Raman Radiation Patterns of Graphene.

We report the angular distribution of the G and 2D Raman scattering from graphene on glass by detecting back focal plane patterns. The G Raman emission can be described by a superposition of two incoherent orthogonal point dipoles oriented in the graphene plane. Due to double resonant Raman scattering, the 2D emission can be represented by the sum of either three incoherent dipoles oriented 120° with respect to each other, or two orthogonal incoherent ones with a 3:1 weight ratio. Parameter-free calculations of the G and 2D intensities are in excellent agreement with the experimental radiation patterns. We show that the 2D polarization ratio and the 2D/G intensity ratio depend on the numerical aperture of the microscope objective. This is due to the depolarization of the emission and excitation light when graphene is on a dielectric substrate, as well as to tight focusing. The polarization contrast decreases substantially for increasing collection angle, due to polarization mixing caused by the air-dielectric interface. This also influences the intensity ratio I(2D)/I(G), a crucial quantity for estimating the doping in graphene. Our results are thus important for the quantitative analysis of the Raman intensities in confocal microscopy. In addition, they are relevant for understanding the influence of signal enhancing plasmonic antenna structures, which typically modify the sample's radiation pattern.

From Highly Crystalline to Outer Surface-Functionalized Covalent Organic Frameworks--A Modulation Approach.

Crystallinity and porosity are of central importance for many properties of covalent organic frameworks (COFs), including adsorption, diffusion, and electronic transport. We have developed a new method for strongly enhancing both aspects through the introduction of a modulating agent in the synthesis. This modulator competes with one of the building blocks during the solvothermal COF growth, resulting in highly crystalline frameworks with greatly increased domain sizes reaching several hundreds of nanometers. The obtained materials feature fully accessible pores with an internal surface area of over 2000 m(2) g(-1). Compositional analysis via NMR spectroscopy revealed that the COF-5 structure can form over a wide range of boronic acid-to-catechol ratios, thus producing frameworks with compositions ranging from highly boronic acid-deficient to networks with catechol voids. Visualization of an -SH-functionalized modulating agent via iridium staining revealed that the COF domains are terminated by the modulator. Using functionalized modulators, this synthetic approach thus also provides a new and facile method for the external surface functionalization of COF domains, providing accessible sites for post-synthetic modification reactions. We demonstrate the feasibility of this concept by covalently attaching fluorescent dyes and hydrophilic polymers to the COF surface. We anticipate that the realization of highly crystalline COFs with the option of additional surface functionality will render the modulation concept beneficial for a range of applications, including gas separations, catalysis, and optoelectronics.