Linearized radially polarized light for improved precision in strain measurements using micro-Raman spectroscopy.

Strain engineering in semiconductor transistor devices has become vital in the semiconductor industry due to the ever-increasing need for performance enhancement at the nanoscale. Raman spectroscopy is a non-invasive measurement technique with high sensitivity to mechanical stress that does not require any special sample preparation procedures in comparison to characterization involving transmission electron microscopy (TEM), making it suitable for inline strain measurement in the semiconductor industry. Indeed, at present, strain measurements using Raman spectroscopy are already routinely carried out in semiconductor devices as it is cost effective, fast and non-destructive. In this paper we explore the usage of linearized radially polarized light as an excitation source, which does provide significantly enhanced accuracy and precision as compared to linearly polarized light for this application. Numerical simulations are done to quantitatively evaluate the electric field intensities that contribute to this enhanced sensitivity. We benchmark the experimental results against TEM diffraction-based techniques like nano-beam diffraction and Bessel diffraction. Differences between both approaches are assigned to strain relaxation due to sample thinning required in TEM setups, demonstrating the benefit of Raman for nondestructive inline testing.

Chemical vapor deposition of monolayer-thin WS2 crystals from the WF6 and H2S precursors at low deposition temperature.

Monolayer-thin WS2 with (0002) texture grows by chemical vapor deposition (CVD) from gas-phase precursors WF6 and H2S at a deposition temperature of 450 °C on 300 mm Si wafers covered with an amorphous Al2O3 starting surface. We investigate the growth and nucleation mechanism during the CVD process by analyzing the morphology of the WS2 crystals. The CVD process consists of two distinct growth regimes. During (i) the initial growth regime, a fast and self-limiting reaction of the CVD precursors with the Al2O3 starting surface forms predominantly monolayer-thin WS2 crystals and AlF3 crystals that completely cover the starting surface. During (ii) the steady-state growth regime, a much slower, anisotropic reaction on the bottom, first WS2 layer proceeds with the next WS2 layer growing preferentially in the lateral dimensions. We propose that the precursor adsorption reaction rate strongly diminishes when the precursors have no more access to the Al2O3 surface as soon as the WS2 layer completely covers the Al2O3 surface and that the WS2 crystal basal planes and AlF3 crystals have a low reactivity for WF6 adsorption at 450 °C. Nonetheless, a second layer of WS2 starts to form before the first WS2 layer completely covers the starting surface, albeit the surface coverage of the second layer is low (<20%, after 25 min of CVD reaction). During the steady-state growth regime, predominantly the WS2 crystals in the second monolayer continue to grow in lateral dimensions up to ∼40 nm. These crystals reach larger lateral dimensions compared to the crystals in the bottom, first layer due to low reactivity for WF6 adsorption on the WS2 basal plane compared to Al2O3. Presumably, they grow laterally by precursor species that adsorb on and diffuse across the WS2 surface, before being incorporated at the more reactive edges of the WS2 crystals in the second layer. Such a process proceeds slowly with only up to 40% surface coverage of the second WS2 layer after 150 min of CVD reaction. The CVD reaction is mediated by the starting surface: WF6 precursor preferentially adsorbs on Al2O3, whereas adsorption is not observed on SiO2. Nevertheless, WS2 grows on SiO2 in close proximity to Al2O3 in 90 nm pitch Al2O3/SiO2 line patterns. Hence, functionalization of the starting surface (e.g., SiO2 with Al2O3) can provide opportunities to grow monolayer-thin WS2 crystals at predetermined locations by selective, lateral growth with tunable crystal size, even at low deposition temperatures.

Laser-assisted atom probe tomography of semiconductors: The impact of the focused-ion beam specimen preparation.

This paper demonstrates the increased light absorption efficiency of semiconducting atom probe tips resulting from focused-ion-beam (FIB) preparation. We use transmission electron microscopy to show that semiconducting tips prepared with FIB are surrounded with an amorphized shell. Photomodulated optical reflectance measurements then provide evidence that FIB-induced damage leads to an increase in both sub- and supra-bandgap light absorption efficiency. Using laser-assisted atom probe tomography (La-APT) measurements, we finally show that, for a nanoscale tip geometry, the laser-induced heating of a tip during La-APT is enhanced by the FIB preparation. We conclude that, upon supra-bandgap illumination, the presence of a FIB-amorphized surface dramatically increases the light-induced heat generation inside semiconducting tips during La-APT. Furthermore, we also deduce that, in the intriguing case of sub-bandgap illumination, the amorphization plays a crucial role in the unexpected light absorption.

Wet-chemical etching of atom probe tips for artefact free analyses of nanoscaled semiconductor structures.

We introduce an innovative specimen preparation method employing the selectivity of a wet-chemical etching step to improve data quality and success rates in the atom probe analysis of contemporary semiconductor devices. Firstly, on the example of an SiGe fin embedded in SiO2 we demonstrate how the selective removal of SiO2 from the final APT specimen significantly improves accuracy and reliability of the reconstructed data. With the oxide removal, we eliminate the origin of shape artefacts, i.e. the formation of a non-hemispherical tip shape, that are typically observed in the reconstructed volume of complex systems. Secondly, using the same approach, we increase success rates to ∼90% for the damage-free, 3D site-specific localization of short (250 nm), vertical Si nanowires at the specimen apex. The impact of the abrupt emitter radius change that is introduced by this specimen preparation method is evaluated as being minor using field evaporation simulation and comparison of different reconstruction schemes. The Ge content within the SiGe fin as well as the 3D boron distribution in the Si NW as resolved by atom probe analysis are in good agreement with TEM/EDS and ToF-SIMS analysis, respectively.

Structural characterization of SnS crystals formed by chemical vapour deposition.

The crystal and defect structure of SnS crystals grown using chemical vapour deposition for application in electronic devices are investigated. The structural analysis shows the presence of two distinct crystal morphologies, that is thin flakes with lateral sizes up to 50 µm and nanometer scale thickness, and much thicker but smaller crystallites. Both show similar Raman response associated with SnS. The structural analysis with transmission electron microscopy shows that the flakes are single crystals of α-SnS with [010] normal to the substrate. Parallel with the surface of the flakes, lamellae with varying thickness of a new SnS phase are observed. High-resolution transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), first-principles simulations (DFT) and nanobeam diffraction (NBD) techniques are employed to characterise this phase in detail. DFT results suggest that the phase is a strain stabilised ß' one grown epitaxially on the α-SnS crystals. TEM analysis shows that the crystallites are also α-SnS with generally the [010] direction orthogonal to the substrate. Contrary to the flakes the crystallites consist of two to four grains which are tilted up to 15° relative to the substrate. The various grain boundary structures and twin relations are discussed. Under high-dose electron irradiation, the SnS structure is reduced and ß-Sn formed. It is shown that this damage only occurs for SnS in direct contact with SiO2 .

Atom probe tomography analysis of SiGe fins embedded in SiO2: Facts and artefacts.

We present atom probe analysis of 40nm wide SiGe fins embedded in SiO2 and discuss the root cause of artefacts observed in the reconstructed data. Additionally, we propose a simple data treatment routine, relying on complementary transmission electron microscopy analysis, to improve compositional analysis of the embedded SiGe fins. Using field evaporation simulations, we show that for high oxide to fin width ratios the difference in evaporation field thresholds between SiGe and SiO2 results in a non-hemispherical emitter shape with a negative curvature in the direction across, but not along the fin. This peculiar emitter shape leads to severe local variations in radius and hence in magnification across the emitter apex causing ion trajectory aberrations and crossings. As shown by our experiments and simulations, this translates into unrealistic variations in the detected atom densities and faulty dimensions in the reconstructed volume, with the width of the fin being up to six-fold compressed. Rectification of the faulty dimensions and density variations in the SiGe fin was demonstrated with our dedicated data treatment routine.

X-ray absorption in pillar shaped transmission electron microscopy specimens.

The dependence of the X-ray absorption on the position in a pillar shaped transmission electron microscopy specimen is modeled for X-ray analysis with single and multiple detector configurations and for different pillar orientations relative to the detectors. Universal curves, applicable to any pillar diameter, are derived for the relative intensities between weak and medium or strongly absorbed X-ray emission. For the configuration as used in 360° X-ray tomography, the absorption correction for weak and medium absorbed X-rays is shown to be nearly constant along the pillar diameter. Absorption effects in pillars are about a factor 3 less important than in planar specimens with thickness equal to the pillar diameter. A practical approach for the absorption correction in pillar shaped samples is proposed and its limitations discussed. The modeled absorption dependences are verified experimentally for pillars with HfO2 and SiGe stacks.

Nucleation and growth mechanisms of Al2O3 atomic layerdeposition on synthetic polycrystalline MoS2.

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) are of great interest for applications in nano-electronic devices. Their incorporation requires the deposition of nm-thin and continuous high-k dielectric layers on the 2D TMDs. Atomic layer deposition (ALD) of high-k dielectric layers is well established on Si surfaces: the importance of a high nucleation density for rapid layer closure is well known and the nucleation mechanisms have been thoroughly investigated. In contrast, the nucleation of ALD on 2D TMD surfaces is less well understood and a quantitative analysis of the deposition process is lacking. Therefore, in this work, we investigate the growth of Al2O3 (using Al(CH3)3/H2O ALD) on MoS2 whereby we attempt to provide a complete insight into the use of several complementary characterization techniques, including X-ray photo-electron spectroscopy, elastic recoil detection analysis, scanning electron microscopy, and time-of-flight secondary ion mass spectrometry. To reveal the inherent reactivity of MoS2, we exclude the impact of surface contamination from a transfer process by direct Al2O3 deposition on synthetic MoS2 layers obtained by a high temperature sulfurization process. It is shown that Al2O3 ALD on the MoS2 surface is strongly inhibited at temperatures between 125°C and 300°C, with no growth occurring on MoS2 crystal basal planes and selective nucleation only at line defects or grain boundaries at MoS2 top surface. During further deposition, the as-formed Al2O3 nano-ribbons grow in both vertical and lateral directions. Eventually, a continuous Al2O3 film is obtained by lateral growth over the MoS2 crystal basal plane, with the point of layer closure determined by the grain size at the MoS2 top surface and the lateral growth rate. The created Al2O3/MoS2 interface consists mainly of van der Waals interactions. The nucleation is improved by contributions of reversible adsorption on the MoS2 basal planes by using low deposition temperature in combination with short purge times. While this results in a more two-dimensional growth, additional H and C impurities are incorporated in the Al2O3 layers. To conclude, our growth study reveals that the inherent reactivity of the MoS2 basal plane for ALD is extremely low, and this confirms the need for functionalization methods of the TMD surface to enable ALD nucleation.

Observation and understanding of anisotropic strain relaxation in selectively grown SiGe fin structures.

The performance of heterogeneous 3D transistor structures critically depends on the composition and strain state of the buffer, channel and source/drain regions. In this paper we used an in-line high resolution x-ray diffraction (HRXRD) tool to study in detail the composition and strain in selectively grown SiGe/Ge fin structures with widths down to 20 nm. For this purpose we arranged fins of identical dimensions into larger arrays which were then analyzed using an x-ray beam several tens of micrometers in size. Asymmetric reciprocal space maps measured both parallel and perpendicular to the fins allowed us to extract the lattice parameters in all three spatial directions. Our results demonstrate an anisotropic in-plane strain state of the selectively grown SiGe buffer in case of narrower fins with significantly reduced relaxation in the direction along the fin. This observation was verified using nano-beam electron diffraction, and is explained based on the reduced probability for dislocation half-loops to evolve in trenches narrower than a few times the critical radius. Moreover, we introduce and discuss in detail a methodology for the determination of the composition in case of an anisotropic in-plane strain state which differs from the procedure commonly used for blanket layers. Our findings verify the importance of in-line HRXRD measurements for process development and monitoring as well as the fundamental study of relaxation and defect formation in confined volumes.

Nanoscopic structural rearrangements of the Cu-filament in conductive-bridge memories.

The electrochemical reactions triggering resistive switching in conductive-bridge resistive random access memory (CBRAM) are spatially confined in few tens of nm(3). The formation and dissolution of nanoscopic Cu-filaments rely on the displacement of ions in such confined volume, and it is driven by the electric field induced ion migration and nanoscaled redox reactions. The stochastic nature of these fundamental processes leads to a large variability of the device performance. In this work, a combination of two- and three-dimensional scanning probe microscopy (SPM) techniques are used to study the conductive filament (CF) formation, rupture and its nanoscopic structural rearrangements. The high spatial confinement of our approach enables to locally induce RS in a confined area and image it in 3D. A conical shape of the CF is consistently observed, indicating that the ion migration is the rate limiting step in the filament formation when using high quality dielectrics as switching layers. The sub-10 nm electrical contact size of the AFM tip is used to study the filament's dissolution and detect the hopping conduction of Cu during the CF rupture. We consistently observe a tunnel gap formation associated with the tip-induced filament reset. Finally, aiming to match the fundamental understanding with the integrated device operations, we apply scalpel SPM to failed memory cells and directly observe the appearance of filament multiplicity as a major source of failures and variability in CBRAM.

Insights into the nanoscale lateral and vertical phase separation in organic bulk heterojunctions via scanning probe microscopy.

Solution processed polymer (donor) and fullerene (acceptor) bulk heterojunctions are widely used as the photo active layer in organic solar cells. Intimate mixing of these two materials is essential for efficient charge separation and transport. Identifying relative positions of acceptor and donor rich regions in the bulk heterojunction with nanometer scale precision is crucial in understanding intricate details of operation. In this work, a combination of Ar(+)2000 gas cluster ion beam and scanning probe microscopy is used to examine the lateral and vertical phase separation within regio-regular poly(3-hexylthiophene)(P3HT):phenyl-C60-butyric acid methyl ester (PCBM) bulk heterojunction. While the Ar(+)2000 gas cluster ion beam is used as a sputter tool to expose the underneath layers, scanning probe microscopy techniques are used to obtain two-dimensional (2D) electrical maps (with sub-2 nm lateral resolution). The electrical mapping is decoded to chemical composition, essentially producing lateral and vertical maps of phase separation. Thermal stress causes large PCBM-rich hillocks to form, and consequently affecting the balance of P3HT:PCBM heterojunctions, hence a negative impact on the efficiency of the solar cell. We further developed a method to analyze the efficiency of exciton dissociation based on the current maps and a loss of 20% in efficiency is observed for thermally degraded samples compared to fresh un-annealed samples.

Outwitting the series resistance in scanning spreading resistance microscopy.

The performance of nanoelectronics devices critically depends on the distribution of active dopants inside these structures. For this reason, dopant profiling has been defined as one of the major metrology challenges by the international technology roadmap of semiconductors. Scanning spreading resistance microscopy (SSRM) has evolved as one of the most viable approaches over the last decade due to its excellent spatial resolution, sensitivity and quantification accuracy. However, in case of advanced device architectures like fins and nanowires a proper measurement of the spreading resistance is often hampered by the increasing impact of parasitic series resistances (e.g. bulk series resistance) arising from the confined nature of the aforementioned structures. In order to overcome this limitation we report in this paper the development and implementation of a novel SSRM mode (fast Fourier transform-SSRM: FFT-SSRM) which essentially decouples the spreading resistance from parasitic series resistance components. We show that this can be achieved by a force modulation (leading to a modulated spreading resistance signal) in combination with a lock-in deconvolution concept. In this paper we first introduce the principle of operation of the technique. We discuss in detail the underlying physical mechanisms as well as the technical implementation on a state-of-the-art atomic force microscope (AFM). We demonstrate the performance of FFT-SSRM and its ability to remove substantial series resistance components in practice. Eventually, the possibility of decoupling the spreading resistance from the intrinsic probe resistance will be demonstrated and discussed.

Field Effect and Strongly Localized Carriers in the Metal-Insulator Transition Material VO(2).

The intrinsic field effect, the change in surface conductance with an applied transverse electric field, of prototypal strongly correlated VO(2) has remained elusive. Here we report its measurement enabled by epitaxial VO(2) and atomic layer deposited high-κ dielectrics. Oxygen migration, joule heating, and the linked field-induced phase transition are precluded. The field effect can be understood in terms of field-induced carriers with densities up to ∼5×10(13) cm(-2) which are trongly localized, as shown by their low, thermally activated mobility (∼1×10(-3) cm(2)/V s at 300 K). These carriers show behavior consistent with that of Holstein polarons and strongly impact the (opto)electronics of VO(2).

Fast Fourier transform scanning spreading resistance microscopy: a novel technique to overcome the limitations of classical conductive AFM techniques.

A new atomic force microscopy (AFM)-based technique named fast Fourier transform scanning spreading-resistance microscopy (FFT-SSRM) has been developed. FFT-SSRM offers the ability to isolate the local spreading resistance (Sr) from the parasitic series resistance (probe, bulk, and back contact). The parasitic series resistance limits the use of classical SSRM in confined volumes and on very highly doped materials, two increasingly important situations in nanoelectronic components. This is realized via a force modulation at controlled frequency (affecting the SR component) and the extraction of the resistance amplitude at the modulation frequency, performing an FFT-based lock-in deconvolution. A systematic evaluation of the FFT-SSRM performances (i.e., resolution, dynamic range, sensitivity, and repeatability) is presented. The impact of various parameters (i.e., modulation frequency and amplitude or cutoff frequency of the current amplifier) on the performances of FFT-SSRM has been evaluated. We demonstrate the possibility to overcome sensitivity losses due to tip saturation in highly doped material and the utility of the technique in two different structures, presenting isolated and confined volumes.

Epitaxial diamond-hexagonal silicon nano-ribbon growth on (001) silicon.

Silicon crystallizes in the diamond-cubic phase and shows only a weak emission at 1.1 eV. Diamond-hexagonal silicon however has an indirect bandgap at 1.5 eV and has therefore potential for application in opto-electronic devices. Here we discuss a method based on advanced silicon device processing to form diamond-hexagonal silicon nano-ribbons. With an appropriate temperature anneal applied to densify the oxide fillings between silicon fins, the lateral outward stress exerted on fins sandwiched between wide and narrow oxide windows can result in a phase transition from diamond-cubic to diamond-hexagonal Si at the base of these fins. The diamond-hexagonal slabs are generally 5-8 nm thick and can extend over the full width and length of the fins, i.e. have a nano-ribbon shape along the fins. Although hexagonal silicon is a metastable phase, once formed it is found being stable during subsequent high temperature treatments even during process steps up to 1050 ºC.

Direct imaging of 3D atomic-scale dopant-defect clustering processes in ion-implanted silicon.

The fabrication of nanoscale semiconductor devices for use in future electronics, energy, and health is among others based on the precise placement of dopant atoms into the crystal lattice of semiconductors and their concurrent or subsequent electrical activation. Dopants are built into the lattice by fabrication processes like ion implantation, plasma-based doping, and thermal annealing. Throughout the fabrication processes fundamental phenomena like dopant diffusion, activation, and clustering occur concurrently with damaging and subsequently recovering the crystal lattice. These processes are described by atomic-scale mechanisms of ion-host atom interaction and have an immense impact on the electrical performance of the resulting devices. Insight in their fundamental nature is of utmost importance for optimizing the performance of nanoscale technologies. In this paper, we demonstrate direct three-dimensional imaging of boron clusters and atoms in crystal defects using field ion microscopy. Our approach allows for the first time the complete characterization of the size and crystallographic orientation of boron-decorated crystal defects. This new method opens a path to image a wide variety of dopant-cluster forms and hence to study the formation and dissolution of boron clusters in silicon on the atomic scale.

Optimal laser positioning for laser-assisted atom probe tomography.

Laser-assisted atom probe tomography is a material analysis method based on field evaporating ions from a tip-shaped sample by a combination of a standing electric field and a short (pico- or femtosecond) laser pulse. The laser-pulse thereby acts as a starting signal for a time-of-flight mass analysis of the ions whereby the thermal energy deposited in the tip by the laser pulse temporarily enables the evaporation of ions from the surface of the tip. Here we will use simulations of the laser absorption on a silicon tip to find the optimal position of the laser spot in order to maximize the mass resolution achieved during the experiments. We will confirm our simulations by showing that the experimentally observed mass resolution indeed changes as predicted by the simulations.

Light absorption in conical silicon particles.

The problem of the absorption of light by a nanoscale dielectric cone is discussed. A simplified solution based on the analytical Mie theory of scattering and absorption by cylindrical objects is proposed and supported by the experimental observation of sharply localized holes in conical silicon tips after high-fluence irradiation. This study reveals that light couples with tapered objects dominantly at specific locations, where the local radius corresponds to one of the resonant radii of a cylindrical object, as predicted by Mie theory.

Quantitative three-dimensional carrier mapping in nanowire-based transistors using scanning spreading resistance microscopy.

The performance of nanoelectronic devices critically depends on the distribution of charge carriers inside such structures. High-vacuum scanning spreading resistance microscopy (HV-SSRM) has established as the method of choice for quantitative 2D-carrier mapping in nanoscale devices during the last decade. However, due to the 3D-nature of these nanoscale device architectures, dopant incorporation and dopant diffusion mechanisms can vary for any of the three dimensions, depending on the particular processes used. Therefore, mapping of carriers in three dimensions with high spatial resolution is inevitable to study and understand the distribution of active dopants in confined 3D-volumes and ultimately to support the process development of next generation devices. In this work, we present for the first time an approach to extend the capabilities of SSRM from an inherent 2D-carrier profiling technique towards a quantitative 3D-characterization technique based on the example of a nanowire (NW)-based heterojunction (SiGe-Si) tunneling transistor. In order to implement a 3D-methodology with a 2D-imaging technique, we acquired 2D-carrier concentration maps on successive cross-section planes through the device of interest. This was facilitated by arranging several devices in a staggered array, allowing to produce a series of cross-sections with incremental offset by a single cleave. A dedicated interpolation algorithm especially suited for structures with rotational symmetry like NWs was developed in order to reconstruct a 3D-carrier distribution map. The validity of the method was assessed by proving the absence of variations in carrier distribution in the third dimension, as expected for NWs etched into a blanket stack.

Electrical tomography using atomic force microscopy and its application towards carbon nanotube-based interconnects.

The fabrication and integration of low-resistance carbon nanotubes (CNTs) for interconnects in future integrated circuits requires characterization techniques providing structural and electrical information at the nanometer scale. In this paper we present a slice-and-view approach based on electrical atomic force microscopy. Material removal achieved by successive scanning using doped ultra-sharp full-diamond probes, manufactured in-house, enables us to acquire two-dimensional (2D) resistance maps originating from different depths (equivalently different CNT lengths) on CNT-based interconnects. Stacking and interpolating these 2D resistance maps results in a three-dimensional (3D) representation (tomogram). This allows insight from a structural (e.g. size, density, distribution, straightness) and electrical point of view simultaneously. By extracting the resistance evolution over the length of an individual CNT we derive quantitative information about the resistivity and the contact resistance between the CNT and bottom electrode.