The richness of optical and electronic properties of graphene attracts enormous interest. Graphene has high mobility and optical transparency, in addition to flexibility, robustness and environmental stability. So far, the main focus has been on fundamental physics and electronic devices. However, we believe its true potential lies in photonics and optoelectronics, where the combination of its unique optical and electronic properties can be fully exploited, even in the absence of a bandgap, and the linear dispersion of the Dirac electrons enables ultrawideband tunability. The rise of graphene in photonics and optoelectronics is shown by several recent results, ranging from solar cells and light-emitting devices to touch screens, photodetectors and ultrafast lasers. Here we review the state-of-the-art in this emerging field.

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Graphene photonics and optoelectronics

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.

Graphene-Based Materials: Synthesis, Characterization, Properties, and Applications

Atomic layer deposition(ALD), a chemical vapor deposition technique based on sequential self-terminating gas–solid reactions, has for about four decades been applied for manufacturing conformal inorganic material layers with thickness down to the nanometer range. Despite the numerous successful applications of material growth by ALD, many physicochemical processes that control ALD growth are not yet sufficiently understood. To increase understanding of ALD processes, overviews are needed not only of the existing ALD processes and their applications, but also of the knowledge of the surface chemistry of specific ALD processes. This work aims to start the overviews on specific ALD processes by reviewing the experimental information available on the surface chemistry of the trimethylaluminum/water process. This process is generally known as a rather ideal ALD process, and plenty of information is available on its surface chemistry. This in-depth summary of the surface chemistry of one representative ALD process aims also to provide a view on the current status of understanding the surface chemistry of ALD, in general. The review starts by describing the basic characteristics of ALD, discussing the history of ALD—including the question who made the first ALD experiments—and giving an overview of the two-reactant ALD processes investigated to date. Second, the basic concepts related to the surface chemistry of ALD are described from a generic viewpoint applicable to all ALD processes based on compound reactants. This description includes physicochemical requirements for self-terminating reactions,reaction kinetics, typical chemisorption mechanisms, factors causing saturation, reasons for growth of less than a monolayer per cycle, effect of the temperature and number of cycles on the growth per cycle (GPC), and the growth mode. A comparison is made of three models available for estimating the sterically allowed value of GPC in ALD. Third, the experimental information on the surface chemistry in the trimethylaluminum/water ALD process are reviewed using the concepts developed in the second part of this review. The results are reviewed critically, with an aim to combine the information obtained in different types of investigations, such as growth experiments on flat substrates and reaction chemistry investigation on high-surface-area materials. Although the surface chemistry of the trimethylaluminum/water ALD process is rather well understood, systematic investigations of the reaction kinetics and the growth mode on different substrates are still missing. The last part of the review is devoted to discussing issues which may hamper surface chemistry investigations of ALD, such as problematic historical assumptions, nonstandard terminology, and the effect of experimental conditions on the surface chemistry of ALD. I hope that this review can help the newcomer get acquainted with the exciting and challenging field of surface chemistry of ALD and can serve as a useful guide for the specialist towards the fifth decade of ALD research.

Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process

An object is to provide a semiconductor device of which a manufacturing process is not complicated and by which cost can be suppressed, by forming a thin film transistor using an oxide semiconductor film typified by zinc oxide, and a manufacturing method thereof. For the semiconductor device, a gate electrode is formed over a substrate; a gate insulating film is formed covering the gate electrode; an oxide semiconductor film is formed over the gate insulating film; and a first conductive film and a second conductive film are formed over the oxide semiconductor film. The oxide semiconductor film has at least a crystallized region in a channel region.

Semiconductor device, and manufacturing method thereof

The chemical and structural analysis of graphene oxide with different degrees of oxidation

Graphene is a one-atom-thick planar sheet of a honeycomb carbon crystal. Its gapless and linear energy spectra of electrons and holes lead to nontrivial features such as giant carrier mobility and broadband flat optical response. In this paper, recent advances in graphene-based devices in terahertz science and technology are reviewed. First, the fundamental basis of the optoelectronic properties of graphene is introduced. Second, synthesis and crystallographic characterization of graphene material are described, particularly focused on the authors' original heteroepitaxial graphene-on-silicon technology. Third, nonequilibrium carrier relaxation and recombination dynamics in optically or electrically pumped graphene are described to introduce a possibility of negative-dynamic conductivity in a wide terahertz range. Fourth, recent theoretical advances towards the creation of current-injection graphene terahertz lasers are described. Fifth, the unique terahertz dynamics of the two-dimensional plasmons in graphene are described. Finally, the advantages of graphene devices for terahertz applications are summarized.

https://iopscience.iop.org/article/10.1088/0022-3727/45/30/303001/pdf

Graphene-based devices in terahertz science and technology

By forming an ultrathin (~100?nm) SiC film on Si substrates and by annealing it at ~1500?K in vacuo, few-layer graphene is formed on Si substrates. Graphene grows on three major low-index surfaces: (1?1?1), (1?0?0) and (1?1?0), allowing us to tune its electronic properties by controlling the crystallographic orientation of the substrate. This graphene on silicon (GOS) technology thus paves the way to industrialization of this new material with inherent excellence. With its feasibility in Si technology, GOS is one of the most promising candidates as a material for Beyond CMOS technology.

https://iopscience.iop.org/article/10.1088/0022-3727/43/37/374012/pdf

Epitaxial graphene on silicon substrates

With its industrial adaptability, epitaxial graphene (EG), formed by a UHV annealing of SiC substrates, is attracting recent attention. While hexagonal SiC bulk substrates have been solely used for this purpose, benefits in use of 3C-SiC virtual substrate founded on Si substrates could be enormous. We have succeeded in fabricating a graphene film on a 3C-SiC(111) virtual substrate, which was preformed on a Si(110) substrate by gas-source molecular beam epitaxy using monomethyl silane. The geometrical matching in this configuration greatly suppresses the strain in the SiC film, which is related to this successful formation of graphene. [DOI: 10.1380/ejssnt.2009.311]

Graphene formation on a 3C-SiC(111) thin film grown on Si(110) substrate

The adsorption of CO2 molecules on monolayer epitaxial graphene on a SiC(0001) surface at 30 K was investigated by temperature-programmed desorption and X-ray photoelectron spectroscopy. The desorption energy of CO2 on graphene was determined to be (30.1–25.1) ± 1.5 kJ/mol at low coverages and approached the sublimation energy of dry ice (27–25 kJ/mol) with increasing the coverage. The adsorption of CO2 on graphene was thus categorized into physisorption, which was further supported by the binding energies of CO2 in core-level spectra. The adsorption states of CO2 on graphene were theoretically examined by means of the van der Waals density functional (vdW-DF) method that includes nonlocal correlation. The experimental desorption energy was successfully reproduced with high accuracy using vdW-DF calculations; the optB86b-vdW functional was found to be most appropriate to reproduce the desorption energy in the present system.

Adsorption of CO2 on Graphene: A Combined TPD, XPS, and vdW-DF Study

By conducting a 1200°C vacuum annealing of a 3C-SiC(111) ultrathin film preformed on a Si(110) surface, we have succeeded in forming a graphene layer on a Si substrate. Raman-scattering spectrum from this surface presents a distinct 2D band, whose deconvolution into four subcomponents indicates that the film mostly consists of a two-layer graphene. The peak position is blue-shifted from that of a free-standing graphene formed by a mechanical exfoliation method, suggesting a compressive stress in the film. [DOI: 10.1380/ejssnt.2009.107]

Maki Suemitsu

Papers

Graphene-based devices in terahertz science and technology

Epitaxial graphene on silicon substrates

Graphene formation on a 3C-SiC(111) thin film grown on Si(110) substrate

Adsorption of CO2 on Graphene: A Combined TPD, XPS, and vdW-DF Study

Raman-Scattering Spectroscopy of Epitaxial Graphene Formed on SiC Film on Si Substrate