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.

Nanotechnology for Electronic Materials and Devices.

The historical scaling down of electronics devices is no longer the main goal of the International Roadmap for Devices and Systems [...].

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.

BiFeO3 films doped in the A or B sites: effects on the structural and morphological properties.

Metal-Organic Chemical Vapor Deposition (MOCVD) has been applied to the fabrication of BiFeO3 films undoped and doped with Ba or Ti on SrTiO3 (100) and YSZ (100) substrates. The films have been deposited using a multi-metal source, consisting of the Bi(phenyl)3, Fe(tmhd)3 and Ba(hfa)2 tetraglyme or Ti(tmhd)2(O-iPr)2 (phenyl = -C6H5, H-tmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = iso-propoxide; H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = CH3O(CH2CH2O)4CH3) precursor mixture. The structural and morphological characterization of films has been carried out using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Chemical compositional studies have been performed by energy dispersive X-ray (EDX) analysis. Structural and morphological characterizations point to the formation of homogeneous and flat surfaces for both undoped and doped BiFeO3 films.

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.

Hydroxycinnamic acids loaded in lipid-core nanocapsules.

Ferulic, caffeic, sinapic, and coumaric acids, belonging to the class of hydroxycinnamic acids (HAs), are bioactive polyphenols widespread in the plant kingdom and present in the human diet. Due to their biological properties and effects in the prevention of various diseases associated with oxidative stress, HAs can be exploited for attractive nutraceutical applications. Starting from this and in order to increase bioaccessibility, we encapsulated HAs in lipid-core nanocapsules (NCs) based on a biodegradable and biocompatible poly(ε-caprolactone) polymer. The results showed that nanoparticles loaded with hydroxycinnamic acids (HA-NCs) have diameter of 224-253 nm, encapsulation efficiency of 53-78%, and are stable over time (30 days). In vitro tests evidenced that NCs are able to preserve HAs in the gastric simulated fluid and release them in the intestinal simulated fluid. The delivery system developed could be employed to create novel functional foods.

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.

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.

Calcium copper-titanate thin film growth: tailoring of the operational conditions through nanocharacterization and substrate nature effects.

A novel approach based on a molten multicomponent precursor source has been applied for the MOCVD fabrication of high-quality CaCu(3)Ti(4)O(12) (CCTO) thin films on various substrates. The adopted in situ strategy involves a molten mixture consisting of Ca(hfa)(2).tetraglyme, Ti(tmhd)(2)(O-iPr)(2), and Cu(tmhd)(2) [Hhfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; tetraglyme = 2,5,8,11,14-pentaoxapentadecane; Htmhd = 2,2,6,6-tetramethyl-3,5-heptandione; O-iPr = isopropoxide] precursors. Film structural and morphological characterizations have been carried out by several techniques [X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM)], and in particular the energy filtered TEM mapping and X-ray energy dispersive (EDX) analysis in TEM mode provided a suitable correlation between nanostructural properties of CCTO films and deposition conditions and/or the substrate nature. Correlation between the nanostructure and optical/dielectric properties has been investigated exploiting spectroscopic ellipsometry.

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.

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

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.

Scanning Probe Microscopy on heterogeneous CaCu3Ti4O12 thin films.

The conductive atomic force microscopy provided a local characterization of the dielectric heterogeneities in CaCu3Ti4O12 (CCTO) thin films deposited by MOCVD on IrO2 bottom electrode. In particular, both techniques have been employed to clarify the role of the inter- and sub-granular features in terms of conductive and insulating regions. The microstructure and the dielectric properties of CCTO thin films have been studied and the evidence of internal barriers in CCTO thin films has been provided. The role of internal barriers and the possible explanation for the extrinsic origin of the giant dielectric response in CCTO has been evaluated.

Nanoscale electrical probing of heterogeneous ceramics: the case of giant permittivity calcium copper titanate (CaCu3Ti4O12).

Scanning Probe Microscopy with conductive tips has been used to image and study the dielectric properties of giant permittivity CaCu3Ti4O12 ceramics at the nanoscale. Since measurements are generally carried out on sections of a sample, particular attention has been devoted to possible artefacts due to surface imperfections, such as substantial surface roughness and/or contamination that can result in controversial interpretation, particularly at nanometric spatial dimensions. A reliable surface investigation has been carried out after the definition of both the physical and geometrical unbiased criteria to avoid any artefacts due to surface roughness and/or anomalous tip-sample contact variations. The presence of insulating grain boundaries and the measurement of a depletion layer at the grain-grain boundary interfaces unambiguously demonstrate the relevance of the Internal Barrier Layer Capacitor effect, among all the proposed physical mechanisms, to explain the giant dielectric behaviour. Such imaging provided a clear correlation between the macroscopic dielectric properties and the nanometric structure at the interfaces. Moreover, the "general criteria" for reliable nanoelectrical characterization as well as the related measurement resolution have been defined.

Nanoscale electro-structural characterisation of ohmic contacts formed on p-type implanted 4H-SiC.

This work reports a nanoscale electro-structural characterisation of Ti/Al ohmic contacts formed on p-type Al-implanted silicon carbide (4H-SiC). The morphological and the electrical properties of the Al-implanted layer, annealed at 1700°C with or without a protective capping layer, and of the ohmic contacts were studied using atomic force microscopy [AFM], transmission line model measurements and local current measurements performed with conductive AFM.The characteristics of the contacts were significantly affected by the roughness of the underlying SiC. In particular, the surface roughness of the Al-implanted SiC regions annealed at 1700°C could be strongly reduced using a protective carbon capping layer during annealing. This latter resulted in an improved surface morphology and specific contact resistance of the Ti/Al ohmic contacts formed on these regions. The microstructure of the contacts was monitored by X-ray diffraction analysis and a cross-sectional transmission electron microscopy, and correlated with the electrical results.

Spontaneous self-assembly of water-soluble nucleotide-calixarene conjugates in small micelles coalescing to microspheres.

Spontaneous self-assembly of calix[4]arenes bearing four 2'-deoxythymidine or 2'-deoxyadenosine nucleotide pendants is investigated using (1)H NMR, exchange NMR, and diffusion ordered NMR spectroscopies and dynamic light scattering. In aqueous medium, the nucleotide-calixarene conjugates, by noncovalent interactions involving both nucleobases and calixarene skeleton, form dimers which self-organize in micelles by increasing the concentration. Microscopic images (scanning electron microscopy and transmission electron microscopy) show that the nucleobase affects the aggregate morphology in the solid state.

Template-free and seedless growth of Pt nanocolumns: imaging and probing their nanoelectrical properties.

The electrical conductivity of platinum nanocolumns has been imaged and measured by conductive atomic force microscopy. The successful syntheses of well-aligned 100-oriented Pt nanocolumns on both random and oriented substrates have been carried out via a simple and seedless metal-organic chemical vapor deposition process. Control of the crystalline quality has been achieved by carefully selecting operational conditions. The growth mechanism, depending on deposition parameters (including deposition temperature, oxygen partial pressures, deposition time, and substrate nature), has been examined in detail.

Recent advances in characterization of CaCu3Ti4O12 thin films by spectroscopic ellipsometric metrology.

CaCu3Ti4O12 (CCTO) thin films were successfully grown on LaAlO3(100) and Pt/TiO2/SiO2/Si(100) substrates by a novel MOCVD approach. Epitaxial CCTO(001) thin films have been obtained on LaAlO3(100) substrates, while polycrystalline CCTO films have been grown on Pt/TiO2/SiO2/Si(100) substrates. Surface morphology and grain size of the different nanostructured deposited films were examined by AFM, and spectroscopic ellipsometry has been used to investigate the electronic part of the dielectric constant (epsilon2). Looking at the epsilon2 curves, it can be seen that by increasing the film structural order, a greater dielectric response has been obtained. The measured dielectric properties accounted for the ratio between grain volumes and grain boundary areas, which is very different in the different structured films.