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This is FY25 Tritium Science Project report. This report explored the diffusion pathways of 3 H across Ni/NiZr-alloy layer/Zircaloy-4 interfaces under different conditions by including impurities such as Sn and defects such as Zr vacancy in the Zircaloy-4 substrate.
Al{sub 2}O{sub 3}/GeO{sub x}/Ge gate stack fabricated by an in situ cycling ozone oxidation (COO) method in the atomic layer deposition (ALD) system at low temperature is systematically investigated. Excellent electrical characteristics such as minimum interface trap density as low as 1.9 × 10{sup 11 }cm{sup −2 }eV{sup −1} have been obtained by COO treatment. The impact of COO treatment against the band alignment of Al{sub 2}O{sub 3} with respect to Ge is studied by x-ray photoelectron spectroscopy (XPS) and spectroscopic ellipsometry (SE). Based on both XPS and SE studies, the origin of gate leakage in the ALD-Al{sub 2}O{sub 3} is attributed to the sub-gap states, which may be correlated to the OH-related groups in Al{sub 2}O{sub 3} network. It is demonstrated that the COO method is effective in repairing the OH-related defects in high-k dielectrics as well as forming superior high-k/Ge interface for high performance Ge MOS devices.
Here, we demonstrate Ga 1-x In x P compositionally graded buffers (CGBs) grown on GaAs with lattice constants between GaAs and InP by hydride vapor phase epitaxy (HVPE). Growth rates were up to ~1 μm/min and threading dislocation density (TDD) was as low as 1.0 x 10 6 cm -2 . We studied the effect of substrate offcut direction, growth rate, and strain grading rate on CGB defect structure. We compared the effect of a “dynamic grading” style, which creates compositional interfaces via mechanical transfer of a substrate between two growth chambers, vs. “static grading” where the CGB grows in a single chamber. Dynamic grading yielded smoother grades with higher relaxation, but TDD was not significantly different between the two styles. Substrate offcut direction was the most important factor for obtaining CGBs with low defect density. (001) substrates offcut towards (111)B yielded smoother CGBs with lower TDD compared to CGBs grown on substrates offcut towards (111)A. Transmission electron microscopy of static and dynamic CGBs grown on A and B-offcuts only found evidence of phase separation in a static A-offcut CGB, indicating that the B offcut limits phase separation, which in turn keeps TDD low. Reduced growth rate led to the appearance CuPt-type atomic ordering, which affected the distribution of dislocations on the active glide planes but did not alter TDD. Higher growth rates led to smoother CGBs and did not appreciably increase TDD as otherwise predicted by steady-state models of plastic relaxation. These results show HVPE’s promise for lattice-mismatched applications and low-c ost InP virtual substrates on GaAs
Understanding the electronic properties between molybdenum disulfide (MoS{sub 2}) and metal electrodes is vital for the designing and realization of nanoelectronic devices. In this work, influence of intrinsic vacancies in monolayer MoS{sub 2} on the electronic structure and electron properties of Au-MoS{sub 2} contacts is investigated using first-principles calculations. Upon formation of vacancies in monolayer MoS{sub 2}, both tunnel barriers and Schottky Barriers between metal Au and monolayer MoS{sub 2} are decreased. Perfect Au-MoS{sub 2} top contact exhibits physisorption interface with rectifying character, whereas Au-MoS{sub 2} contact with Mo-vacancy shows chemisorption interface with Ohmic character. Partial density of states and electron density of defective Au-MoS{sub 2} top contacts are much higher than those of perfect one, indicating the lower contact resistance and higher electron injection efficiency of defective Au-MoS{sub 2} top contacts. Notably, Mo-vacancy in monolayer MoS{sub 2} is beneficial to get high quality p-type Au-MoS{sub 2} top contact, whereas S-vacancy in monolayer MoS{sub 2} is favorable to achieve high quality n-type Au-MoS{sub 2} top contact. Our results provide guidelines for designing and fabrication of novel 2D nanoelectronic devices.
Graphical abstract: - Highlights: • New concept for providing extended oxidation resistance to Ni-based superalloys. • Oxygen-defective nanostructured oxide coatings reduce the oxygen partial pressure at the substrate interface. • Pre-oxidation of the substrate during annealing with the formation of alpha-alumina. • Growth of CeAlO{sub 3} perovskite enhancing the adherence of the ceria top coat. • Microstructural stability of the coating system with no SRZ formation upon exposure. - Abstract: Aluminide-coated Ni-based superalloys are prone to microstructural instabilities during long-term exposure at high temperature with the growth of a secondary reaction zone (SRZ) detrimental from a mechanical viewpoint. This has been since overcome by the use of thermodynamically stable coatings (γ-Ni/γ′-Ni{sub 3}Al). However, additions of Pt and Hf are required to provide the formation of an exclusive α-Al{sub 2}O{sub 3} scale and improved oxidation resistance in cyclic and isothermal regimes. The present work proposes a new coating system that relies on the use of a superficial nanostructured functional oxide providing the establishment of a stable alumina while avoiding SRZ formation. Tailored oxygen-defective and multi-cracked coatings were designed for 2nd generation Ni-based superalloys and generated by electrosynthesis using a water-based solution. Cyclic oxidation tests were carried out at 1100 °C in air and the oxidation properties and the microstructural stability of the coating system were demonstrated.
Utilization of core–shell rather than monometallic nanocrystals (NCs) facilitates fine-tuning of NC properties for applications. However, compositional evolution via intermixing can degrade these properties prompting recent experimental studies. We develop an atomistic-level stochastic model for vacancy-mediated intermixing exploiting a formalism which allows incorporation at an ab initio density functional theory level of not just the thermodynamics of vacancy formation, but also relevant diffusion barriers for a vast number of possible local environments (in the core and in the shell, at the interface, and in the intermixed phase). This facilitates a predictive treatment and comprehensive understanding of intermixing on the relevant time scale (e.g., 10 1 –10 3 s). In contrast, previous modeling at the atomistic level utilized only unrealistic generic prescriptions of barriers or employed simplified continuum treatments. For Au@Ag octahedral core–cubic shell NCs, our modeling not only captures the experimentally observed rate or time scale for intermixing of ~100 s at 450 °C for 60 nm NCs, but also elucidates the underlying rate controlling processes and the effective intermixing barrier.
A study of the thermally activated negative fixed charges Q{sub tot} and the interface trap densities D{sub it} at the interface between Si and thermal atomic-layer-deposited amorphous Al{sub 2}O{sub 3} layers is presented. The thermal activation of Q{sub tot} and D{sub it} was conducted at annealing temperatures between 220 °C and 500 °C for durations between 3 s and 38 h. The temperature-induced differences in Q{sub tot} and D{sub it} were measured using the characterization method called corona oxide characterization of semiconductors. Their time dependency were fitted using stretched exponential functions, yielding activation energies of E{sub A} = (2.2 ± 0.2) eV and E{sub A} = (2.3 ± 0.7) eV for Q{sub tot} and D{sub it}, respectively. For annealing temperatures from 350 °C to 500 °C, the changes in Q{sub tot} and D{sub it} were similar for both p- and n-type doped Si samples. In contrast, at 220 °C the charging process was enhanced for p-type samples. Based on the observations described in this contribution, a charging model leading to Q{sub tot} based on an electron hopping process between the silicon and Al{sub 2}O{sub 3} through defects is proposed.
Complex oxide interfaces have been one of the central focuses in condensed matter physics and material science. Over the past decade, aberration corrected scanning transmission electron microscopy and spectroscopy has proven to be invaluable to visualize and understand the emerging quantum phenomena at an interface. In this paper, we briefly review some recent progress in the utilization of electron microscopy to probe interfaces. Furthermore, we discuss several important challenges for electron microscopy to advance our understanding on interface phenomena, from the perspective of variable temperature, magnetism, electron energy loss spectroscopy analysis, electronic symmetry, and defects probing.
Nuclear graphite IG-110 and NBG-18 were examined using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscope (SEM) and high resolution transmission electron microscope (HR-TEM) to understand the structure and microstructure of nuclear graphite. The lattice parameter (a), degree of graphitization ( ), crystallite size parallel and perpendicular to c-direction (Lc and L ), anisotropy (B), as well as in-plane crystallite size (La) were calculated and compared based on XRD patterns and Raman spectra. Results indicate that IG-110 has a larger crystallite size and higher degree of graphitization, but lower anisotropy than NBG-18. These differences are attributed to the properties of coke source and manufacturing processes. Additionally, the shape of the pores and crystallized filler particles, the interface between binders and fillers, Mrozowski cracks and nano-cracks, and the defects of disclination were observed and characterized from SEM and HR-TEM images. The similarities and differences in microstructure between IG-110 and NBG-18 are discussed. The results in this work provide useful information to guide selection of nuclear graphite for the design of next generation nuclear plants (NGNP).
High quality GaInAsSb/AlGaAsSb quantum wells (QWs) have been grown by molecular beam epitaxy using proper interface treatments. By controlling the group-V elements at interfaces, we obtained excellent optical quality QWs, which were free from undesired localized trap states, which may otherwise severely affect the exciton recombination. Strong and highly efficient exciton emissions up to room temperature with a wavelength of 2.2 μm were observed. A comprehensive investigation on the QW quality was carried out using temperature dependent and power dependent photoluminescence (PL) measurements. The PL emission intensity remains nearly constant at low temperatures and is free from the PL quenching from the defect induced localized states. The temperature dependent emission energy had a bulk-like behavior, indicating high quality well/barrier interfaces. Because of the uniformity of the QWs and smooth interfaces, the low temperature limit of inhomogeneous line width broadening is as small as 5 meV.
Nanoscale materials modified by crystal defects exhibit significantly different behaviours upon chemical reactions such as oxidation, catalysis, lithiation and epitaxial growth. However, unveiling the exact defect-controlled reaction dynamics (e.g. oxidation) at atomic scale remains a challenge for applications. Here, using in situ high-resolution transmission electron microscopy and first-principles calculations, we reveal the dynamics of a general site-selective oxidation behaviour in nanotwinned silver and palladium driven by individual stacking-faults and twin boundaries. The coherent planar defects crossing the surface exhibit the highest oxygen binding energies, leading to preferential nucleation of oxides at these intersections. Planar-fault mediated diffusion of oxygen atoms is shown to catalyse subsequent layer-by-layer inward oxide growth via atomic steps migrating on the oxide-metal interface. These findings provide an atomistic visualization of the complex reaction dynamics controlled by planar defects in metallic nanostructures, which could enable the modification of physiochemical performances in nanomaterials through defect engineering.
We demonstrate reduced surface recombination velocity (SRV) and enhanced power-conversion efficiency (PCE) in mixed-cation mixed-halide perovskite solar cells by using (3-aminopropyl)trimethoxysilane (APTMS) as a surface passivator. We show the APTMS serves to passivate defects at the perovskite surface, while also decoupling the perovskite from detrimental interactions at the C 60 interface. We measure a SRV of ~125 ± 14 cm/s, and a concomitant increase of ~100 meV in quasi-Fermi level splitting in passivated devices compared to the controls. We use time-resolved photoluminescence and excitation-correlation photoluminescence spectroscopy to show that APTMS passivation effectively suppresses non-radiative recombination. We show that APTMS improves both the fill factor and open-circuit voltage (V OC ), increasing V OC from 1.03 V for control devices to 1.09 V for APTMS-passivated devices, and leads to a PCE increase from 15.90% to 18.03%. Here, we attribute the enhanced performance to reduced defect density resulting in suppressed nonradiative recombination and lower SRV at the perovskite/transport layer interface.
Silicon germanium (SiGe) is a multifunctional material considered for quantum computing, neuromorphic devices, and CMOS transistors. However, implementation of SiGe in nanoscale electronic devices necessitates suppression of surface states dominating the electronic properties. The absence of a stable and passive surface oxide for SiGe results in the formation of charge traps at the SiGe-oxide interface induced by GeOx. In an ideal ALD process in which oxide is grown layer by layer, the GeO x formation should be prevented with selective surface oxidation (i.e., formation of an SiO x interface) by controlling the oxidant dose in the first few ALD cycles of the oxide deposition on SiGe. However, in a real ALD process, the interface evolves during the entire ALD oxide deposition due to diffusion of reactant species through the gate oxide. In this work, this diffusion process in nonideal ALD is investigated and exploited: the diffusion through the oxide during ALD is utilized to passivate the interfacial defects by employing ozone as a secondary oxidant. Periodic ozone exposure during gate oxide ALD on SiGe is shown to reduce the integrated trap density (D it ) across the band gap by nearly 1 order of magnitude in Al 2 O 3 (<6 × 10 10 cm -2 ) and in HfO 2 (<3.9 × 10 11 cm -2 ) by forming a SiO x -rich interface on SiGe. Depletion of Ge from the interfacial layer (IL) by enhancement of volatile GeO x formation and consequent desorption from the SiGe with ozone insertion during the ALD growth process is confirmed by electron energy loss spectroscopy (STEM-EELS) and hypothesized to be the mechanism for reduction of the interfacial defects. In this work, the nanoscale mechanism for defect suppression at the SiGe-oxide interface is demonstrated, which is engineering of diffusion species in the ALD process due to facile diffusion of reactant species in nonideal ALD.
Transistor heterostructures with high-carrier-mobility have been studied. It is shown that, as the {gamma}-irradiation dose {Phi} increases, their degradation occurs in the following sequence. (i) At {Phi} < 10{sup 7} rad, the GaAs surface layer is damaged to a depth of 10 nm due to a >0.2-eV decrease in the diffusion energy of intrinsic defects and, probably, atmospheric oxygen. (ii) At {Phi} > 10{sup 7} rad, highly structurally disordered regions larger than 1 {mu}m are formed near microscopic defects or dislocations. (iii) At {Phi} > 10{sup 8} rad, there occurs degradation of the internal AlGaAs/InGaAs/GaAs interfaces and the working channel. An effective method for studying the degradation processes in heterostructures is to employ a set of structural diagnostic methods to analyze processes of radiation-induced and aging degradation, in combination with theoretical simulation of the occurring processes.
The atomic-resolved reversal of the polarity across an antiphase boundary (APB) was observed in GaSb films grown on Si by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The investigation of the interface structure at the origin of the APB reveals that coalescence of two domains with Ga-prelayer and Sb-prelayer causes the sublattice reversal. The local strain and lattice rotation distributions of the APB, attributed to the discordant bonding length at the APB with the surrounding GaSb lattice, were further studied using the geometric phase analysis technique. The crystallographic characteristics of the APBs and their interaction with other planar defects were observed with HAADF-STEM. The quantitative agreement between experimental and simulated images confirms the observed polarities in the acquired HAADF-STEM data. The self-annihilation mechanism of the APBs is addressed based on the rotation induced by anti-site bonds and APBs' faceting.
Point defects in semiconductors are attractive candidates for quantum information science applications owing to their ability to act as spin-photon interface or single-photon emitters. However, the coupling between the change of dipole moment upon electronic excitation and stray electric fields in the vicinity of the defect, an effect known as Stark shift, can cause significant spectral diffusion in the emitted photons. In this work, using first principles computations, we revisit the methodology to compute the Stark shift of point defects up to the second order. The approach consists of applying an electric field on a defect in a slab and monitoring the changes in the computed zero-phonon line (i.e., difference in energy between the ground and excited state) obtained from constraining the orbital occupations (constrained-DFT). Here, we study the Stark shift of the negatively charged nitrogen-vacancy (NV) center in diamond using this slab approach. We discuss and compare two approaches to ensure a negatively charged defect in a slab and we show that converged values of the Stark shift measured by the change in dipole moment between the ground and excited states (Δμ) can be obtained. We obtain a Stark shift of Δμ = 2.68D using the semilocal GGA-PBE functional and of Δμ = 2.23D using the HSE hybrid functional. These values are in good agreement with experimental results. We also show that modern theory of polarization can be used on constrained-DFT to obtain Stark shifts in very good agreement with the slab computations.
This paper describes the development of a third-generation charge optimized many-body (COMB3) potential for Al-C and its application to the investigation of aluminum/graphene nanostructures. In particular, the new COMB3 potential was used to investigate the interactions of aluminum surfaces with pristine and defective graphene sheets. Classical molecular dynamics simulations were performed at temperatures of 300–900 K to investigate the structural evolution of these interfaces. In this work, the results indicate that, although the interfaces between Al and graphene are mostly weakly bonded, aluminum carbide can form under the right conditions, including the presence of vacancy defects in graphene, undercoordinated Al in surface regions with sharp boundaries, and at high temperatures. COMB3 potentials were further used to examine a new method to transfer graphene between Al surfaces as well as between Al and Cu surfaces by controlling the angle of graphene between the two surfaces. The findings indicate that, by controlling the peeling angles, it is possible to transfer graphene without any damage from the surface having greater graphene/surface adhesion to another surface with less adhesion.
Visualizing molecular crystalline domains and influence of substrate defects are important in understanding the charge transport in organic thin film devices. Vacuum evaporated tetracene films of four monolayers on hydrogen-terminated Si(001)-2x1 substrate, as a prototypical system, have been studied with ex situ atomic force microscopy (AFM), transverse shear microscopy (TSM), friction force microscopy (FFM), and low-energy electron microscopy (LEEM). Two differently oriented in-plane lattice domains are found due to the symmetry of the substrate lattice, with no visible azimuthal twist between adjacent molecular layers in surface islands, indicating significant bulk-like crystallization in the film. Meanwhile, two types of subdomains are observed inside of each in-plane lattice domain. The subdomains are anisotropic in shape, and their sizes and distribution are highly influenced by the substrate atomic steps. TSM and FFM measurements indicate that these subdomains result from molecule-tilt orderings within the bulk-like lattice domains. Lastly, TSM evidently shows a sensitivity to probe vertical molecule-tilt anisotropy for the molecular crystals, in addition to its known ability to map the lateral lattice orientations.