Influence of the Emitter Shape on the Field-of-View in Atom Probe Tomography.

Atom probe tomography (APT) is a unique analytical technique that offers three-dimensional elemental mapping with a spatial resolution down to the sub-nanometer. When APT is applied on complex heterogenous systems and/or under certain experimental conditions, that is, laser illumination, the specimen shape can deviate from an ideal hemisphere. Insufficient consideration of this aspect can introduce artifacts in the reconstructed dataset, ultimately degrading its spatial accuracy. So far, there has been limited investigation into the detailed evolution of emitter shape and its impact on the field-of-view (FOV). In this study, we numerically and experimentally investigated the FOV for asymmetric emitters and its evolution throughout the analysis depth. Our analysis revealed that, for asymmetric emitters, the ions evaporated from the topmost region of the specimen (summit) project approximately to the detector center. Furthermore, we demonstrated the implications of this finding on the FOV location for asymmetric emitters. Based on our findings, the location of the center of the FOV can deviate from the specimen central axis with an evolution depending on the evolution of the emitter shape. This study highlights the importance of accounting for the specimen shape when developing advanced data reconstruction schemes to enhance spatial resolution and accuracy.

A Bottom-Up Volume Reconstruction Method for Atom Probe Tomography.

This paper describes a reconstruction method for atom probe tomography based on a bottom-up approach accounting for (i) the final tip morphology (which is frequently induced by inhomogeneous evaporation probabilities across the tip surface due to laser absorption, heat diffusion effects, and inhomogeneous material properties), (ii) the limited (and changing) field of view, and (iii) the detector efficiency. The reconstruction starts from the final tip morphology and reverses the evaporation sequence through the pseudo-deposition of defined small reconstruction volumes, which are then stacked together to create the full three-dimensional (3D) tip. The subdivision in small reconstruction volumes allows the scheme to account for the changing tip shape and field of view as evaporation proceeds. Atoms within the same small reconstruction volume are reconstructed at once by placing atoms back onto their possible lattice sites through a trajectory-matching process involving simulated and experimental hit maps. As the ejected ion trajectories are simulated using detailed electrostatic modeling inside the chamber, no simplifications have been imposed on the shape of the trajectories, projection laws, or tip surface. We demonstrate the superior performance of our approach over the conventional reconstruction method (Bas) for an asymmetrical tip shape.

A Correlative ToF-SIMS/SPM Methodology for Probing 3D Devices.

With the continuous miniaturization and increasing complexity of the devices used in nanotechnology, there is a pressing need for characterization techniques with nm-scale 3D-spatial resolution. Unfortunately, techniques like Secondary Ion Mass Spectrometry (SIMS) fail to reach the required lateral resolution. For this reason, new concepts and approaches, including the combination of different complementary techniques, have been developed in over the past years to try to overcome some of the challenges. Beyond the problem of spatial resolution in a 3D SIMS experiment, one is also faced with the impact of changes in topography during the analysis. These are quite difficult to identify because they originate from the different sputter rates of the various materials and or phases in a heterogeneous system and are notorious at the interfaces between organic and inorganic layers. As each of these materials will erode at a different velocity, accurate 3D-analysis will require means to establish a spatially resolved relation between ion bombardment time and depth. Inevitably such a nonhomogeneous erosion will lead to the development of surface topography. The impact of these effects can be overcome provided one can capture the time and spatially dependent surface erosion (velocity) with high spatial resolution during the course of a profiling experiment. Incorporating a Scanning Probe Microscope (SPM) unit which provides topography measurements with high spatial resolution, into a SIMS tool (e.g., Time of Flight (ToF) SIMS) with means to alternate between SPM and SIMS measurements, is one approach to meet that demand for complementary topographical information allowing accurate 3D chemical imaging. In this paper, the result of integrating a SPM module into a ToF-SIMS system is presented illustrating the improvements in 3D data accuracy which can be obtained when analyzing complex 3D-systems.

Size-dependent optical properties of periodic arrays of semiconducting nanolines.

We study the size-dependent optical properties of periodic arrays of semiconducting nanolines in the near-infrared to near-ultraviolet spectral range, where the absorption of the semiconductor increases. Using band structure calculations, we demonstrate that specific dimensions allow the slow down of the light, resulting in an enhanced absorption as compared to bulk material once the extinction coefficient of the semiconductor becomes comparable to its refractive index. Further, the refractive properties of the arrays can be tailored beyond the values of the constituting materials when the extinction coefficient of the semiconductor exceeds its refractive index. To confirm our theoretical findings, we propose a simple semi-analytical model for the light interactions with such structures and validate it with experimental reflectance spectra collected on arrays for the next-generation transistors.

Unravelling stacking order in epitaxial bilayer MX2 using 4D-STEM with unsupervised learning.

Following an extensive investigation of various monolayer transition metal dichalcogenides (MX2), research interest has expanded to include multilayer systems. In bilayer MX2, the stacking order strongly impacts the local band structure as it dictates the local confinement and symmetry. Determination of stacking order in multilayer MX2 domains usually relies on prior knowledge of in-plane orientations of constituent layers. This is only feasible in case of growth resulting in well-defined triangular domains and not useful in-case of closed layers with hexagonal or irregularly shaped islands. Stacking order can be discerned in the reciprocal space by measuring changes in diffraction peak intensities. Advances in detector technology allow fast acquisition of high-quality four-dimensional datasets which can later be processed to extract useful information such as thickness, orientation, twist and strain. Here, we use 4D scanning transmission electron microscopy combined with multislice diffraction simulations to unravel stacking order in epitaxially grown bilayer MoS2. Machine learning based data segmentation is employed to obtain useful statistics on grain orientation of monolayer and stacking in bilayer MoS2.

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.

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.

Imaging the Three-Dimensional Conductive Channel in Filamentary-Based Oxide Resistive Switching Memory.

Filamentary-based oxide resistive memory is considered as a disruptive technology for nonvolatile data storage and reconfigurable logic. Currently accepted models explain the resistive switching in these devices through the presence/absence of a conductive filament (CF) that is described as a reversible nanosized valence-change in an oxide material. During device operation, the CF cycles billion of times at subnanosecond speed, using few tens of microamperes as operating current and thus determines the whole device's performance. Despite its importance, the CF observation is hampered by the small filament size and its minimal compositional difference with the surrounding material. Here we show an experimental solution to this problem and provide the three-dimensional (3D) characterization of the CF in a scaled device. For this purpose we have recently developed a tomography technique which combines the high spatial resolution of scanning probe microscopy with subnanometer precision in material removal, leading to a true 3D-probing metrology concept. We locate and characterize in three-dimensions the nanometric volume of the conductive filament in state-of-the-art bipolar oxide-based devices. Our measurements demonstrate that the switching occurs through the formation of a single conductive filament. The filaments exhibit sizes below 10 nm and present a constriction near the oxygen-inert electrode. Finally, different atomic-size contacts are observed as a function of the programming current, providing evidence for the filament's nature as a defects modulated quantum contact.

Three-dimensional observation of the conductive filament in nanoscaled resistive memory devices.

The basic unit of information in filamentary-based resistive switching memories is physically stored in a conductive filament. Therefore, the overall performance of the device is indissolubly related to the properties of such filament. In this Letter, we report for the first time on the three-dimensional (3D) observation of the shape of the conductive filament. The observation of the filament is done in a nanoscale conductive-bridging device, which is programmed under real operative conditions. To obtain the 3D-information we developed a dedicated tomography technique based on conductive atomic force microscopy. The shape and size of the conductive filament are obtained in three-dimensions with nanometric resolution. The observed filament presents a conical shape with the narrow part close to the inert-electrode. On the basis of this shape, we conclude that the dynamic filament-growth is limited by the cation transport. In addition, we demonstrate the role of the programming current, which clearly influences the physical-volume of the induced conductive filaments.

Three-dimensional doping and diffusion in nano scaled devices as studied by atom probe tomography.

Nowadays, technological developments towards advanced nano scale devices such as FinFETs and TFETs require a fundamental understanding of three-dimensional doping incorporation, activation and diffusion, as these details directly impact decisive parameters such as gate overlap and doping conformality and thus the device performance. Whereas novel doping methods such as plasma doping are presently exploited to meet these goals, their application needs to be coupled with new metrology approaches such as atom probe tomography, which provides the 3D-dopant distribution with atomic resolution. In order to highlight the relevant processes in terms of dopant conformality, 3D-diffusion, dopant activation and dopant clustering, in this paper we report on 3D-doping and diffusion phenomena in silicon FinFET devices. Through the use of atom probe tomography we determine the dopant distribution in a fully completed device which has been doped using the concept of self-regulatory plasma doping (SRPD). We extract the dopant conformality and spatial extent of this doping process and demonstrate that after annealing the resulting 3D-doping profiles and gate overlap are dependent on the details of the plasma doping process. We also demonstrate that the concentration-dependent 3D-diffusion process leads to concentration gradients which are different for the vertical versus the lateral direction. Through a statistical analysis of the dopant atom distributions we can identify dopant clustering in high concentration regions and correlate this with details of the dopant activation and, eventually, the device performance.

Quantification of area-selective deposition on nanometer-scale patterns using Rutherford backscattering spectrometry.

We present a site-specific elemental analysis of nano-scale patterns whereby the data acquisition is based on Rutherford backscattering spectrometry (RBS). The analysis builds on probing a large ensemble of identical nanostructures. This ensures that a very good limit of detection can be achieved. In addition, the analysis exploits the energy loss effects of the backscattered ions within the nanostructures to distinguish signals coming from different locations of the nanostructures. The spectrum deconvolution is based on ion-trajectory calculations. With this approach, we analyse the Ru area-selective deposition on SiO2-TiN line-space patterns with a linewidth of 35 nm and a pitch of 90 nm. We quantify the selectivity and the Ru local areal density on the top versus on the sidewall of the SiO2 lines. The sensitivity to probe ruthenium deposited on the various surfaces is as low as 1013 atoms/cm2. The analysis is quantitative, traceable, and highly accurate thanks to the intrinsic capabilities of RBS.

Field dependent study on the impact of co-evaporated multihits and ion pile-up for the apparent stoichiometric quantification of GaN and AlN.

For atom probe tomography, multihits and any associated ion pile-up are viewed as an "Achilles" heel when trying to establish accurate stoichiometric quantification. A significant reason for multihits and ion pile-up is credited to co-evaporation events. The impact is the underestimation of one or more elements present due to detector inadequacies when the field evaporated ions are spatially and temporally close. Nitride materials, especially GaN and AlN, have been shown to suffer a strong field dependent compositional bias, with N having the characteristics for being a species prone to ion pile-up. In this paper we have explored through field dependent measurements on GaN and AlN the associated impact of co-evaporated multihits and ion pile-up. To achieve this a normal CAMECA electrode along with a specially modified GRID electrode, which was designed to manipulate co-evaporated ions and hence ion pile-up, were employed. From our results and in-depth analysis, any co-evaporation and associated ion pile-up is found to be either very small, or not species dependent. Thus, ion pile-up cannot be attributed as the cause for the significant N underestimation observed in these materials.

Grain-boundary segregation of magnesium in doped cuprous oxide and impact on electrical transport properties.

In this study, we report the segregation of magnesium in the grain boundaries of magnesium-doped cuprous oxide (Cu2O:Mg) thin films as revealed by atom probe tomography and the consequences of the dopant presence on the temperature-dependent Hall effect properties. The incorporation of magnesium as a divalent cation was achieved by aerosol-assisted metal organic chemical vapour deposition, followed by thermal treatments under oxidizing conditions. We observe that, in comparison with intrinsic cuprous oxide, the electronic transport is improved in Cu2O:Mg with a reduction of resistivity to 13.3 ± 0.1 Ω cm, despite the reduction of hole mobility in the doped films, due to higher grain-boundary scattering. The Hall carrier concentration dependence with temperature showed the presence of an acceptor level associated with an ionization energy of 125 ± 9 meV, similar to the energy value of a large size impurity-vacancy complex. Atom probe tomography shows a magnesium incorporation of 5%, which is substantially present at the grain boundaries of the Cu2O.

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.

Application of electron channeling contrast imaging to 3D semiconductor structures through proper detector configurations.

Nowadays electron channeling contrast imaging (ECCI) is widely used to characterize crystalline defects on blanket semiconductors. Its further application in the semiconductor industry is however challenged by the emerging rise of nanoscale 3D heterostructures. In this study, an angular multi-segment detector is utilized in backscatter geometry to investigate the application of ECCI to the defect analysis of 3D semiconductor structures such as III/V nano-ridges. We show that a low beam energy of 5 keV is more favorable and that the dimension of 3D structures characterized by ECCI can be scaled down to ~ 28 nm. Furthermore, the impact of device edges on the collected ECCI image is investigated and correlated with tool parameters and cross-section profiles of the 3D structures. It is found that backscattered electrons (BSE) emitted from the device edge sidewalls and generating the bright edges (edge effects), share a similar angular distribution to those emitted from the surface. We show that the collection of low angle BSEs can suppressed the edge effects, however, at the cost of losing the defect contrast. A positive stage bias suppresses edge effects by removing the inelastically backscattered electrons from the sidewalls, but low loss BSEs from the sidewalls still contribute to the ECCI micrographs. On the other hand, if segments of an angular backscatter (ABS) detector are properly aligned with the nano-ridges, BSEs emitted from the sidewall and the surface can be separated, thus leading to the completely absence of one bright edge on the surface without compromise of the defect contrast. The merging of two such ECCI images reveals the nano-ridge surface without edge effects.

Potential sources of compositional inaccuracy in the atom probe tomography of InxGa1-xAs.

With the objective of applying laser-assisted atom probe tomography to compositional analysis within nanoscale InGaAs devices, experimental conditions that may provide an accurate composition estimate were sought by extensively studying an InGaAs blanket film. Overall, the determined arsenic atomic fraction was found to exhibit an electric field dependent deficiency, which was more pronounced at low field conditions. Although the determined group III site-fraction also showed a (weak) field-dependent deficiency at low field conditions, it remained invariant with analysis conditions and in close agreement with the nominal value at higher field. In this study, we investigate and discuss the mechanisms that could potentially contribute to As underestimation. Given the field dependence observed, the phenomena occurring between low and high field conditions are compared. At low field, the tendency of As to field evaporate in significant amounts as multiply charged cluster ions (Asni+ with n as large as 9 and i = 1,2,3) is shown to be a significant source of compositional inaccuracy. These clusters may lead to peak overlap in the mass spectrum (e.g. the peak at 150 Da may represent As42+ or As2+ or both), thereby creating an uncertainty in the quantification. Emitted clusters may also dissociate with the likelihood of neutral generation and multi-hit losses being non-negligible. Experimental studies and density functional theory calculations are presented to characterize cluster stability and its contribution to measurement uncertainty. Under high field conditions, although fewer clusters are detected and the composition appears more accurate, the emergence of two additional mechanisms, i.e., multi-hits and DC evaporation, may degrade the data quality. The challenges in evaluating the impact of all these loss mechanisms are examined in detail. Finally, we show that for InGaAs under UV illumination, due to the laser-tip interaction, the resulting asymmetric electric field distribution across the apex introduces local atomic fraction variations.

Enhancing the defect contrast in ECCI through angular filtering of BSEs.

In this study, an annular multi-segment backscattered electron (BSE) detector is used in back scatter geometry to investigate the influence of the angular distribution of BSE on the crystalline defect contrast in electron channeling contrast imaging (ECCI). The study is carried out on GaAs and Ge layers epitaxially grown on top of silicon (Si) substrates, respectively. The influence of the BSE detection angle and landing energy are studied to identify the optimal ECCI conditions. It is demonstrated that the angular selection of BSEs exhibits strong effects on defect contrast formation with variation of beam energies. In our study, maximum defect contrast can be obtained at BSE detection angles 53-65° for the investigated energies 5, 10 and 20 keV. In addition, it is found that higher beam energy is favorable to reveal defects with stronger contrast whereas lower energy ( ≤ 5 keV) is favorable for revealing crystalline defects as well as with topographic features on the surface. Our study provides optimal ECCI conditions, and therefore enables a precise and fast detection of threading dislocations in lowly defective materials and nanoscale 3D semiconductor structures where signal to noise ratio is especially important. A comparison of ECCI with BSE and secondary electron imaging further demonstrates the strength of ECCI in term of simultaneous detection of defects and morphology features such as terraces with atomic step heights.

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.

Atom probe of GaN/AlGaN heterostructures: The role of electric field, sample crystallography and laser excitation on quantification.

Scaling and non-planar architectures are key factors helping to advance the semiconductor field. Accurate 3-dimensional atomic scale information is therefore sought but this presents a significant metrology challenge. Atom probe tomography has emerged as a strong candidate to fulfill this role, but before it can be considered an accurate and precise metrology method, numerous difficulties need to be overcome. In this paper we highlight some of these in respect to the analysis of GaN/AlGaN device heterostructures. Although a significant range of conditions for accurate GaN stoichiometric analysis were readily achieved, a more limited range of analysis conditions that yielded an accurate Al site fraction for AlGaN was observed because the Al was typically overestimated. Moreover, the low index planes of the material resulted in pole and zone lines given their lower evaporation fields and are clearly observed on the detector due to related ion trajectory aberrations representative of local field variations present. As a result of the strong compositional bias of GaN analysis with field, the Ga and N concentrations were found to vary by ∼20 at.% over the tip apex. For the AlGaN this variation was smaller (<4 at.%), even for a similar magnitude of tip field variation.

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.