atomic carbon source, which we have not observed in the MBE growth of graphene with the sublimation carbon source.

High-temperature molecular beam epitaxy of hexagonal boron nitride layers

The growth and properties of hexagonal boron nitride (hBN) have recently attracted much attention due to applications in graphene-based monolayer thick two dimensional (2D)-structures and at the same time as a wide band gap material for deep-ultraviolet device (DUV) applications. The authors present their results in the high-temperature plasma-assisted molecular beam epitaxy (PA-MBE) of hBN monolayers on highly oriented pyrolytic graphite substrates. Their results demonstrate that PA-MBE growth at temperatures ∼1390 °C can achieve mono- and few-layer thick hBN with a control of the hBN coverage and atomically flat hBN surfaces which is essential for 2D applications of hBN layers. The hBN monolayer coverage can be reproducible controlled by the PA-MBE growth temperature, time and B:N flux ratios. Significantly thicker hBN layers have been achieved at higher B:N flux ratios. The authors observed a gradual increase of the hBN thickness from 40 to 70 nm by decreasing the growth temperature from 1390 to 1080 °C. However, by decreasing the MBE growth temperature below 1250 °C, the authors observe a rapid degradation of the optical properties of hBN layers. Therefore, high-temperature PA-MBE, above 1250 °C, is a viable approach for the growth of high-quality hBN layers for 2D and DUV applications.The growth and properties of hexagonal boron nitride (hBN) have recently attracted much attention due to applications in graphene-based monolayer thick two dimensional (2D)-structures and at the same time as a wide band gap material for deep-ultraviolet device (DUV) applications. The authors present their results in the high-temperature plasma-assisted molecular beam epitaxy (PA-MBE) of hBN monolayers on highly oriented pyrolytic graphite substrates. Their results demonstrate that PA-MBE growth at temperatures ∼1390 °C can achieve mono- and few-layer thick hBN with a control of the hBN coverage and atomically flat hBN surfaces which is essential for 2D applications of hBN layers. The hBN monolayer coverage can be reproducible controlled by the PA-MBE growth temperature, time and B:N flux ratios. Significantly thicker hBN layers have been achieved at higher B:N flux ratios. The authors observed a gradual increase of the hBN thickness from 40 to 70 nm by decreasing the growth temperature from 1390 to 1080 °...

Lattice-Matched Epitaxial Graphene Grown on Boron Nitride

Lattice-matched graphene on hexagonal boron nitride is expected to lead to the formation of a band gap but requires the formation of highly strained material and has not hitherto been realized. We demonstrate that aligned, lattice-matched graphene can be grown by molecular beam epitaxy using substrate temperatures in the range 1600-1710 °C and coexists with a topologically modified moiré pattern with regions of strained graphene which have giant moiré periods up to ∼80 nm. Raman spectra reveal narrow red-shifted peaks due to isotropic strain, while the giant moiré patterns result in complex splitting of Raman peaks due to strain variations across the moiré unit cell. The lattice-matched graphene has a lower conductance than both the Frenkel-Kontorova-type domain walls and also the topological defects where they terminate. We relate these results to theoretical models of band gap formation in graphene/boron nitride heterostructures.

Moiré-modulated conductance of hexagonal boron nitride tunnel barriers

Monolayer hexagonal boron nitride (hBN) tunnel barriers investigated using conductive atomic force microscopy reveal moiré patterns in the spatial maps of their tunnel conductance consistent with the formation of a moiré superlattice between the hBN and an underlying highly ordered pyrolytic graphite (HOPG) substrate. This variation is attributed to a periodc modulation of the local density of states and occurs for both exfoliated hBN barriers and epitaxially grown layers. The epitaxial barriers also exhibit enhanced conductance at localized subnanometer regions which are attributed to exposure of the substrate to a nitrogen plasma source during the high temperature growth process. Our results show clearly a spatial periodicity of tunnel current due to the formation of a moiré superlattice and we argue that this can provide a mechanism for elastic scattering of charge carriers for similar interfaces embedded in graphene/hBN resonant tunnel diodes.

Corrigendum: Hexagonal Boron Nitride Tunnel Barriers Grown on Graphite by High Temperature Molecular Beam Epitaxy

Scientific Reports 6: Article number: 34474; published online: 29 September 2016; updated: 08 May 2017. As the authors of references 25 and 26 also employed plasma-assisted molecular beam epitaxy for the synthesis of hexagonal boron nitride films, the authors would like to make the following changesto the Introduction section of their Article: