Continuous wafer-scale graphene on cubic-SiC（O01）

The atomic and electronic structure of graphene synthesized on commercially available cubic-SiC（001）/Si（001） wafers have been studied by low energy electron microscopy （LEEM）, scanning tunneling microscopy （STM）, low energy electron diffraction （LEED）, and angle resolved photoelectron spectroscopy （ARPES）. LEEM and STM data prove the wafer-scale continuity and uniform thickness of the graphene overlayer on SIC（001）. LEEM, STM and ARPES studies reveal that the graphene overlayer on SIC（001） consists of only a few monolayers with physical properties of quasi-freestanding graphene. Atomically resolved STM and micro-LEED data show that the top graphene layer consists of nanometer-sized domains with four different lattice orientations connected through the 〈110〉-directed boundaries. ARPES studies reveal the typical electron spectrum of graphene with the Dirac points close to the Fermi level. Thus, the use of technologically relevant SiC（001）/Si（001） wafers for graphene fabrication repre-sents a realistic way of bridging the gap between the outstanding properties of graphene and their applications.     

Layer‐by‐Layer Decoupling of Twisted Graphene Sheets Epitaxially Grown on a Metal Substrate

The electronic properties of graphene can be efficiently altered upon interaction with the underlying substrate resulting in a dramatic change of charge carrier behavior. Here, the evolution of the local electronic properties of epitaxial graphene on a metal upon the controlled formation of multilayers, which are produced by intercalation of atomic carbon in graphene/Ir(111), is investigated. Using scanning tunneling microscopy and Landau‐level spectroscopy, it is shown that for a monolayer and bilayers with small‐angle rotations, Landau levels are fully suppressed, indicating that the metal–graphene interaction is largely confined to the first graphene layer. Bilayers with large twist angles as well as twisted trilayers demonstrate a sequence of pronounced Landau levels characteristic for a free‐standing graphene monolayer pointing toward an effective decoupling of the top layer from the metal substrate. These findings give evidence for the controlled preparation of epitaxial graphene multilayers with a different degree of decoupling, which represent an ideal platform for future electronic and spintronic applications.     

Ti/n型6H-SiC(0001)接触界面的研究

用同步辐射光电子能谱(SRPES)和X射线光电子能谱(XPS)的方法研究了Ti/n型6H-SiC(0001)的接触界面。Ti/n型6H-SiC(0001)样品采用磁控溅射的方法获得,然后将表面的Ti用氩离子刻蚀的方法慢慢刻蚀掉,Ti2p3/2用XPS测得,结合能从刻蚀时间为245 min的457.86 eV逐渐移动到刻蚀时间为255 min时的457.57 eV,移动约为0.3 eV。Si2p用同步辐射光测得,结合能从刻蚀245 min时的101.12 eV移动到干净的100.67 eV,峰形状未发生变化,表明Ti与衬底之间没有发生化学反应,SiC的价带发生弯曲,形成的势垒高度为0.89 eV。向SiC上蒸Si 2.5 min,退火30 min,观察LEED花样,发现当发射电流为30mA,能量37 eV时,SiC表面有√3*√3重构,发射电流为40 mA时,有6√3*6√3的重构。     

Electronic Characterization of Organic Thin Films by Kelvin Probe Force Microscopy

This review highlights the potential of Kelvin probe force microscopy (KPFM) beyond imaging to simultaneously study structural and electronic properties of functional surfaces and interfaces. This is of paramount importance since it is well established that a solid surface possesses different properties than the bulk material. The versatility of the technique allows one to carry out investigations in a non‐invasive way for different environmental conditions and sample types with resolutions of a few nanometers and some millivolts. KPFM can be used to acquire a wide knowledge of the overall electronic and electrical behavior of a sample surface. Moreover, by KPFM it is possible to study complex electronic phenomena in supramolecular engineered systems and devices. The combination of such a methodology with external stimuli, e.g., light irradiation, opens new doors to the exploration of processes occurring in nature or in artificial complex architectures. Therefore, KPFM is an extremely powerful technique that permits the unraveling of electronic (dynamic) properties of materials, enabling the optimization of the design and performance of new devices based on organic‐semiconductor nanoarchitectures.     

On‐Surface Synthesis of 8‐ and 10‐Armchair Graphene Nanoribbons

Armchair graphene nanoribbons (AGNRs) with 8 and 10 carbon atoms in width (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces via lateral fusion of nanoribbons that belong to different subfamilies. Poly‐para‐phenylene (3‐AGNR) chains are pre‐synthesized as ladder ribbons on Au (111). Subsequently, synthesized 5‐ and 7‐AGNRs can laterally fuse with 3‐AGNRs upon annealing at higher temperature, producing 8‐ and 10‐AGNRs, respectively. The synthetic process, and their geometric and electronic structures are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). STS investigations reveal the band gap of 10‐AGNR (2.0 ± 0.1 eV) and a large apparent band gap of 8‐AGNRs (2.3 ± 0.1 eV) on Au (111) surface.     

In situ high-temperature scanning tunneling microscopy study of bilayer graphene growth on 6H-SiC(0001)

Using in situ high-temperature (1395 K), ultra-high vacuum, scanning tunneling microscopy (STM), we investigated the growth of bilayer graphene on 6H-SiC(0001). From the STM images, we measured areal coverages of SiC and graphene as a function of annealing time and found that graphene grows at the expense of SiC. Graphene domains were observed to grow, at comparable rates, at (I) graphene-free SiC step edges, (II) graphene-SiC interfaces, and (III) the existing graphene domain edges. Based upon our results, we suggest that the rate-limiting step controlling bilayer graphene growth is the desorption of Si from the substrate.     

Indium Nitride at the 2D Limit

The properties of 2D InN are predicted to substantially differ from the bulk crystal. The predicted appealing properties relate to strong in‐ and out‐of‐plane excitons, high electron mobility, efficient strain engineering of their electronic and optical properties, and strong application potential in gas sensing. Until now, the realization of 2D InN remained elusive. In this work, the formation of 2D InN and measurements of its bandgap are reported. Bilayer InN is formed between graphene and SiC by an intercalation process in metal–organic chemical vapor deposition (MOCVD). The thickness uniformity of the intercalated structure is investigated by conductive atomic force microscopy (C‐AFM) and the structural properties by atomic resolution transmission electron microscopy (TEM). The coverage of the SiC surface is very high, above 90%, and a major part of the intercalated structure is represented by two sub‐layers of indium (In) bonded to nitrogen (N). Scanning tunneling spectroscopy (STS) measurements give a bandgap value of 2 ± 0.1 eV for the 2D InN. The stabilization of 2D InN with a pragmatic wide bandgap and high lateral uniformity of intercalation is demonstrated.     

Electronic structures of an epitaxial graphene monolayer on SiC(0001) after gold intercalation: a first-principles study

The atomic and electronic structures of an Au-intercalated graphene monolayer on the SiC(0001) surface were investigated using first-principles calculations. The unique Dirac cone of graphene near the K?point reappeared as the monolayer was intercalated by Au atoms. Coherent interfaces were used to study the mismatch and the strain at the boundaries. Our calculations showed that the strain at the graphene/Au and Au/SiC(0001) interfaces also played a key role in the electronic structures. Furthermore, we found that at an Au coverage of 3/8?ML, Au intercalation leads to a strong n-type doping of graphene. At 9/8?ML, it exhibited a weak p-type doping, indicative that graphene was not fully decoupled from the substrate. The shift in the Dirac point resulting from the electronic doping was not only due to the different electronegativities but also due to the strain at the interfaces. Our calculated positions of the Dirac points are consistent with those observed in the ARPES experiment (Gierz et al 2010 Phys. Rev. B 81 235408).     

Structural and electronic decoupling of C₆₀ from epitaxial graphene on SiC

We have investigated the initial stages of growth and the electronic structure of C(60) molecules on graphene grown epitaxially on SiC(0001) at the single-molecule level using cryogenic ultrahigh vacuum scanning tunneling microscopy and spectroscopy. We observe that the first layer of C(60) molecules self-assembles into a well-ordered, close-packed arrangement on graphene upon molecular deposition at room temperature while exhibiting a subtle C(60) superlattice. We measure a highest occupied molecular orbital-lowest unoccupied molecular orbital gap of ～3.5 eV for the C(60) molecules on graphene in submonolayer regime, indicating a significantly smaller amount of charge transfer from the graphene to C(60) and substrate-induced screening as compared to C(60) adsorbed on metallic substrates. Our results have important implications for the use of graphene for future device applications that require electronic decoupling between functional molecular adsorbates and substrates.     

Structure and chemical reactivity of lithium-doped graphene on hydrogen-saturated silicon carbide

Herein, we studied the structure and hydrogenation of graphene supported on hydrogen-terminated SiC, with intercalated Li atoms. Strong nonbonded interactions occur between graphene and the Si–H groups. The latter were found to be significantly augmented by the intercalation of Li atoms, which enhanced the SiH::pi interactions. Although the electronic structure of graphene did not experience significant changes when supported on hydrogen-terminated SiC, a small gap of 0.04 eV was computed at the HSEH1PBE/6-31G* level. The clustering of Li atoms over graphene was prevented by the SiC support. A significant enhancement of reactivity could be corroborated due to the presence of intercalated Li atoms, given that the C–H binding energy was increased by almost 1 eV with respect to pristine graphene. We expect that hydrogen-terminated SiC with intercalated Li atoms can be used to enhance the chemical reactivity of graphene, given that it strongly interacts with graphene but does not compete for the electrons donated by Li.     

Locally resolved surface photo voltage spectroscopy on Zn-doped CuInS2 polycrystalline thin films

Incorporation of small amounts of Zinc (< 1 at.%) in polycrystalline CuInS₂ thin films for solar cells leads to an increased open circuit voltage. Here we investigate the optoelectronic effect of Zn doping by local surface photovoltage spectroscopy (SPS). SPS is measured using Kelvin probe force microscopy (KPFM) to obtain the surface photovoltage (SPV) and SPS with high lateral resolution, and thereby study the homogeneity of the doping. In our KPFM experimental setup, illumination is realized by a Xe arc lamp and monochromator in the visible spectrum range by means of an optical fiber into the UHV system of the KPFM.We compare CuInS₂ thin film samples with and without Zn doping. The pure CuInS₂ samples show a sharp onset of SPV at the band gap of 1.48 eV, whereas for Zn-doped CuInS₂ we observe a two step onset, with a steep increase of SPV at 1.48 eV. However, already below this band gap, we observe a slight SPV response, even down to about 1.40 eV. This indicates the presence of states in the band gap, likely resulting from disorder induced by the Zn-doping. The absence of lateral differences in the observed SPV spectra favors an explanation by Urbach-tails over the possible existence of a Zn foreign phase. These results are in agreement with transmission/absorption measurements.     

Raman spectroscopy and imaging of graphene

Graphene has many unique properties that make it an ideal material for fundamental studies as well as for potential applications. Here we review recent results on the Raman spectroscopy and imaging of graphene. We show that Raman spectroscopy and imaging can be used as a quick and unambiguous method to determine the number of graphene layers. The strong Raman signal of single layer graphene compared to graphite is explained by an interference enhancement model. We have also studied the effect of substrates, the top layer deposition, the annealing process, as well as folding (stacking order) on the physical and electronic properties of graphene. Finally, Raman spectroscopy of epitaxial graphene grown on a SiC substrate is presented and strong compressive strain on epitaxial graphene is observed. The results presented here are highly relevant to the application of graphene in nano-electronic devices and help in developing a better understanding of the physical and electronic properties of graphene. This article is published with open access at Springerlink.com     

Surface morphology control of the SiC (0001) substrate during the graphene growth

Abstract

The dependence of surface morphology of the SiC(0001) substrate on the rate with which it is heated up to the temperature of graphene growth was studied by three techniques: atomic force microscopy, Raman spectroscopy and Kelvin probe force microscopy. The study was carried out for the rates of substrates heating ranging from 100?°C/min to 320?°C/min. As a result, it was found out that both the width of the terraces forming on the surface of SiC substrate and the uniformity of the graphene layers covering these terraces significantly depend on the applied rate of the heating. It was also shown that the most homogeneous monolayer graphene with the minimum of double-layers inclusions is formed if the rate of SiC heating is about 250?°C/min.     

Single‐ and Double‐Sided Chemical Functionalization of Bilayer Graphene

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X‐ray photoelectron spectroscopy. Single‐ and double‐sided chemical functionalization are found to give very different results: single‐sided modified bilayers show relatively high mobility (200–600 cm² V^?1 s^?1 at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double‐sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single‐sided modification of bilayers) for sensors and transistors and new graphene‐derivatives materials (through double‐sided modification).     

Inducing electronic changes in graphene through silicon (100) substrate modification

We have performed scanning tunneling microscopy and spectroscopy (STM/STS) measurements as well as ab initio calculations for graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces. In order to experimentally study the same graphene piece on both substrates, we develop a method to depassivate hydrogen from under graphene monolayers on the Si(100)/H surface. Our work represents the first demonstration of successful and reproducible depassivation of hydrogen from beneath monolayer graphene flakes on Si(100)/H by electron-stimulated desorption. Ab initio simulations combined with STS taken before and after hydrogen desorption demonstrate that graphene interacts differently with the clean and H-passivated Si(100) surfaces. The Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer. The local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.     

Scalable templated growth of graphene nanoribbons on SiC

In spite of its excellent electronic properties, the use of graphene in field-effect transistors is not practical at room temperature without modification of its intrinsically semimetallic nature to introduce a bandgap. Quantum confinement effects can create a bandgap in graphene nanoribbons, but existing nanoribbon fabrication methods are slow and often produce disordered edges that compromise electronic properties. Here, we demonstrate the self-organized growth of graphene nanoribbons on a templated silicon carbide substrate prepared using scalable photolithography and microelectronics processing. Direct nanoribbon growth avoids the need for damaging post-processing. Raman spectroscopy, high-resolution transmission electron microscopy and electrostatic force microscopy confirm that nanoribbons as narrow as 40 nm can be grown at specified positions on the substrate. Our prototype graphene devices exhibit quantum confinement at low temperatures (4 K), and an on-off ratio of 10 and carrier mobilities up to 2,700 cm(2) V(-1) s(-1) at room temperature. We demonstrate the scalability of this approach by fabricating 10,000 top-gated graphene transistors on a 0.24-cm(2) SiC chip, which is the largest density of graphene devices reported to date.     

Photoemission studies of the vicinal SiC(100) 4° surface and the Cs/SiC(100) 4° interface

Photoemission studies of the electronic structure of the vicinal SiC(100) 4° surface, which was grown using a new substrate atom substitution method, and the Cs/SiC(100) 4° interface have been performed for the first time. The modification of spectra of the valence band and C 1s and Si 2p core levels in the process of formation of the Cs/SiC(100) 4° interface was analyzed. The suppression of the surface SiC state with a binding energy of 2.8 eV and the formation of a cesium-induced state with a binding energy of 10.5 eV were observed. The modification of the complex component structure in the spectrum of C 1s core level has been detected and examined for the first time. It was found that Cs adsorption on the vicinal SiC(100) 4° surface results in intercalation of graphene islands on SiC(100) 4° with Cs atoms.     

Graphoepitaxy of High‐Quality GaN Layers on Graphene/6H–SiC

The implementation of graphene layers in gallium nitride (GaN) heterostructure growth can solve self‐heating problems in nitride‐based high‐power electronic and light‐emitting optoelectronic devices. In the present study, high‐quality GaN layers are grown on patterned graphene layers and 6H–SiC by metalorganic chemical vapor deposition. A periodic pattern of graphene layers is fabricated on 6H–SiC by using polymethyl methacrylate deposition and electron beam lithography, followed by etching using an Ar/O₂ gas atmosphere. Prior to GaN growth, an AlN buffer layer and an Al_0.2Ga_0.8N transition layer are deposited. The atomic structures of the interfaces between the 6H–SiC and graphene, as well as between the graphene and AlN, are studied using scanning transmission electron microscopy. Phase separation of the Al_0.2Ga_0.8N transition layer into an AlN and GaN superlattice is observed. Above the continuous graphene layers, polycrystalline defective GaN is rapidly overgrown by better quality single‐crystalline GaN from the etched regions. The lateral overgrowth of GaN results in the presence of a low density of dislocations (≈10⁹ cm⁻²) and inversion domains and the formation of a smooth GaN surface.     

2D AlN Layers Sandwiched Between Graphene and Si Substrates

Due to the superior thickness‐dependent properties, 2D materials have exhibited great potential for applications in next‐generation optoelectronic devices. Despite the significant progress that has been achieved, the synthesis of 2D AlN remains challenging. This work reports on the epitaxial growth of 2D AlN layers via utilizing physically transferred graphene on Si substrates by metal–organic chemical vapor deposition. The 2D AlN layers sandwiched between graphene and Si substrates are confirmed by annular bright‐field scanning transmission electron microscopy and the effect of hydrogenation on the formation of 2D AlN layers is clarified by theoretical calculations with first‐principles calculations based on density functional theory. Moreover, the bandgap of as‐grown 2D AlN layers is theoretically predicted to be ≈9.63 eV and is experimentally determined to be 9.20–9.60 eV. This ultrawide bandgap semiconductor shows great promise in deep‐ultraviolet optoelectronic applications. These results are expected to support innovative and front‐end development of optoelectronic devices.     

Complex investigation of electronic structure transformations in Lead Sulphide nanoparticles using a set of electron spectroscopy techniques

It has been reported recently that kinetic energy of photoelectrons emitted from core levels decreases with decreasing of the nanocrystal size. This phenomenon is called the size shift. The size shift value is the same for donor and acceptor in the compound. The present work is aimed on the explanation of this phenomenon. Crystals of lead sulfide PbS with different size from 50 to 350 nm were grown by chemical bath deposition (CBD) technique from alkaline solution onto Si and GaAs substrates. The morphology and size of crystals were analyzed by high resolution scanning electron microscopy (HRSEM). Complex electron spectroscopy investigations of electronic structure were carried out. In recent experiments X-ray photoelectron spectroscopy (XPS) was used for determination of Pb 4f, and S 2p electronic level positions and their size shifts. To explain the observed dependences in this work, we applied the following methods: analysis of PbS valence band (VB) and Pb 5d electronic level structure in the range ∼0-30 eV by XPS, high resolution electron energy losses spectroscopy (HREELS) for analysis of band gap transformations and work function measurements by Kelvin probe microscopy for the contact potential difference (CPD). The influence of work function increasing, widening of the band gap, transformations in VB and inter-level energy distances with decreasing of nanocrystal size on the size shift function ΔE(R) is discussed.