Interface Properties of MoS2 van der Waals Heterojunctions with GaN.

The combination of the unique physical properties of molybdenum disulfide (MoS2) with those of gallium nitride (GaN) and related group-III nitride semiconductors have recently attracted increasing scientific interest for the realization of innovative electronic and optoelectronic devices. A deep understanding of MoS2/GaN interface properties represents the key to properly tailor the electronic and optical behavior of devices based on this heterostructure. In this study, monolayer (1L) MoS2 was grown on GaN-on-sapphire substrates by chemical vapor deposition (CVD) at 700 °C. The structural, chemical, vibrational, and light emission properties of the MoS2/GaN heterostructure were investigated in detail by the combination of microscopic/spectroscopic techniques and ab initio calculations. XPS analyses on as-grown samples showed the formation of stoichiometric MoS2. According to micro-Raman spectroscopy, monolayer MoS2 domains on GaN exhibit an average n-type doping of (0.11 ± 0.12) × 1013 cm-2 and a small tensile strain (ε ≈ 0.25%), whereas an intense light emission at 1.87 eV was revealed by PL analyses. Furthermore, a gap at the interface was shown by cross-sectional TEM analysis, confirming the van der Waals (vdW) bond between MoS2 and GaN. Finally, density functional theory (DFT) calculations of the heterostructure were carried out, considering three different configurations of the interface, i.e., (i) an ideal Ga-terminated GaN surface, (ii) the passivation of Ga surface by a monolayer of oxygen (O), and (iii) the presence of an ultrathin Ga2O3 layer. This latter model predicts the formation of a vdW interface and a strong n-type doping of MoS2, in closer agreement with the experimental observations.

Al2O3 Layers Grown by Atomic Layer Deposition as Gate Insulator in 3C-SiC MOS Devices.

Metal-oxide-semiconductor (MOS) capacitors with Al2O3 as a gate insulator are fabricated on cubic silicon carbide (3C-SiC). Al2O3 is deposited both by thermal and plasma-enhanced Atomic Layer Deposition (ALD) on a thermally grown 5 nm SiO2 interlayer to improve the ALD nucleation and guarantee a better band offset with the SiC. The deposited Al2O3/SiO2 stacks show lower negative shifts of the flat band voltage VFB (in the range of about -3 V) compared with the conventional single SiO2 layer (in the range of -9 V). This lower negative shift is due to the combined effect of the Al2O3 higher permittivity (ε = 8) and to the reduced amount of carbon defects generated during the short thermal oxidation process for the thin SiO2. Moreover, the comparison between thermal and plasma-enhanced ALD suggests that this latter approach produces Al2O3 layers possessing better insulating behavior in terms of distribution of the leakage current breakdown. In fact, despite both possessing a breakdown voltage of 26 V, the T-ALD Al2O3 sample is characterised by a higher current density starting from 15 V. This can be attributable to the slightly inferior quality (in terms of density and defects) of Al2O3 obtained by the thermal approach and, which also explains its non-uniform dC/dV distribution arising by SCM maps.

Structural and Insulating Behaviour of High-Permittivity Binary Oxide Thin Films for Silicon Carbide and Gallium Nitride Electronic Devices.

High-κ dielectrics are insulating materials with higher permittivity than silicon dioxide. These materials have already found application in microelectronics, mainly as gate insulators or passivating layers for silicon (Si) technology. However, since the last decade, the post-Si era began with the pervasive introduction of wide band gap (WBG) semiconductors, such as silicon carbide (SiC) and gallium nitride (GaN), which opened new perspectives for high-κ materials in these emerging technologies. In this context, aluminium and hafnium oxides (i.e., Al2O3, HfO2) and some rare earth oxides (e.g., CeO2, Gd2O3, Sc2O3) are promising high-κ binary oxides that can find application as gate dielectric layers in the next generation of high-power and high-frequency transistors based on SiC and GaN. This review paper gives a general overview of high-permittivity binary oxides thin films for post-Si electronic devices. In particular, focus is placed on high-κ binary oxides grown by atomic layer deposition on WBG semiconductors (silicon carbide and gallium nitride), as either amorphous or crystalline films. The impacts of deposition modes and pre- or postdeposition treatments are both discussed. Moreover, the dielectric behaviour of these films is also presented, and some examples of high-κ binary oxides applied to SiC and GaN transistors are reported. The potential advantages and the current limitations of these technologies are highlighted.

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization.

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800 °C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2-3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS2 was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A1g-E2g Raman modes revealed a compressive strain (ε ≈ -0.78 ± 0.18%) and the coexistence of n- and p-type doped areas in the few-layer MoS2 on SiO2, where the p-type doping is probably due to the presence of residual MoO3. Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS2, which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS2 films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS2 flakes.

Highly Homogeneous Current Transport in Ultra-Thin Aluminum Nitride (AlN) Epitaxial Films on Gallium Nitride (GaN) Deposited by Plasma Enhanced Atomic Layer Deposition.

This paper reports an investigation of the structural, chemical and electrical properties of ultra-thin (5 nm) aluminum nitride (AlN) films grown by plasma enhanced atomic layer deposition (PE-ALD) on gallium nitride (GaN). A uniform and conformal coverage of the GaN substrate was demonstrated by morphological analyses of as-deposited AlN films. Transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) analyses showed a sharp epitaxial interface with GaN for the first AlN atomic layers, while a deviation from the perfect wurtzite stacking and oxygen contamination were detected in the upper part of the film. This epitaxial interface resulted in the formation of a two-dimensional electron gas (2DEG) with a sheet charge density ns ≈ 1.45 × 1012 cm-2, revealed by Hg-probe capacitance-voltage (C-V) analyses. Nanoscale resolution current mapping and current-voltage (I-V) measurements by conductive atomic force microscopy (C-AFM) showed a highly homogeneous current transport through the 5 nm AlN barrier, while a uniform flat-band voltage (VFB ≈ 0.3 V) for the AlN/GaN heterostructure was demonstrated by scanning capacitance microscopy (SCM). Electron transport through the AlN film was shown to follow the Fowler-Nordheim (FN) tunneling mechanism with an average barrier height of <ΦB> = 2.08 eV, in good agreement with the expected AlN/GaN conduction band offset.

Strain, Doping, and Electronic Transport of Large Area Monolayer MoS2 Exfoliated on Gold and Transferred to an Insulating Substrate.

Gold-assisted mechanical exfoliation currently represents a promising method to separate ultralarge (centimeter scale) transition metal dichalcogenide (TMD) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between Au and chalcogen atoms is key to achieving this nearly perfect 1L exfoliation yield. On the other hand, it may significantly affect the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area 1L MoS2 exfoliated on ultraflat Au films (0.16-0.21 nm roughness) and finally transferred to an insulating Al2O3 substrate. Raman mapping and correlative analysis of the E' and A1' peak positions revealed a moderate tensile strain (ε ≈ 0.2%) and p-type doping (n ≈ -0.25 × 1013 cm-2) of 1L MoS2 in contact with Au. Nanoscale resolution current mapping and current-voltage (I-V) measurements by conductive atomic force microscopy (C-AFM) showed direct tunneling across the 1L MoS2 on Au, with a broad distribution of tunneling barrier values (ΦB from 0.7 to 1.7 eV) consistent with p-type doping of MoS2. After the final transfer of 1L MoS2 on Al2O3/Si, the strain was converted to compressive strain (ε ≈ -0.25%). Furthermore, an n-type doping (n ≈ 0.5 × 1013 cm-2) was deduced by Raman mapping and confirmed by electrical measurements of an Al2O3/Si back-gated 1L MoS2 transistor. These results provide a deeper understanding of the Au-assisted exfoliation mechanism and can contribute to its widespread application for the realization of novel devices and artificial vdW heterostructures.

Conductive Atomic Force Microscopy of Semiconducting Transition Metal Dichalcogenides and Heterostructures.

Semiconducting transition metal dichalcogenides (TMDs) are promising materials for future electronic and optoelectronic applications. However, their electronic properties are strongly affected by peculiar nanoscale defects/inhomogeneities (point or complex defects, thickness fluctuations, grain boundaries, etc.), which are intrinsic of these materials or introduced during device fabrication processes. This paper reviews recent applications of conductive atomic force microscopy (C-AFM) to the investigation of nanoscale transport properties in TMDs, discussing the implications of the local phenomena in the overall behavior of TMD-based devices. Nanoscale resolution current spectroscopy and mapping by C-AFM provided information on the Schottky barrier uniformity and shed light on the mechanisms responsible for the Fermi level pinning commonly observed at metal/TMD interfaces. Methods for nanoscale tailoring of the Schottky barrier in MoS2 for the realization of ambipolar transistors are also illustrated. Experiments on local conductivity mapping in monolayer MoS2 grown by chemical vapor deposition (CVD) on SiO2 substrates are discussed, providing a direct evidence of the resistance associated to the grain boundaries (GBs) between MoS2 domains. Finally, C-AFM provided an insight into the current transport phenomena in TMD-based heterostructures, including lateral heterojunctions observed within MoxW1-xSe2 alloys, and vertical heterostructures made by van der Waals stacking of different TMDs (e.g., MoS2/WSe2) or by CVD growth of TMDs on bulk semiconductors.

Dynamic Modification of Fermi Energy in Single-Layer Graphene by Photoinduced Electron Transfer from Carbon Dots.

Graphene (Gr)-a single layer of two-dimensional sp2 carbon atoms-and Carbon Dots (CDs)-a novel class of carbon nanoparticles-are two outstanding nanomaterials, renowned for their peculiar properties: Gr for its excellent charge-transport, and CDs for their impressive emission properties. Such features, coupled with a strong sensitivity to the environment, originate the interest in bringing together these two nanomaterials in order to combine their complementary properties. In this work, the investigation of a solid-phase composite of CDs deposited on Gr is reported. The CD emission efficiency is reduced by the contact of Gr. At the same time, the Raman analysis of Gr demonstrates the increase of Fermi energy when it is in contact with CDs under certain conditions. The interaction between CDs and Gr is modeled in terms of an electron-transfer from photoexcited CDs to Gr, wherein an electron is first transferred from the carbon core to the surface states of CDs, and from there to Gr. There, the accumulated electrons determine a dynamical n-doping effect modulated by photoexcitation. The CD-graphene interaction unveiled herein is a step forward in the understanding of the mutual influence between carbon-based nanomaterials, with potential prospects in light conversion applications.

Advances in the fabrication of graphene transistors on flexible substrates.

Graphene is an ideal candidate for next generation applications as a transparent electrode for electronics on plastic due to its flexibility and the conservation of electrical properties upon deformation. More importantly, its field-effect tunable carrier density, high mobility and saturation velocity make it an appealing choice as a channel material for field-effect transistors (FETs) for several potential applications. As an example, properly designed and scaled graphene FETs (Gr-FETs) can be used for flexible high frequency (RF) electronics or for high sensitivity chemical sensors. Miniaturized and flexible Gr-FET sensors would be highly advantageous for current sensors technology for in vivo and in situ applications. In this paper, we report a wafer-scale processing strategy to fabricate arrays of back-gated Gr-FETs on poly(ethylene naphthalate) (PEN) substrates. These devices present a large-area graphene channel fully exposed to the external environment, in order to be suitable for sensing applications, and the channel conductivity is efficiently modulated by a buried gate contact under a thin Al2O3 insulating film. In order to be compatible with the use of the PEN substrate, optimized deposition conditions of the Al2O3 film by plasma-enhanced atomic layer deposition (PE-ALD) at a low temperature (100 °C) have been developed without any relevant degradation of the final dielectric performance.

Interface Electrical Properties of Al2O3 Thin Films on Graphene Obtained by Atomic Layer Deposition with an in Situ Seedlike Layer.

High-quality thin insulating films on graphene (Gr) are essential for field-effect transistors (FETs) and other electronics applications of this material. Atomic layer deposition (ALD) is the method of choice to deposit high-κ dielectrics with excellent thickness uniformity and conformal coverage. However, to start the growth on the sp2 Gr surface, a chemical prefunctionalization or the physical deposition of a seed layer are required, which can effect, to some extent, the electrical properties of Gr. In this paper, we report a detailed morphological, structural, and electrical investigation of Al2O3 thin films grown by a two-steps ALD process on a large area Gr membrane residing on an Al2O3-Si substrate. This process consists of the H2O-activated deposition of a Al2O3 seed layer a few nanometers in thickness, performed in situ at 100 °C, followed by ALD thermal growth of Al2O3 at 250 °C. The optimization of the low-temperature seed layer allowed us to obtain a uniform, conformal, and pinhole-free Al2O3 film on Gr by the second ALD step. Nanoscale-resolution mapping of the current through the dielectric by conductive atomic force microscopy (CAFM) demonstrated an excellent laterally uniformity of the film. Raman spectroscopy measurements indicated that the ALD process does not introduce defects in Gr, whereas it produces a partial compensation of Gr unintentional p-type doping, as confirmed by the increase of Gr sheet resistance (from ∼300 Ω/sq in pristine Gr to ∼1100 Ω/sq after Al2O3 deposition). Analysis of the transfer characteristics of Gr field-effect transistors (GFETs) allowed us to evaluate the relative dielectric permittivity (ε = 7.45) and the breakdown electric field (EBD = 7.4 MV/cm) of the Al2O3 film as well as the transconductance and the holes field-effect mobility (∼1200 cm2 V-1 s-1). A special focus has been given to the electrical characterization of the Al2O3-Gr interface by the analysis of high frequency capacitance-voltage measurements, which allowed us to elucidate the charge trapping and detrapping phenomena due to near-interface and interface oxide traps.

Metal-Organic Chemical Vapor Deposition (MOCVD) Synthesis of Heteroepitaxial Pr0.7Ca0.3MnO3 Films: Effects of Processing Conditions on Structural/Morphological and Functional Properties.

Calcium-doped praseodymium manganite films (Pr0.7Ca0.3MnO3, PCMO) were prepared by metal-organic chemical vapor deposition (MOCVD) on SrTiO3 (001) and SrTiO3 (110) single-crystal substrates. Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial PCMO phase films. Energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS) characterization was used to confirm lateral and vertical composition and the purity of the deposited films. Magnetic measurements, obtained in zero-field-cooling (ZFC) and field-cooling (FC) modes, provided evidence of the presence of a ferromagnetic (FM) transition temperature, which was correlated to the transport properties of the film. The functional properties of the deposited films, combined with the structural and chemical characterization collected data, indicate that the MOCVD approach represents a suitable route for the growth of pure, good quality PCMO for the fabrication of novel spintronic devices.