Gabriele Fisichella

Microscopic mechanisms of graphene electrolytic delamination from metal substrates

In this paper, hydrogen bubbling delamination of graphene (Gr) from copper using a strong electrolyte (KOH) water solution was performed, focusing on the effect of the KOH concentration (CKOH) on the Gr delamination rate. A factor of ∼10 decrease in the time required for the complete Gr delamination from Cu cathodes with the same geometry was found increasing CKOH from ∼0.05 M to ∼0.60 M. After transfer of the separated Gr membranes to SiO2 substrates by a highly reproducible thermo-compression printing method, an accurate atomic force microscopy investigation of the changes in Gr morphology as a function of CKOH was performed. Supported by these analyses, a microscopic model of the delamination process has been proposed, where a key role is played by graphene wrinkles acting as nucleation sites for H2 bubbles at the cathode perimeter. With this approach, the H2 supersaturation generated at the electrode for different electrolyte concentrations was estimated and the inverse dependence of td on CKOH was quantitatively explained. Although developed in the case of Cu, this analysis is generally valid and can be applied to describe the electrolytic delamination of graphene from several metal substrates.

From Schottky to Ohmic graphene contacts to AlGaN/GaN heterostructures: Role of the AlGaN layer microstructure

The electrical behaviour of graphene (Gr) contacts to AlxGa1−xN/GaN heterostructures has been investigated, focusing, in particular, on the impact of the AlGaN microstructure on the current transport at Gr/AlGaN interface. Two Al0.25Ga0.75N/GaN heterostructures with very different quality in terms of surface roughness and defectivity, as evaluated by atomic force microscopy (AFM) and transmission electron microscopy, were compared in this study, i.e., a uniform and defect-free sample and a sample with a high density of typical V-defects, which locally cause a reduction of the AlGaN thickness. Nanoscale resolution current voltage (I-V) measurements by an Au coated conductive AFM tip were carried out at several positions both on the bare and Gr-coated AlGaN surfaces. Rectifying contacts were found onto both bare AlGaN surfaces, but with a more inhomogeneous and lower Schottky barrier height (ΦB ≈ 0.6 eV) for AlGaN with V-defects, with respect to the case of the uniform AlGaN (ΦB ≈ 0.9 eV). Instead, very dif...

Micro- and nanoscale electrical characterization of large-area graphene transferred to functional substrates

Summary Chemical vapour deposition (CVD) on catalytic metals is one of main approaches for high-quality graphene growth over large areas. However, a subsequent transfer step to an insulating substrate is required in order to use the graphene for electronic applications. This step can severely affect both the structural integrity and the electronic properties of the graphene membrane. In this paper, we investigated the morphological and electrical properties of CVD graphene transferred onto SiO2 and on a polymeric substrate (poly(ethylene-2,6-naphthalene dicarboxylate), briefly PEN), suitable for microelectronics and flexible electronics applications, respectively. The electrical properties (sheet resistance, mobility, carrier density) of the transferred graphene as well as the specific contact resistance of metal contacts onto graphene were investigated by using properly designed test patterns. While a sheet resistance R sh ≈ 1.7 kΩ/sq and a specific contact resistance ρc ≈ 15 kΩ·μm have been measured for graphene transferred onto SiO2, about 2.3× higher R sh and about 8× higher ρc values were obtained for graphene on PEN. High-resolution current mapping by torsion resonant conductive atomic force microscopy (TRCAFM) provided an insight into the nanoscale mechanisms responsible for the very high ρc in the case of graphene on PEN, showing a ca. 10× smaller “effective” area for current injection than in the case of graphene on SiO2.

Ambipolar MoS2 Transistors by Nanoscale Tailoring of Schottky Barrier Using Oxygen Plasma Functionalization

One of the main challenges to exploit molybdenum disulfide (MoS2) potentialities for the next-generation complementary metal oxide semiconductor (CMOS) technology is the realization of p-type or ambipolar field-effect transistors (FETs). Hole transport in MoS2 FETs is typically hampered by the high Schottky barrier height (SBH) for holes at source/drain contacts, due to the Fermi level pinning close to the conduction band. In this work, we show that the SBH of multilayer MoS2 surface can be tailored at nanoscale using soft O2 plasma treatments. The morphological, chemical, and electrical modifications of MoS2 surface under different plasma conditions were investigated by several microscopic and spectroscopic characterization techniques, including X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), conductive AFM (CAFM), aberration-corrected scanning transmission electron microscopy (STEM), and electron energy loss spectroscopy (EELS). Nanoscale current-voltage mapping by CAFM showed that the SBH maps can be conveniently tuned starting from a narrow SBH distribution (from 0.2 to 0.3 eV) in the case of pristine MoS2 to a broader distribution (from 0.2 to 0.8 eV) after 600 s O2 plasma treatment, which allows both electron and hole injection. This lateral inhomogeneity in the electrical properties was associated with variations of the incorporated oxygen concentration in the MoS2 multilayer surface, as shown by STEM/EELS analyses and confirmed by ab initio density functional theory (DFT) calculations. Back-gated multilayer MoS2 FETs, fabricated by self-aligned deposition of source/drain contacts in the O2 plasma functionalized areas, exhibit ambipolar current transport with on/off current ratio Ion/Ioff ≈ 103 and field-effect mobilities of 11.5 and 7.2 cm2 V-1 s-1 for electrons and holes, respectively. The electrical behavior of these novel ambipolar devices is discussed in terms of the peculiar current injection mechanisms in the O2 plasma functionalized MoS2 surface.

High permittivity cerium oxide thin films on AlGaN/GaN heterostructures

Cerium oxide (CeO2) thin films have been grown by metal-organic chemical vapor deposition on AlGaN/GaN heterostructures and their insulating properties as gate dielectric layer have been explored. The deposited thin films have been found to be textured on the GaN based heterostructures and exhibited a permittivity of 26. This high permittivity value and large band gap are certainly advantageous with respect to other reported materials for the metal insulator semiconductor high electron mobility transistor application. The reduced leakage current density clearly suggests that these CeO2 films are very promising as gate dielectric for AlGaN/GaN transistors low power consumption technology.

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.

Impact of contact resistance on the electrical properties of MoS2 transistors at practical operating temperatures

Molybdenum disulphide (MoS2) is currently regarded as a promising material for the next generation of electronic and optoelectronic devices. However, several issues need to be addressed to fully exploit its potential for field effect transistor (FET) applications. In this context, the contact resistance, R C, associated with the Schottky barrier between source/drain metals and MoS2 currently represents one of the main limiting factors for suitable device performance. Furthermore, to gain a deeper understanding of MoS2 FETs under practical operating conditions, it is necessary to investigate the temperature dependence of the main electrical parameters, such as the field effect mobility (μ) and the threshold voltage (V th). This paper reports a detailed electrical characterization of back-gated multilayer MoS2 transistors with Ni source/drain contacts at temperatures from T = 298 to 373 K, i.e., the expected range for transistor operation in circuits/systems, considering heating effects due to inefficient power dissipation. From the analysis of the transfer characteristics (I D−V G) in the subthreshold regime, the Schottky barrier height (ΦB ≈ 0.18 eV) associated with the Ni/MoS2 contact was evaluated. The resulting contact resistance in the on-state (electron accumulation in the channel) was also determined and it was found to increase with T as R C proportional to T 3.1. The contribution of R C to the extraction of μ and V th was evaluated, showing a more than 10% underestimation of μ when the effect of R C is neglected, whereas the effect on V th is less significant. The temperature dependence of μ and V th was also investigated. A decrease of μ proportional to 1/T α with α = 1.4 ± 0.3 was found, indicating scattering by optical phonons as the main limiting mechanism for mobility above room temperature. The value of V th showed a large negative shift (about 6 V) increasing the temperature from 298 to 373 K, which was explained in terms of electron trapping at MoS2/SiO2 interface states.

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.

In-situ monitoring by Raman spectroscopy of the thermal doping of graphene and MoS2 in O2-controlled atmosphere

The effects of temperature and atmosphere (air and O2) on the doping of monolayers of graphene (Gr) on SiO2 and Si substrates, and on the doping of MoS2 multilayer flakes transferred on the same substrates have been investigated. The investigations were carried out by in situ micro-Raman spectroscopy during thermal treatments up to 430 °C, and by atomic force microscopy (AFM). The spectral positions of the G and 2D Raman bands of Gr undergo only minor changes during treatment, while their amplitude and full width at half maximum (FWHM) vary as a function of the temperature and the used atmosphere. The thermal treatments in oxygen atmosphere show, in addition to a thermal effect, an effect attributable to a p-type doping through oxygen. The thermal broadening of the line shape, found during thermal treatments by in situ Raman measurements, can be related to thermal phonon effects. The absence of a band shift results from the balance between a red shift due to thermal effects and a blue shift induced by doping. This shows the potential of in situ measurements to follow the doping kinetics. The treatment of MoS2 in O2 has evidenced a progressive erosion of the flakes without relevant spectral changes in their central zone during in situ measurements. The formation of MoO3 on the edges of the flakes is observed indicative of the oxygen-activated transformation.

Challenges in graphene integration for high-frequency electronics

This paper provides an overview of the state-of-the-art research on graphene (Gr) for high-frequency (RF) devices. After discussing current limitations of lateral Gr RF transistors, novel vertical devices concepts such as the Gr Base Hot Electron Transistor (GBHET) will be introduced and the main challenges in Gr integration within these architectures will be discussed. In particular, a GBHET device based on Gr/AlGaN/GaN heterostructure will be considered. An approach to the fabrication of this heterostructure by transfer of CVD grown Gr on copper to the AlGaN surface will be presented. The morphological and electrical properties of this system have been investigated at nanoscale by atomic force microscopy (AFM) and conductive atomic force microscopy (CAFM). In particular, local current-voltage measurements by the CAFM probe revealed the formation of a Schottky contact with low barrier height (∼0.41 eV) and excellent lateral uniformity between Gr and AlGaN. Basing on the electrical parameters extracted fr...