The impact of focused ion beam induced damage on scanning spreading resistance microscopy measurements.

Scanning Spreading Resistance Microscopy is a well-established technique for obtaining quantitative two- and three-dimensional carrier profiles in semiconductor devices with sub-nm spatial resolution. However, for sub-100 nm devices, the use of focused ion beam becomes inevitable for exposing the region of interest on a sample cross section. In this work, we investigate the impact of the focused ion beam milling on spreading resistance analysis and we show that the electrical effect of the focused ion beam extends far beyond the amorphous region and depends on the dopant concentration, ion beam energy, impact angle, and current density. For example, for dopant concentrations between 1.0 × 1020 and 1.5 × 1016 cm-3 we observe dopant deactivation at least between 23 and 175 nm for a glancing 30 keV ion beam. Further, we show that dopant deactivation is caused by defect diffusion during milling and is not directly impacted by the presence of Gallium in the sample. Later, we also discuss potential ways to mitigate these effects.

Ferroelectricity in Si-Doped Hafnia: Probing Challenges in Absence of Screening Charges.

The ability to develop ferroelectric materials using binary oxides is critical to enable novel low-power, high-density non-volatile memory and fast switching logic. The discovery of ferroelectricity in hafnia-based thin films, has focused the hopes of the community on this class of materials to overcome the existing problems of perovskite-based integrated ferroelectrics. However, both the control of ferroelectricity in doped-HfO2 and the direct characterization at the nanoscale of ferroelectric phenomena, are increasingly difficult to achieve. The main limitations are imposed by the inherent intertwining of ferroelectric and dielectric properties, the role of strain, interfaces and electric field-mediated phase, and polarization changes. In this work, using Si-doped HfO2 as a material system, we performed a correlative study with four scanning probe techniques for the local sensing of intrinsic ferroelectricity on the oxide surface. Putting each technique in perspective, we demonstrated that different origins of spatially resolved contrast can be obtained, thus highlighting possible crosstalk not originated by a genuine ferroelectric response. By leveraging the strength of each method, we showed how intrinsic processes in ultrathin dielectrics, i.e., electronic leakage, existence and generation of energy states, charge trapping (de-trapping) phenomena, and electrochemical effects, can influence the sensed response. We then proceeded to initiate hysteresis loops by means of tip-induced spectroscopic cycling (i.e., "wake-up"), thus observing the onset of oxide degradation processes associated with this step. Finally, direct piezoelectric effects were studied using the high pressure resulting from the probe's confinement, noticing the absence of a net time-invariant piezo-generated charge. Our results are critical in providing a general framework of interpretation for multiple nanoscale processes impacting ferroelectricity in doped-hafnia and strategies for sensing it.

Carrier profiling with fast Fourier transform scanning spreading resistance microscopy: A case study for Ge, GaAs, InGaAs, and InP.

Quantitative scanning spreading resistance microscopy is currently a powerful method for carrier profiling in scaled nanoelectronic devices. Faced with the further reduction of dimensions and increasing architecture complexity, a force modulation method was developed to address the challenges associated with parasitic series resistances. Called fast Fourier transform scanning spreading resistance microscopy, the method has been shown to increase dynamic range when profiling Si devices and retains the doping contrast even in the presence of a series resistance. In this work we systematically investigate the potential of fast Fourier transform scanning spreading resistance microscopy for Ge, GaAs, InP, and InGaAs, presenting a quantitative comparison with Si as well as a more in-depth understanding of the capabilities and limitations of the method. Our results show that both GaAs and InP greatly benefit, with a significantly larger dynamic range and the ability to filter undesired series resistances. Doping concentration contrast in the presence of a series resistance can also be maintained in Ge but with high noise. For InGaAs there are only minor benefits. These findings prove that fast Fourier transform scanning spreading resistance microscopy is a valuable extension to regular scanning spreading resistance microscopy for more accurate carrier profiling in Si and non-Si materials, especially in architectures where parasitic series resistances are present.

Effects of buried grain boundaries in multilayer MoS2.

Two-dimensional transition metal dichalcogenides have been the focus of intense research for their potential application in novel electronic and optoelectronic devices. However, growth of large area two-dimensional transition metal dichalcogenides invariably leads to the formation of grain boundaries that can significantly degrade electrical transport by forming large electrostatic barriers. It is therefore critical to understand their effect on the electronic properties of two-dimensional semiconductors. Using MoS2 as an example material, we are able to probe grain boundaries in top and buried layers using conductive atomic force microscopy. We find that the electrical radius of the grain boundary extends approximately 2 nm from the core into the pristine material. The presence of grain boundaries affects electrical conductivity not just within its own layer, but also in the surrounding layers. Therefore, electrical grain size is always smaller than the physical size, and decreases with increasing thickness of the MoS2. These results signify that the number of layers in synthetically grown 2D materials must ideally be limited for device applications.

Revealing the 3-dimensional shape of atom probe tips by atomic force microscopy.

For the very first time, atomic force microscopy is used to determine quantitatively the 3-dimensional shape of an atom probe tip, which is key towards improved accuracy and understanding of artefacts in atom probe tomography. We have successfully measured by atomic force microscopy the apex and shank region of 3 different atom probe tips, of which two show (severe) deviations from a hemisphere due to either non-uniform laser light absorption or the presence of two different materials. Clearly, our method which overcomes the challenge of aligning two very sharp tips on top of each other, offers new pathways to study physical mechanisms in (laser-assisted) atom probe. It represents an important step towards improved reconstruction algorithms as the image formation in atom probe tomography is based on the intricate link between the tip shape (down to the atomic level), the electric field distribution and the ions' flight path towards the detector. Further on, present reconstruction algorithms solely account for a hemispherical tip shape, which does not hold true for most applications and results in complex artefacts. Therefore our method is an attractive novel approach to assess the 3D tip shape.

Layer-controlled epitaxy of 2D semiconductors: bridging nanoscale phenomena to wafer-scale uniformity.

The rapid cadence of MOSFET scaling is stimulating the development of new technologies and accelerating the introduction of new semiconducting materials as silicon alternative. In this context, 2D materials with a unique layered structure have attracted tremendous interest in recent years, mainly motivated by their ultra-thin body nature and unique optoelectronic and mechanical properties. The development of scalable synthesis techniques is obviously a fundamental step towards the development of a manufacturable technology. Metal-organic chemical vapor deposition has recently been used for the synthesis of large area TMDs, however, an important milestone still needs to be achieved: the ability to precisely control the number of layers and surface uniformity at the nano-to micro-length scale to obtain an atomically flat, self-passivated surface. In this work, we explore various fundamental aspects involved in the chemical vapor deposition process and we provide important insights on the layer-dependence of epitaxial MoS2 film's structural properties. Based on these observations, we propose an original method to achieve a layer-controlled epitaxy of wafer-scale TMDs.

Mesoscopic physical removal of material using sliding nano-diamond contacts.

Wear mechanisms including fracture and plastic deformation at the nanoscale are central to understand sliding contacts. Recently, the combination of tip-induced material erosion with the sensing capability of secondary imaging modes of AFM, has enabled a slice-and-view tomographic technique named AFM tomography or Scalpel SPM. However, the elusive laws governing nanoscale wear and the large quantity of atoms involved in the tip-sample contact, require a dedicated mesoscale description to understand and model the tip-induced material removal. Here, we study nanosized sliding contacts made of diamond in the regime whereby thousands of nm3 are removed. We explore the fundamentals of high-pressure tip-induced material removal for various materials. Changes in the load force are systematically combined with AFM and SEM to increase the understanding and the process controllability. The nonlinear variation of the removal rate with the load force is interpreted as a combination of two contact regimes each dominating in a particular force range. By using the gradual transition between the two regimes, (1) the experimental rate of material eroded on each tip passage is modeled, (2) a controllable removal rate below 5 nm/scan for all the materials is demonstrated, thus opening to future development of 3D tomographic AFM.

Evolution of the structure and chemical state of Pd nanoparticles during the in situ catalytic reduction of NO with H2.

An in-depth understanding of the fundamental structure of catalysts during operation is indispensable for tailoring future efficient and selective catalysts. We report the evolution of the structure and oxidation state of ZrO(2)-supported Pd nanocatalysts (∼5 nm) during the in situ reduction of NO with H(2) using X-ray absorption fine-structure spectroscopy and X-ray photoelectron spectroscopy. Prior to the onset of the reaction (≤120 °C), a NO-induced redispersion of our initial metallic Pd nanoparticles over the ZrO(2) support was observed, and Pd(δ+) species were detected. This process parallels the high production of N(2)O observed at the onset of the reaction (>120 °C), while at higher temperatures (≥150 °C) the selectivity shifts mainly toward N(2) (∼80%). Concomitant with the onset of N(2) production, the Pd atoms aggregate again into large (6.5 nm) metallic Pd nanoparticles, which were found to constitute the active phase for the H(2)-reduction of NO. Throughout the entire reaction cycle, the formation and stabilization of PdO(x) was not detected. Our results highlight the importance of in situ reactivity studies to unravel the microscopic processes governing catalytic reactivity.

Structure, chemical composition, and reactivity correlations during the in situ oxidation of 2-propanol.

Unraveling the complex interaction between catalysts and reactants under operando conditions is a key step toward gaining fundamental insight in catalysis. We report the evolution of the structure and chemical composition of size-selected micellar Pt nanoparticles (∼1 nm) supported on nanocrystalline γ-Al(2)O(3) during the catalytic oxidation of 2-propanol using X-ray absorption fine-structure spectroscopy. Platinum oxides were found to be the active species for the partial oxidation of 2-propanol (<140 °C), while the complete oxidation (>140 °C) is initially catalyzed by oxygen-covered metallic Pt nanoparticles, which were found to regrow a thin surface oxide layer above 200 °C. The intermediate reaction regime, where the partial and complete oxidation pathways coexist, is characterized by the decomposition of the Pt oxide species due to the production of reducing intermediates and the blocking of O(2) adsorption sites on the nanoparticle surface. The high catalytic activity and low onset reaction temperature displayed by our small Pt particles for the oxidation of 2-propanol is attributed to the large amount of edge and corner sites available, which facilitate the formation of reactive surface oxides. Our findings highlight the decisive role of the nanoparticle structure and chemical state in oxidation catalytic reactions.