By combining non-contact atomic force microscopy (nc-AFM) and Kelvin probe microscopy (KPFM) in ultra high vacuum environment (UHV), we directly measure the height and work function of graphene monolayer on the Si-face of 6H-SiC(0001) with a precision that allows us to differentiate three different types of graphene structures : zero layer graphene (ZLG), Quasi free-standing monolayer graphene (QFMLG) and bilayer graphene (BLG). The height and work function of ZLG are 2.62 ± 0.22 Å and 4.42 ± 0.05 eV respectively, when they are 4.09 ± 0.11 Å and 4.63 ± 0.05 eV for QFMLG. The work function is 4.83 ± 0.05 eV for the BLG. Unlike any other available technique, the local nc-AFM/KPFM dual probe makes it possible to directly identify the nature of nanometer-sized graphene islands that constitute the early nuclei of graphene monolayer grown on 6H-SiC(0001) by chemical vapor deposition.

The integration of graphene (Gr) with nitride semiconductors is highly interesting for applications in high-power/high-frequency electronics and optoelectronics. In this work, we demonstrated the direct growth of Gr on Al0.5Ga0.5N/sapphire templates by propane (C3H8) chemical vapor deposition at a temperature of 1350 °C. After optimization of the C3H8 flow rate, a uniform and conformal Gr coverage was achieved, which proved beneficial to prevent degradation of AlGaN morphology. X-ray photoemission spectroscopy revealed Ga loss and partial oxidation of Al in the near-surface AlGaN region. Such chemical modification of a ∼2 nm thick AlGaN surface region was confirmed by cross-sectional scanning transmission electron microscopy combined with electron energy loss spectroscopy, which also showed the presence of a bilayer of Gr with partial sp2/sp3 hybridization. Raman spectra indicated that the deposited Gr is nanocrystalline (with domain size ∼7 nm) and compressively strained. A Gr sheet resistance of ∼15.8 kΩ sq-1 was evaluated by four-point-probe measurements, consistently with the nanocrystalline nature of these films. Furthermore, nanoscale resolution current mapping by conductive atomic force microscopy indicated local variations of the Gr carrier density at a mesoscopic scale, which can be ascribed to changes in the charge transfer from the substrate due to local oxidation of AlGaN or to the presence of Gr wrinkles.

The family of III-Nitride semiconductors has been under intensive research for almost 30 years and has revolutionized lighting applications at the dawn of the 21st century. However, besides the developments and applications achieved, nitride alloys continue to fuel the quest for novel materials and applications. We report on the synthesis of a new nitride-based compound by using annealing of AlN heteroepitaxial layers under a Si-atmosphere at temperatures between 1350 degrees C and 1550 degrees C. The structure and stoichiometry of this compound are investigated by high resolution transmission electron microscopy (TEM) techniques and energy dispersive X-Ray (EDX) spectroscopy. Results are supported by density functional theory (DFT) calculations. The identified structure is a derivative of the parent wurtzite AlN crystal where the anion sublattice is fully occupied by N atoms and the cation sublattice is the stacking of 2 different planes along <0001>: The first one exhibits a x3 periodicity along <11-20> with 1/3 of the sites being vacant. The rest of the sites in the cation sublattice are occupied by an equal number of Si and Al atoms. Assuming a semiconducting alloy, a range of stoichiometries is proposed, Al5+alpha Si5+delta N12 with a being between -2/3 and 1/4 and delta between 0 and 3/4.

We report on the synthesis of new nitride-based compound by using annealing of AlN heteroepitaxial layers under a Si-atmosphere at temperatures between 1350$^\circ$C and 1550$^\circ$C. The structure and stoichiometry of this compound are investigated by high-resolution scanning transmission electron microscopy (HRSTEM), energy dispersive X-Ray (EDX) spectroscopy, and density functional theory (DFT) calculations. The identified structure is a derivative of the parent wurtzite AlN crystal where anion sublattice is fully occupied by N atoms and the cation sublattice is the stacking of 2 different planes along . The first one exhibits a $\times$3 periodicity along with 1/3 of the sites being vacant. The rest of the sites in the cation sublattice are occupied by equal number of Si and Al atoms. Assuming a semiconducting alloy, which is expected to have a wide band gap, a range of stoichiometries is proposed, Al$_{5+\alpha}$Si$_{5+\delta}$N$_{12}$, with $\alpha$ being between 0 and 1/3 and $\delta$ between 0 and 1/4.

This work presents the measurements of the Kapitza thermal boundary resistance (TBR) between two types of graphene monolayers epitaxially grown on the silicon face of SiC(0001) substrates by chemical vapor deposition. The studied systems consist of a graphene layer either separated from the bulk SiC by a carbon rich interface layer (called buffer layer BL) exhibiting a 63×63R30° surface reconstruction or quasifreestanding on the substrate, which will be referred to as QFSMG (for the quasifreestanding monolayer of graphene). The equivalent graphene monolayers' thermal resistances (ratio between the layer thickness and its thermal conductivity) and their respective TBR with the SiC substrates were characterized using a high frequency photothermal radiometry technique in order to distinguish the difference between the two interfaces. The results display a larger TBR through the BL compared to a lower one across the QFSMG. It is suggested that beyond generally used models, the presence of electronic coupling between the QFSMG and the SiC may create new channels for heat conduction at the interface. These results give new insights into the thermal transport at the nanoscale using epitaxial graphene monolayers for better usage in heat management applications (e.g., thermal diodes or thermal transistors).

The properties of group III-Nitrides (III-N) such as a large direct bandgap, high melting point, and high breakdown voltage make them very attractive for optoelectronic applications. However, conventional epitaxy on SiC and sapphire substrates results in strained and defective films with consequently poor device performance. In this work, by studying the nucleation of GaN on graphene/SiC by MOVPE, we unambiguously demonstrate the possibility of remote van der Waals epitaxy. By choosing the appropriate growth conditions, GaN crystals can grow either in-plane misoriented or fully epitaxial to the substrate. The adhesion forces across the GaN and graphene interface are very weak and the micron-scale nuclei can be easily moved around. The combined use of x-ray diffraction and transmission electron microscopy demonstrate the growth of stress-free and dislocation-free crystals. The high quality of the crystals was further confirmed by photoluminescence measurements. First principles calculations additionally highlighted the importance of the polarity of the underlying substrate. This work lays the first brick towards the synthesis of high quality III-N thin films grown via van der Waals epitaxy.

The family of III-Nitride semiconductors has been under intensive research for almost 30 years and has revolutionized lighting applications at the dawn of the 21st century. However, besides the developments and applications achieved, nitride alloys continue to fuel the quest for novel materials and applications. We report on the synthesis of a new nitride-based compound by using annealing of AlN heteroepitaxial layers under a Si-atmosphere at temperatures between 1350 °C and 1550 °C. The structure and stoichiometry of this compound are investigated by high resolution transmission electron microscopy (TEM) techniques and energy dispersive X-Ray (EDX) spectroscopy. Results are supported by density functional theory (DFT) calculations. The identified structure is a derivative of the parent wurtzite AlN crystal where the anion sublattice is fully occupied by N atoms and the cation sublattice is the stacking of 2 different planes along <0001>: The first one exhibits a ×3 periodicity along <11–20> with 1/3 of the sites being vacant. The rest of the sites in the cation sublattice are occupied by an equal number of Si and Al atoms. Assuming a semiconducting alloy, a range of stoichiometries is proposed, Al5+αSi5+δN12 with α being between −2/3 and 1/4 and δ between 0 and 3/4.

Nanopendeo-epitaxy of gallium nitride (GaN) is considered in this study as a way of producing freestanding GaN with reduced strain and threading dislocation density (TDD) for optoelectronic applications. The novelty of this work lies in the use of silicon on insulator (SOI) substrates patterned into nano-pillars down to the buried oxide (BOX). We actually want to benefit from the creeping properties of SiO2 at the growth temperature of GaN for strain relaxation and grain-boundary dislocations reduction. In this paper, we report on the fabrication of 40x40 mu m(2) and 300x300 mu m(2) freestanding GaN platelets, up to 10 mu m-thick, spontaneously separated from the initial pillars. Structural and optical characterizations show that the platelets are crack-free and almost fully relaxed, with a TDD of similar to 4x10(8)/cm(2). We underline the different benefits of this approach, but most importantly, we believe that it will be the founding-brick for transferable GaN-based devices.

A few years ago, we demonstrated that graphene can markedly surpass GaAs/AlGaAs semiconductor heterostructures for the implementation of the quantum Hall resistance standard in relaxed experimental conditions, while preserving a state-of-the-art accuracy [1]. This paper describes supplementary quantum transport experiments performed on a significant number of graphene based quantum Hall devices obtained from graphene grown by CVD on SiC, like the one used for the above-mentioned demonstration, and with similar process and preparation. The objectives were to investigate the sample-to-sample reproducibility of the electronic properties and device performance, the structural key control parameter and the underpinning physics.

In this chapter, the operating principles of an ideal hot electron transistor (HET) will be introduced, illustrating the device's direct current (DC) characteristics and discussing the impact of the main physical parameters on the DC figures of merit (current transit ratio and current gain) and on the alternating current (AC) figures of merit (f max and f T ). Therefore, an historical perspective on the attempted implementations of this device concept will be provided, starting from the first proposal of a metal base HET to more recent implementations, such as the nitride semiconductors–based HETs and the Gr base HET (GBHET). The theoretical DC and AC performances of GBHETs will be discussed and state-of-the-art GBHETs will be presented. The last section of the chapter will present open issues and new ideas to improve the performances of GBHETs.

The hot electron transistor (HET) is an unipolar majority carrier vertical device with great potential for high frequency (THz) applications. Recently, graphene (Gr) heterostructures with Nitrides have been considered as a promising material system to implement this device concept, with GaN/AlGaN (or GaN/AlN) working as emitter/emitter‐base barrier and Gr as the ultrathin base enabling ballistic transit of hot electrons. In this work, the main issues related to the fabrication of Gr/Nitrides heterojunctions are discussed. An optimized transfer procedure of large‐area Gr membranes onto AlGaN/GaN grown on Si(111) is illustrated. In particular, a soft O2 plasma pretreatment of the AlGaN surface is found to greatly improve the Gr adhesion, resulting in a reduced cracks density. A nanoscale electrical characterization of the obtained Gr/AlGaN/GaN heterostructures was carried out by conductive atomic force microscopy, to evaluate the effect of typical nanometric corrugations (wrinkles) of the Gr membrane on the current transport. These morphological features introduce resistive contributions both to the lateral current transport in the Gr membrane and to the vertical current injection across the heterojunction. The impact of these results on the relevant electrical parameters (i.e., the base resistance and the emitter‐base injection efficiency) of a HET based on this heterostructure is also discussed.

Thermodynamic simulations of SiC hydrogen annealing illustrating the impossibility of graphene formation due to the high pressure of C–H gases.

Graphene and AlN are promising materials, interesting to combine together. In this study, we will present first results for direct growth of graphene on bulk AlN and on AlN templates using chemical vapor deposition, including the annealing of these substrates at high temperatures. Atomic force microscopy (AFM) enabled us to study the evolution of the AlN surface morphology after annealing and growth. Few-layer graphene deposition is demonstrated on the basis of X-ray photoemission and Raman spectroscopy. (C) 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

AlN thin films, grown on (0001) sapphire substrates by molecular beam epitaxy (MBE), were annealed at high temperature (up to 1650 °C) in flowing N2. X-ray diffraction (XRD) studies, combined with Williamson-Hall and Srikant plots, have shown that annealing leads to a strong reduction of both edge and mixed threading dislocation densities, as confirmed by transmission electron microscopy (TEM) images, up to 75%. Moreover, it is found that annealing at high temperatures allows the relaxation of the tensile strain in the AlN film due to the growth process. In addition, the morphological properties of the films were determined by atomic force microscopy (AFM) and show that the annealing conditions have a strong impact on the surface morphology and roughness. Finally, an annealing at 1550 °C for 20 min appears as an ideal tradeoff to enhance the structural properties while preserving the initial AlN surface morphology.

Graphene is a two-dimensional material belonging to the family of carbon allotropes, consisting of a stable single atomic layer owing to strong in-plane chemical bonds between carbon atoms. It can be identified as a gapless semiconductor with a linear energy dispersion near the Dirac points, which facilitates ballistic carrier transport. In addition, similarly to any semiconductor, it is possible to control its electrical properties under the influence of an external electric field, resulting in the tuning of its carrier density and doping type, i.e. electrons or holes. Graphene can be elaborated by different techniques and approaches. In this present work, we have considered the direct growth on silicon carbide (SiC) by chemical vapor deposition (CVD) with an external carbon source. This approach which has started to be developed in our laboratory since 2010 is very promising since it allows to control the graphene properties by manipulating the growth parameters. Our objective in this manuscript is to give further insights into this growth technique and to study its potential for the growth of graphene. For this purpose, we have discussed in details different aspects of the growth, starting with thermodynamic simulations to understand the chemistry behind our distinct growth approach. We have also investigated the influence of the different growth parameters, such as the growth time, the propane flow rate and other parameters on the growth of graphene and its properties. However, we mainly focused on two major factors: the hydrogen amount in the gas mixture, especially since the growth is carried out under hydrogen and argon, and the substrate’s miscut angle. Our investigations revealed that the graphene structure can be altered depending on the hydrogen percentage in the gas mixture considered for the growth. For low hydrogen percentage, the graphene growth is associated with a (6√3×6√3) interface reconstruction, whereas for high hydrogen percentage, the graphene layer is dominated by in-plane rotational disorder. These observations are related to the hydrogen intercalation at the interface between the graphene layer and the SiC substrate, which can allow or prohibit the formation of the (6√3×6√3) interface reconstruction as we have discussed thoroughly in this manuscript. The presence of two graphene structures was expected to impact the strain within the graphene layer. For this reason, we have discussed in details the origins of the strain in graphene and attempted to correlate the hydrogen intercalation at the interface to the strain amount. Furthermore, the substrate’s miscut angle was also found to have a direct influence on the growth of graphene, mainly affecting the morphology but also the strain within the graphene layer. In light of the different studies and results, we were able to combine the ideal growth parameters to produce state-of-the art graphene, while demonstrating the possibility of tuning its electrical properties with the growth conditions. In a second part of this work, we extended our study to the growth of graphene on III-nitrides semiconductors. We have considered substrates and templates such as bulk aluminum nitride (AlN), AlN/SiC and AlN/sapphire, which opens new opportunities for innovative applications. The growth of graphene was preceded by an annealing study on the different AlN substrates, in an attempt to enhance their surface quality, but also to test their stability at the temperatures necessary for the growth of graphene. Although the AlN film was found to be unable to withstand the high temperature in some cases, an enhancement of the crystalline quality was detected, attributed to the annealing effect.

In this study we report the growth of graphene on different silicon carbide substrates by chemical vapor deposition (CVD) in order to understand the influence of the substrate offcut on the graphene layers. For this purpose, graphene was grown on substrates with different offcuts, under hydrogen-argon atmosphere, and analyzed using AFM, LEED and Raman spectroscopy. We discuss the morphology and strain in graphene, and finally the ideal offcut for graphene growth.