Graphene has attracted tremendous research interest in recent years, owing to its exceptional properties. The scaled-up and reliable production of graphene derivatives, such as graphene oxide (GO) and reduced graphene oxide (rGO), offers a wide range of possibilities to synthesize graphene-based functional materials for various applications. This critical review presents and discusses the current development of graphene-based composites. After introduction of the synthesis methods for graphene and its derivatives as well as their properties, we focus on the description of various methods to synthesize graphene-based composites, especially those with functional polymers and inorganic nanostructures. Particular emphasis is placed on strategies for the optimization of composite properties. Lastly, the advantages of graphene-based composites in applications such as the Li-ion batteries, supercapacitors, fuel cells, photovoltaic devices, photocatalysis, as well as Raman enhancement are described (279 references).

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Graphene-based composites

The transition from an indirect to direct bandgap in transition metal dichalcogenides has been observed in samples with thicknesses ranging from 8 to 1 monolayers by angle-resolved photoemission spectroscopy.

/pdf/direct-observation-of-the-transition-from-indirect-to-direct-4uqe38juj2.pdf

Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe2

The discovery of graphene and other two-dimensional (2D) materials together with recent advances in exfoliation techniques have set the foundations for the manufacturing of single layered sheets from any layered 3D material. The family of 2D materials encompasses a wide selection of compositions including almost all the elements of the periodic table. This derives into a rich variety of electronic properties including metals, semimetals, insulators and semiconductors with direct and indirect band gaps ranging from ultraviolet to infrared throughout the visible range. Thus, they have the potential to play a fundamental role in the future of nanoelectronics, optoelectronics and the assembly of novel ultrathin and flexible devices. We categorize the 2D materials according to their structure, composition and electronic properties. In this review we distinguish atomically thin materials (graphene, silicene, germanene, and their saturated forms; hexagonal boron nitride; silicon carbide), rare earth, semimetals, transition metal chalcogenides and halides, and finally synthetic organic 2D materials, exemplified by 2D covalent organic frameworks. Our exhaustive data collection presented in this Atlas demonstrates the large diversity of electronic properties, including band gaps and electron mobilities. The key points of modern computational approaches applied to 2D materials are presented with special emphasis to cover their range of application, peculiarities and pitfalls.

https://www.rsc.org/suppdata/cs/c4/c4cs00102h/c4cs00102h1.pdf

An atlas of two-dimensional materials

We report on a strong photoluminescence (PL) enhancement of monolayer MoS2 through defect engineering and oxygen bonding. Micro-PL and Raman images clearly reveal that the PL enhancement occurs at cracks/defects formed during high-temperature annealing. The PL enhancement at crack/defect sites could be as high as thousands of times after considering the laser spot size. The main reasons of such huge PL enhancement include the following: (1) the oxygen chemical adsorption induced heavy p doping and the conversion from trion to exciton; (2) the suppression of nonradiative recombination of excitons at defect sites, which was verified by low-temperature PL measurements. First-principle calculations reveal a strong binding energy of ∼2.395 eV for an oxygen molecule adsorbed on a S vacancy of MoS2. The chemically adsorbed oxygen also provides a much more effective charge transfer (0.997 electrons per O2) compared to physically adsorbed oxygen on an ideal MoS2 surface. We also demonstrate that the defect enginee...

Strong Photoluminescence Enhancement of MoS2 through Defect Engineering and Oxygen Bonding

Different C–N bonding configurations in nitrogen (N) doped carbon materials have different electronic structures. Carbon materials doped with only one kind of C–N bonding configuration are an excellent platform for studying doping effects on the electronic structure and physical/chemical properties. Here we report synthesis of single layer graphene doped with pure pyridinic N by thermal chemical vapour deposition of hydrogen and ethylene on Cu foils in the presence of ammonia. By adjusting the flow rate of ammonia, the atomic ratio of N and C can be modulated from 0 to 16%. The domain like distribution of N incorporated in graphene was revealed by the imaging of Raman spectroscopy and time-of-flight secondary ion mass spectrometry. The ultraviolet photoemission spectroscopy investigation demonstrated that the pyridinic N efficiently changed the valence band structure of graphene, including the raising of density of π states near the Fermi level and the reduction of work function. Such pyridinic N doping in carbon materials was generally considered to be responsible for their oxygen reduction reaction (ORR) activity. The 2e reduction mechanism of ORR on our CNxgraphene revealed by rotating disk electrode voltammetry indicated that the pyridinic N may not be an effective promoter for ORR activity of carbon materials as previously expected.

https://www3.ntu.edu.sg/home/yuting/papers/Pyridinic%20N%20doped%20graphene.pdf

Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property

Nanoscale gaps in metal films enable strong field enhancements in plasmonic structures. However, the reliable fabrication of ultrasmall gaps (<10 nm) for real applications is still challenging. In this work, we report a method to directly and reliably fabricate sub-10-nm gaps in plasmonic structures without restrictions on pattern design. This method is based on a lift-off process using high-resolution electron-beam lithography with a negative-tone hydrogen silsesquioxane (HSQ) resist, where the resulting nanogap size is determined by the width of the patterned HSQ structure, which could be written at less than 10 nm. With this method, we fabricated densely packed gold nanostructures of varying geometries separated by ultrasmall gaps. By controlling structure sizes during lithography with nanometer precision, the plasmon resonances of the resulting patterns could be accurately tuned. Optical and surface-enhanced Raman scattering (SERS) measurements on the patterned structures show that this technique has ...

Direct and Reliable Patterning of Plasmonic Nanostructures with Sub-10-nm Gaps

Ordered array of Au semishells on TiO2 spheres with controlled size are prepared by combining the nanosphere self-assembly and atomic layer deposition (ALD). This ordered 2-D structure with designed array of metal nanogaps can be used as an ultrasensitive surface-enhanced Raman scattering (SERS) substrate with high reproducibility and stability. More importantly, the SERS substrates are recyclable, as enabled by their self-cleaning function due to the TiO2 photocatalytic degradation of the target molecules. The high SERS sensitivity and recyclability are demonstrated by the detection of Rhodamine 6G (R6G) and brilliant cresyl blue (BCB) molecules. As both the nanosphere lithography and ALD are scalable processes, such 2-D ordered substrates may find applications in chemical sensing.

Ordered Array of Gold Semishells on TiO2 Spheres: An Ultrasensitive and Recyclable SERS Substrate

In this work, we performed a systematic study on the photoluminescence and scattering spectra of individual gold nanostructures that were lithographically defined. We identify the role of plasmons in photoluminescence as modulating the energy transfer between excited electrons and emitted photons. By comparing photoluminescence spectra with scattering spectra, we observed that the photoluminescence of individual gold nanostructures showed the same dependencies on shape, size, and plasmon coupling as the particle plasmon resonances. Our results provide conclusive evidence that the photoluminescence in gold nanostructures indeed occurs via radiative damping of plasmon resonances driven by excited electrons in the metal itself. Moreover, we provide new insight on the underlying mechanism based on our analysis of a reproducible blue shift of the photoluminescence peak (relative to the scattering peak) and observation of an incomplete depolarization of the photoluminescence.

Plasmon-modulated photoluminescence of individual gold nanostructures.

Although new spintronic devices based on the giant spin-orbit splitting of single-layer MoS2 have been proposed, such splitting has not been studied effectively in experiments. This Letter reports the valence band spin-orbit splitting in single-layer MoS2 for the first time, probed by the triply resonant Raman scattering process. We found that upon 325 nm laser irradiation, the second order overtone and combination Raman modes of single-layer MoS2 are dramatically enhanced. Such resonant Raman enhancement arises from the electron-two-phonon triple resonance via the deformation potential and Frohlich interaction. As a sensitive and precise probe for the spin-orbit splitting, the triply resonant Raman scattering will provide a new and independent route to study the spin characteristics of MoS2.

Spin-Orbit Splitting in Single-Layer MoS2 Revealed by Triply Resonant Raman Scattering

Though the SERS effect based on pristine MoS2 is hardly observed, however, the plasma treated MoS2 nanoflakes can be used as an ideal substrate for surface enhanced Raman scattering. It is proved that the structural disorder induced generation of local dipoles and adsorption of oxygen on the plasma treated MoS2 nanosheets are the two basic and important driven forces for the enhancement of Raman signals of surface adsorbed R6G molecules.

Hailong Hu

Papers

Direct and Reliable Patterning of Plasmonic Nanostructures with Sub-10-nm Gaps

Ordered Array of Gold Semishells on TiO2 Spheres: An Ultrasensitive and Recyclable SERS Substrate

Plasmon-modulated photoluminescence of individual gold nanostructures.

Spin-Orbit Splitting in Single-Layer MoS2 Revealed by Triply Resonant Raman Scattering

Plasma modified MoS2 nanoflakes for surface enhanced Raman scattering