Crystalline defect analysis in epitaxial Si0.7Ge0.3 layer using site-specific ECCI-STEM.

Electron channeling contrast imaging (ECCI) is a powerful technique to characterize the structural defects present in a sample and to obtain relevant statistics about their density. Using ECCI, such defects can only be properly visualized, if the information depth is larger than the depth at which defects reside. Furthermore, a systematic correlation of the features observed by ECCI with the defect nature, confirmed by a complementary technique, is required for defect analysis. Therefore, we present in this paper a site-specific ECCI-scanning transmission electron microscopy (STEM) inspection. Its value is illustrated by the application to a partially relaxed epitaxial Si0.7Ge0.3 on a Si substrate. All experiments including the acquisition of ECCI micrographs, the carbon marking and STEM specimen preparation by focused ion beam, and the in-situ-subsequent-STEM-in-scanning electron microscopy (SEM) characterization were executed in one SEM/FIB-based system, thus significantly improving the analysis efficiency. The ECCI information depth in Si0.7Ge0.3 has been determined through measuring stacking fault widths using different beam energies. ECCI is further utilized to localize the defects for STEM sample preparation and in-situ-subsequent-STEM-in-SEM investigation. This method provides a correlative 2.5D defect analysis from both the surface and cross-section. Using these techniques, the nature of different line-featured defects in epilayers can be classified, as illustrated by our study on Si0.7Ge0.3, which helps to better understand the formation of those detrimental defects.

A chemisorbed interfacial layer for seeding atomic layer deposition on graphite.

The integration of graphene, and more broadly two-dimensional materials, into devices and hybrid materials often requires the deposition of thin films on their usually inert surface. As a result, strategies for the introduction of surface reactive sites have been developed but currently pose a dilemma between robustness and preservation of the graphene properties. A method is reported here for covalently modifying graphitic surfaces, introducing functional groups that act as reactive sites for the growth of high quality dielectric layers. Aryl diazonium species containing tri-methoxy groups are covalently bonded (grafted) to highly oriented pyrolytic graphite (HOPG) and graphene, acting as seeding species for atomic layer deposition (ALD) of Al2O3, a high-κ dielectric material. A smooth and uniform dielectric film growth is confirmed by scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrical measurements. Raman spectroscopy showed that the aryl groups gradually detach from the graphitic surface during the Al2O3 ALD process at 150 °C, with the surface reverting back to the original sp2-hybridized state and without damaging the dielectric layer. Thus, the grafted aryl groups can act as a sacrificial seeding layer after healing the defects of the graphitic surface with annealing treatment.

Engineering Wafer-Scale Epitaxial Two-Dimensional Materials through Sapphire Template Screening for Advanced High-Performance Nanoelectronics.

In view of its epitaxial seeding capability, c-plane single crystalline sapphire represents one of the most enticing, industry-compatible templates to realize manufacturable deposition of single crystalline two-dimensional transition metal dichalcogenides (MX2) for functional, ultrascaled, nanoelectronic devices beyond silicon. Despite sapphire being atomically flat, the surface topography, structure, and chemical termination vary between sapphire terraces during the fabrication process. To date, it remains poorly understood how these sapphire surface anomalies affect the local epitaxial registry and the intrinsic electrical properties of the deposited MX2 monolayer. Therefore, molybdenum disulfide (MoS2) is deposited by metal-organic chemical vapor deposition (MOCVD) in an industry-standard epitaxial reactor on two types of c-plane sapphire with distinctly different terrace and step dimensions. Complementary scanning probe microscopy techniques reveal an inhomogeneous conductivity profile in the first epitaxial MoS2 monolayer on both sapphire templates. MoS2 regions with poor conductivity correspond to sapphire terraces with uncontrolled topography and surface structure. By intentionally applying a substantial off-axis cut angle (1° in this work), the sapphire terrace width and step height-and thus also surface structure-become more uniform across the substrate and MoS2 conducts the current more homogeneously. Moreover, these effects propagate into the extrinsic MoS2 device performance: the field-effect transistor variability reduces both within and across wafers at higher median electron mobility. Carefully controlling the sapphire surface topography and structure proves an essential prerequisite to systematically study and control the MX2 growth behavior and capture the influence on its structural and electrical properties.

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.

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.

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.

Non-destructive characterization of extended crystalline defects in confined semiconductor device structures.

Semiconductor heterostructures are at the heart of most nanoelectronic and photonic devices such as advanced transistors, lasers, light emitting diodes, optical modulators and photo-detectors. However, the performance and reliability of the respective devices are often limited by the presence of crystalline defects which arise from plastic relaxation of misfit strain present in these heterogeneous systems. To date, characterizing the nature and distribution of such defects in 3D nanoscale devices precisely and non-destructively remains a critical metrology challenge. In this paper we demonstrate that electron channeling contrast imaging (ECCI) is capable of analyzing individual dislocations and stacking faults in confined 3D nanostructures, thereby fulfilling the aforementioned requirements. For this purpose we imaged the intensity of electrons backscattered from the sample under test under controlled diffraction conditions using a scanning electron microscope (SEM). In contrast to transmission electron microscopy (TEM) analysis, no electron transparent specimens need to be prepared. This enables a significant reduction of the detection limit (i.e. lowest defect density that can be assessed) as our approach facilitates the analysis of large sampling volumes, thereby providing excellent statistics. We applied the methodology to SiGe nanostructures grown by selective area epitaxy to study in detail how the nature and distribution of crystalline defects are affected by the dimensions of the structure. By comparing our observations with the results obtained using X-ray diffraction, TEM and chemical defect etching, we could verify the validity of the method. Our findings firmly establish that ECCI must be considered the method of choice for analyzing the crystalline quality of 3D semiconductor heterostructures with excellent precision even at low defect densities. As such, the technique aids in better understanding of strain relaxation and defect formation mechanisms at the nanoscale and, moreover, facilitates the development and fabrication of next generation nanoelectronic and photonic devices.

Tomographic Mapping Analysis in the Depth Direction of High-Ge-Content SiGe Layers with Compositionally Graded Buffers Using Nanobeam X-ray Diffraction.

A high-Ge-content Si1-yGey/compositionally graded Si1-xGex-stacked structure grown on Si(001) is now considered to be an important platform for the realization of advanced nanometer-scale complementary metal oxide semiconductor devices with high-mobility channel materials, such as III-V materials and Ge, and monolithically integrated photonic modules. The performance of such advanced devices is critically influenced by crystalline inhomogeneity in the stacked structure; therefore, precise characterization of the crystallinity is important. In particular, the development of a characterization method not only for in-plane crystallinity but also for in-depth crystallinity is strongly required. This is because the crystalline quality of the constant composition Si1-yGey is sensitively dependent on that of the compositionally graded Si1-xGex layers underneath. Here, we have demonstrated in-depth tomographic mapping of a high-Ge-content Si1-yGey/compositionally graded Si1-xGex-stacked structure using position-dependent ω-2θ map measurement using nanobeam X-ray diffraction. This mapping technique is based on the correspondence of each 2θ value in the ω-2θ map to the lattice constant of stacked layers in the depth direction. Application of the proposed analytical procedure provides tomographic maps of the local variation in lattice plane tilting (VLPT) from the obtained ω-2θ maps. It is quantitatively verified that the local crystallinity in the layer at a certain depth is strongly influenced by that underneath the layer. The correlation between the local VLPT and real structural defects in the stacked structure is also discussed in detail.

Two-dimensional WS2 nanoribbon deposition by conversion of pre-patterned amorphous silicon.

We present a method for area selective deposition of 2D WS2 nanoribbons with tunable thickness on a dielectric substrate. The process is based on a complete conversion of a pre-patterned, H-terminated Si layer to metallic W by WF6, followed by in situ sulfidation by H2S. The reaction process, performed at 450 °C, yields nanoribbons with lateral dimension down to 20 nm and with random basal plane orientation. The thickness of the nanoribbons is accurately controlled by the thickness of the pre-deposited Si layer. Upon rapid thermal annealing at 900 °C under inert gas, the WS2 basal planes align parallel to the substrate.

Observation of surface Dirac cone in high-quality ultrathin epitaxial Bi2Se3 topological insulator on AlN(0001) dielectric.

Bi2Se3 topological insulators (TIs) are grown on AlN(0001)/Si(111) substrates by molecular beam epitaxy. In a one-step growth at optimum temperature of 300 °C, Bi2Se3 bonds strongly with AlN without forming interfacial reaction layers. This produces high epitaxial quality Bi2Se3 single crystals with a perfect registry with the substrate and abrupt interfaces, allowing thickness scaling down to three quintuple layers (QL) without jeopardizing film quality. It is found by angle-resolved photoelectron spectroscopy that, remarkably, Bi2Se3 films maintain the 3D TI properties at very low thickness of 3QL (∼2.88 nm), exhibiting top surface gapless metallic states in the form of a Dirac cone.

Atomic imaging of nucleation of trimethylaluminum on clean and H2O functionalized Ge(100) surfaces.

The direct reaction of trimethylaluminum (TMA) on a Ge(100) surface and the effects of monolayer H(2)O pre-dosing were investigated using ultrahigh vacuum techniques, such as scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). At room temperature (RT), a saturation TMA dose produced 0.8 monolayers (ML) of semi-ordered species on a Ge(100) surface due to the dissociative chemisorption of TMA. STS confirmed the chemisorption of TMA passivated the bandgap states due to dangling bonds. By annealing the TMA-dosed Ge surface, the STM observed coverage of TMA sites decreased to 0.4 ML at 250 °C, and to 0.15 ML at 450 °C. XPS analysis showed that only carbon content was reduced during annealing, while the Al coverage was maintained at 0.15 ML, consistent with the desorption of methyl (-CH(3)) groups from the TMA adsorbates. Conversely, saturation TMA dosing at RT on the monolayer H(2)O pre-dosed Ge(100) surface followed by annealing at 200 °C formed a layer of Ge-O-Al bonds with an Al coverage a factor of two greater than the TMA only dosed Ge(100), consistent with Ge-OH activation of TMA chemisorption and Ge-H blocking of CH(3) chemisorption. The DFT shows that the reaction of TMA has lower activation energy and is more exothermic on Ge-OH than Ge-H sites. It is proposed that the H(2)O pre-dosing enhances the concentration of adsorbed Al and forms thermally stable Ge-O-Al bonds along the Ge dimer row which could serve as a nearly ideal atomic layer deposition nucleation layer on Ge(100) surface.