Research

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14 pages, 2070 KiB

Open AccessFeature PaperArticle

Electronic Structure of Nitrogen- and Phosphorus-Doped Graphenes Grown by Chemical Vapor Deposition Method

by L. G. Bulusheva, V. E. Arkhipov, K. M. Popov, V. I. Sysoev, A. A. Makarova and A. V. Okotrub

Materials 2020, 13(5), 1173; https://doi.org/10.3390/ma13051173 - 06 Mar 2020

Cited by 22 | Viewed by 3503

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, [...] Read more.

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, respectively. The electronic structure of the films transferred onto SiO₂/Si wafers by wet etching of copper substrates is studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy using a synchrotron radiation source. Annealing in an ultra-high vacuum at ca. 773 K allows for the removal of impurities formed on the surface of films during the synthesis and transfer procedure and changes the chemical state of nitrogen in nitrogen-doped graphene. Core level XPS spectra detect a low n-type doping of graphene film when nitrogen or phosphorous atoms are incorporated in the lattice. The electrical sheet resistance increases in the order: graphene < P-graphene < N-graphene. This tendency is related to the density of defects evaluated from the ratio of intensities of Raman peaks, valence band XPS and NEXAFS spectroscopy data. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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18 pages, 3841 KiB

Open AccessArticle

Understanding Graphene Response to Neutral and Charged Lead Species: Theory and Experiment

by Ivan Shtepliuk, Maria Francesca Santangelo, Mikhail Vagin, Ivan G. Ivanov, Volodymyr Khranovskyy, Tihomir Iakimov, Jens Eriksson and Rositsa Yakimova

Materials 2018, 11(10), 2059; https://doi.org/10.3390/ma11102059 - 22 Oct 2018

Cited by 12 | Viewed by 3565

Abstract

Deep understanding of binding of toxic Lead (Pb) species on the surface of two-dimensional materials is a required prerequisite for the development of next-generation sensors that can provide fast and real-time detection of critically low concentrations. Here we report atomistic insights into the [...] Read more.

Deep understanding of binding of toxic Lead (Pb) species on the surface of two-dimensional materials is a required prerequisite for the development of next-generation sensors that can provide fast and real-time detection of critically low concentrations. Here we report atomistic insights into the Lead behavior on epitaxial graphene (Gr) on silicon carbide substrates by thorough complementary study of voltammetry, electrical characterization, Raman spectroscopy, and Density Functional Theory (DFT). It is verified that the epitaxial graphene exhibits quasi-reversible anode reactions in aqueous solutions, providing a well-defined redox peak for Pb species and good linearity over a concentration range from 1 nM to 1 µM. The conductometric approach offers another way to investigate Lead adsorption, which is based on the formations of stable charge-transfer complexes affecting the p-type conductivity of epitaxial graphene. Our results suggest the adsorption ability of the epitaxial graphene towards divalent Lead ions is concentration-dependent and tends to saturate at higher concentrations. To elucidate the mechanisms responsible for Pb adsorption, we performed DFT calculations and estimated the solvent-mediated interaction between Lead species in different oxidative forms and graphene. Our results provide central information regarding the energetics and structure of Pb-graphene interacting complexes that underlay the adsorption mechanisms of neutral and divalent Lead species. Such a holistic understanding favors design and synthesis of new sensitive materials for water quality monitoring. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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10 pages, 1380 KiB

Open AccessArticle

Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties

by Wei-Hao Huang, Cheng-Hsuan Lin, Ben-Son Lin and Chia-Liang Sun

Materials 2018, 11(10), 1989; https://doi.org/10.3390/ma11101989 - 15 Oct 2018

Cited by 16 | Viewed by 4652

Abstract

Chemical vapor deposition (CVD) graphene is reported to effectively prevent the penetration of outer factors and insulate the underneath metals, hence achieving an anticorrosion purpose. However, there is little knowledge about their characteristics and corresponding corrosion properties, especially for those prepared under different [...] Read more.

Chemical vapor deposition (CVD) graphene is reported to effectively prevent the penetration of outer factors and insulate the underneath metals, hence achieving an anticorrosion purpose. However, there is little knowledge about their characteristics and corresponding corrosion properties, especially for those prepared under different parameters at low temperatures. Using electron cyclotron resonance chemical vapor deposition (ECR-CVD), we can successfully prepare graphene nanostructures on copper (Cu) at temperatures lower than 600 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and potentiodynamic polarization measurements were used to characterize these samples. In simulated seawater, i.e., 3.5 wt.% sodium chloride (NaCl) solution, the corrosion current density of one graphene-coated Cu fabricated at 400 °C can be 1.16 × 10⁻⁵ A/cm², which is one order of magnitude lower than that of pure Cu. Moreover, the existence of tall graphene nanowalls was found not to be beneficial to the protection as a consequence of their layered orientation. These correlations among the morphology, structure, and corrosion properties of graphene nanostructures were investigated in this study. Therefore, the enhanced corrosion resistance in selected cases suggests that the low-temperature CVD graphene under appropriate conditions would be able to protect metal substrates against corrosion. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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9 pages, 1827 KiB

Open AccessArticle

Fluorescence Studies of the Interplay between Metal-Enhanced Fluorescence and Graphene-Induced Quenching

by Kamil Wiwatowski, Paweł Podlas, Magdalena Twardowska and Sebastian Maćkowski

Materials 2018, 11(10), 1916; https://doi.org/10.3390/ma11101916 - 09 Oct 2018

Cited by 4 | Viewed by 2500

Abstract

Fluorescence microscopy and spectroscopy were applied for studying the optical properties of a hybrid nanostructure, in which we combine plasmon-induced metal enhanced fluorescence with energy transfer to epitaxial graphene. Covering the layer of silver islands with a monolayer graphene, while turning on the [...] Read more.

Fluorescence microscopy and spectroscopy were applied for studying the optical properties of a hybrid nanostructure, in which we combine plasmon-induced metal enhanced fluorescence with energy transfer to epitaxial graphene. Covering the layer of silver islands with a monolayer graphene, while turning on the efficient energy transfer from emitters, only moderately affects the enhancement of fluorescence attributed to the plasmon resonance in metallic nanostructures—as evidenced by the analysis of fluorescence decays. The results show that it is feasible to combine the properties of graphene with metal-enhanced fluorescence. The importance of the layer thickness of the emitters is also pointed out. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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11 pages, 1819 KiB

Open AccessArticle

Energy Transfer from Photosystem I to Thermally Reduced Graphene Oxide

by Karolina Sulowska, Kamil Wiwatowski, Piotr Szustakiewicz, Justyna Grzelak, Wiktor Lewandowski and Sebastian Mackowski

Materials 2018, 11(9), 1567; https://doi.org/10.3390/ma11091567 - 30 Aug 2018

Cited by 4 | Viewed by 3485

Abstract

The energy transfer from photosynthetic complex photosystem I to thermally reduced graphene oxide was studied using fluorescence microscopy and spectroscopy, and compared against the structure in which monolayer epitaxial graphene was used as the energy acceptor. We find that the properties of reduced [...] Read more.

The energy transfer from photosynthetic complex photosystem I to thermally reduced graphene oxide was studied using fluorescence microscopy and spectroscopy, and compared against the structure in which monolayer epitaxial graphene was used as the energy acceptor. We find that the properties of reduced graphene oxide (rGO) as an energy acceptor is qualitatively similar to that of epitaxial graphene. Fluorescence quenching, which in addition to shortening of fluorescence decay, is a signature of energy transfer varies across rGO substrates and correlates with the transmission pattern. We conclude that the efficiency of the energy transfer depends on the number of rGO layers in the flakes and decreases with this number. Furthermore, careful analysis of fluorescence imaging data confirms that the energy transfer efficiency dependence on the excitation wavelength, also varies with the number of rGO flakes. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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14 pages, 4910 KiB

Open AccessArticle

Interband Absorption in Few-Layer Graphene Quantum Dots: Effect of Heavy Metals

by Ivan Shtepliuk and Rositsa Yakimova

Materials 2018, 11(7), 1217; https://doi.org/10.3390/ma11071217 - 16 Jul 2018

Cited by 13 | Viewed by 3844

Abstract

Monolayer, bilayer, and trilayer graphene quantum dots (GQDs) with different binding abilities to elemental heavy metals (HMs: Cd, Hg, and Pb) were designed, and their electronic and optical properties were investigated theoretically to understand deeply the optical response under heavy metal exposure. To [...] Read more.

Monolayer, bilayer, and trilayer graphene quantum dots (GQDs) with different binding abilities to elemental heavy metals (HMs: Cd, Hg, and Pb) were designed, and their electronic and optical properties were investigated theoretically to understand deeply the optical response under heavy metal exposure. To gain insight into the nature of interband absorption, we performed density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations for thickness-varying GQDs. We found that the interband absorption in GQDs can be efficiently tuned by controlling the thickness of GQDs to attain the desirable coloration of the interacting complex. We also show that the strength of the interaction between GQDs and Cd, Hg, and Pb is strongly dependent on the number of sp²-bonded layers. The results suggest that the thickness of GQDs plays an important role in governing the hybridization between locally-excited (LE) and charge-transfer (CT) states of the GQDs. Based on the partial density-of-states (DOS) analysis and in-depth knowledge of excited states, the mechanisms underlying the interband absorption are discussed. This study suggests that GQDs would show an improved sensing performance in the selective colorimetric detection of lead by the thickness control. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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10 pages, 4620 KiB

Open AccessArticle

Fast and Cost-Effective Synthesis of High-Quality Graphene on Copper Foils Using High-Current Arc Evaporation

by Helge Lux, Matthias Edling, Peter Siemroth and Sigurd Schrader

Materials 2018, 11(5), 804; https://doi.org/10.3390/ma11050804 - 16 May 2018

Cited by 3 | Viewed by 2951

Abstract

In this paper, we present an innovative and ultra-fast process for the deposition of high-quality graphene on different metal foils and thin metal films. The graphene layer can be homogeneously deposited in only 30 s process time. Due to the weak adhesion to [...] Read more.

In this paper, we present an innovative and ultra-fast process for the deposition of high-quality graphene on different metal foils and thin metal films. The graphene layer can be homogeneously deposited in only 30 s process time. Due to the weak adhesion to the substrate material, the monolayer graphene is easy to transfer using the established processes. For the production, we use magnetic filtered high-current arc evaporation (Φ-HCA) with a solid, graphitic carbon source. This ultra-fast growth process can pave the way towards a cost-effective graphene synthesis for the mass production e.g., in a roll-to-roll process, avoiding time consuming established processes. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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Review

Jump to: Research

29 pages, 11796 KiB

Open AccessReview

Graphene-Based Light Sensing: Fabrication, Characterisation, Physical Properties and Performance

by Adolfo De Sanctis, Jake D. Mehew, Monica F. Craciun and Saverio Russo

Materials 2018, 11(9), 1762; https://doi.org/10.3390/ma11091762 - 18 Sep 2018

Cited by 42 | Viewed by 8364

Abstract

Graphene and graphene-based materials exhibit exceptional optical and electrical properties with great promise for novel applications in light detection. However, several challenges prevent the full exploitation of these properties in commercial devices. Such challenges include the limited linear dynamic range (LDR) of graphene-based [...] Read more.

Graphene and graphene-based materials exhibit exceptional optical and electrical properties with great promise for novel applications in light detection. However, several challenges prevent the full exploitation of these properties in commercial devices. Such challenges include the limited linear dynamic range (LDR) of graphene-based photodetectors, the lack of efficient generation and extraction of photoexcited charges, the smearing of photoactive junctions due to hot-carriers effects, large-scale fabrication and ultimately the environmental stability of the constituent materials. In order to overcome the aforementioned limits, different approaches to tune the properties of graphene have been explored. A new class of graphene-based devices has emerged where chemical functionalisation, hybridisation with light-sensitising materials and the formation of heterostructures with other 2D materials have led to improved performance, stability or versatility. For example, intercalation of graphene with FeCl

_{3}

is highly stable in ambient conditions and can be used to define photo-active junctions characterized by an unprecedented LDR while graphene oxide (GO) is a very scalable and versatile material which supports the photodetection from UV to THz frequencies. Nanoparticles and quantum dots have been used to enhance the absorption of pristine graphene and to enable high gain thanks to the photogating effect. In the same way, hybrid detectors made from stacked sequences of graphene and layered transition-metal dichalcogenides enabled a class of devices with high gain and responsivity. In this work, we will review the performance and advances in functionalised graphene and hybrid photodetectors, with particular focus on the physical mechanisms governing the photoresponse, the performance and possible future paths of investigation. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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10 pages, 3275 KiB

Open AccessFeature PaperReview

In Situ Room Temperature Electron-Beam Driven Graphene Growth from Hydrocarbon Contamination in a Transmission Electron Microscope

by Mark H Rummeli, Yumo Pan, Liang Zhao, Jing Gao, Huy Q Ta, Ignacio G. Martinez, Rafael G. Mendes, Thomas Gemming, Lei Fu, Alicja Bachmatiuk and Zhongfan Liu

Materials 2018, 11(6), 896; https://doi.org/10.3390/ma11060896 - 26 May 2018

Cited by 13 | Viewed by 5520

Abstract

The excitement of graphene (as well as 2D materials in general) has generated numerous procedures for the fabrication of graphene. Here we present a mini-review on a rather less known, but attractive, in situ means to fabricate graphene inside a transmission electron microscope [...] Read more.

The excitement of graphene (as well as 2D materials in general) has generated numerous procedures for the fabrication of graphene. Here we present a mini-review on a rather less known, but attractive, in situ means to fabricate graphene inside a transmission electron microscope (TEM). This is achieved in a conventional TEM (viz. no sophisticated specimen holders or microscopes are required) and takes advantage of inherent hydrocarbon contamination as a carbon source. Both catalyst free and single atom catalyst approaches are reviewed. An advantage of this technique is that not only can the growth process be imaged in situ, but this can also be achieved with atomic resolution. Moreover, in the future, one can anticipate such approaches enabling the growth of nano-materials with atomic precision. Full article

(This article belongs to the Special Issue Carbon Nanomaterials: Graphene, Nanoribbons and Quantum dots)

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