We investigate the evolution of the cross-plane thermal conductivity $κ$ of superlattices (SLs) as interfaces change from perfectly abrupt to totally intermixed, by using non-equilibrium molecular dynamics simulations in combination with the spectral heat current calculations. We highlight the role of surface-interdiffusion-driven intermixing by calculating the $κ$ of SLs with changing interface roughness, whose tuning allows for the $κ$ values much lower than the "alloy limit" and the abrupt interface limit in same cases. The interplay between alloy and interface scattering in different frequency ranges provides a physical basis to predict a minimum of thermal conductivity. More specifically, we also explore how the interface roughness affects the thermal conductivities for SLs materials with a broad span of atomic mass and bond strength. In particular, we find that (i) only when the "spacer" thickness of SLs increases up to a critical value the $κ$ of rough SLs can break the corresponding "alloy limit". (ii) Whether the $κ$ changes monotonically as interface roughness strongly depends on the period length and intrinsic behavior of phonon transport for SLs materials. Especially, for the SL with large period length, there exists an optimal interface roughness which can minimize the thermal conductivity. (iii) Surface-interdiffusion-driven intermixing is more effective in achieving the low $κ$ below the alloy limit for SL materials with large mass mismatch than with small one. (iv) It's possible for SLs materials with large lattice mismatch (i.e., bond strength) to design an ideally abrupt interface structure with $κ$ much below the "alloy limit". These results have a clear implications for optimization of thermal transport for heat management and for the development of thermoelectric materials.
The ion-sputtering induced transient enhanced intermixing has been studied by molecular dynamics (MD) simulations in Pt/Ti and its anomalous nature has been explained as a superdiffusive transient enhanced interdiffusion. We find ballistic mixing and a robust mass effect in Pt/Ti. The sum of the square of atomic displacements ($<R^2>$) asymptotically grows nonlinearily and scales as $N^2$ and $\sim t^2$, where $N$ and $t$ are the ion-number fluence and the time of ion-sputtering, respectively. This anomalous behavior explains the high diffusity tail in the concentration profile obtained by Aug…
Molecular dynamics simulation of Al/Ni multilayered foils reveals a range of different reaction pathways depending on the temperature of the reaction. At the highest temperatures Fickian interdiffusion dominates the intermixing process. At intermediate temperatures Ni dissolution into the Al liquid becomes the dominant mechanism for intermixing prior to formation of the B2 intermetallic phase. At lower temperatures the B2 intermetallic forms early in the reaction process precluding both of these mechanisms. Interdiffusion and dissolution activation energies as well as diffusion prefactors are …
We examine the interdiffusion in multicomponent systems using the approach analogically to one developed earlier for description of interdiffusion in binary alloys. This approach in opposite to traditional theory, takes into consideration an active role of vacancies, equilibrium distribution of which is not supposed. In this case, in equations for flux components there are contributions conditioned by vacancy concentration gradient. As the vacancy diffusion coefficient is much larger than those for the components, a counteraction to this process will equalize the fluxes of components and, cons…
A high-throughput experimental approach is presented to extract the anisotropic interdiffusion coefficient by combining information over the composition profiles obtained by the electron probe microanalysis (EPMA) and the grain orientation spectrum by the electron backscatter diffraction (EBSD) on polycrystalline diffusion couples. Following the forward-simulation scheme, the interdiffusion coefficients in grains with diverse orientation are obtained and subsequently used to determine the anisotropic interdiffusion coefficients perpendicular (D_\perp (x)) and parallel (D_\parallel (x)) to the …
The ion-sputtering induced intermixing is studied by molecular dynamics (MD) simulations and by Auger electron spectroscopy depth profiling (AES-DP) analysis in Pt/Ti/Si substrate (Pt/Ti) and Ta/Ti/Pt/Si substrate (Ti/Pt) multilayers. Experimental evidence is found for the asymmetry of intermixing in Pt/Ti and in Ti/Pt. An unexpected enhancement of the injection of the heavy Pt atoms into the Ti substrate is observed both by AES-DP and by MD simulations. In Ti/Pt we get a much weaker interdiffusion than in Pt/Ti. The asymmetry is explained by the backscattering of hyperthermal particles at the…
The problem of estimation of the tracer diffusion coefficients is solved by utilizing a novel tracer-interdiffusion couple technique even in the absence suitable radioisotope of one of the components and absence of reliable thermodynamic parameters. This is demonstrated by generating reliable and reproducible mobility data in the alloys of the Fe-Ga system with a strong composition dependence of the diffusion coefficients. Tracer- (59Fe) and inter-diffusion are simultaneously measured in three couples Fe/Fe-16Ga, Fe/Fe-24Ga and Fe-16Ga/Fe-24Ga at 1143 K. The results obtained for the couples wi…
Tracking atomic-scale interdiffusion in immiscible bimetallic nanoparticles via four-dimensional electron tomography
Beijing National Laboratory for Molecular Sciences, Center for Integrated Spectroscopy, College of Chemistry and Molecular Engineering, Peking University（北京大学化学与分子工程学院集成光谱中心北京分子科学国家实验室）
The different mechanisms involved in the alloying of epitaxial nanocrystals are reported in this letter. Intermixing during growth, surface diffusion and intra-island diffusion were investigated by varying the growth conditions and annealing environments during chemical vapor deposition. The relative importance of each mechanism was evaluated in determining a particular composition profile for dome-shaped Ge:Si (001) islands. For samples grown at a faster rate, intermixing during growth was reduced. Si surface diffusion dominates during H$_2$ annealing whereas Ge surface diffusion and intra-is…
It is shown that the well-known blue-shift of the fundamental absorption edge in as-deposited compositionally modulated amorphous Si/Ge and As6Se94/Se80Te20 multilayers (with periods of 4-8 nm) is further enhanced due to the thermal or laser-induced intermixing of adjacent layers. The laser-induced intermixing process, as supported by experiments and model calculations, can be attributed to both the local heating and photo-effects in As6Se94/Se80Te20 multilayers, while only the thermal effects were observed for Si/Ge multilayers. Structural transformations, based on this enhanced interdiffusio…
Group IV semiconductor alloys and heterostructures such as SiGe, GeSn, Ge/Si and SiGe:C have been widely used and under extensive research for applications in major microelectronic and photonic devices. In the growth and processing of these materials, nanometer scale interdiffusion happens that are generally undesirable for device performance. With higher Ge molar fractions and higher compressive strains, Si-Ge interdiffusion can be much faster than dopant diffusion. However, Si-Ge interdiffusion behaviors have not been well understood until recent years. Much less studies are available for Ge…
We have measured an Ag/Al interface specific resistance, 2AR(Ag/Al)(111) = 1.4 fOhm-m^2, that is twice that predicted for a perfect interface, 50% larger than for a 2 ML 50%-50% alloy, and even larger than our newly predicted 1.3 fOhmm^2 for a 4 ML 50%-50% alloy. Such a large value of 2ARAg/Al(111) confirms a predicted sensitivity to interfacial disorder and suggests an interface greater than or equal to 4 ML thick. From our calculations, a predicted anisotropy ratio, 2AR(Ag/Al)(001)/2AR(Ag/Al)(111), of more then 4 for a perfect interface, should be reduced to less than 2 for a 4 ML interface,…
The estimation of (n-1)2 interdiffusion coefficients in an n component system requires (n-1) diffusion paths to intersect or pass closely in the (n-1) dimensional space according to the body diagonal diffusion couple method. These interdiffusion coefficients are related to n(n-1) intrinsic (or n tracer diffusion coefficients), which cannot be estimated easily following the Kirkendall marker experiment in a multicomponent system despite their importance for understanding the atomic mechanism of diffusion and the physico-mechanical properties of materials. In this study, the estimation of tracer…
We describe epitaxial Ge/Si multilayers with cross-plane thermal conductivities which can be systematically reduced to exceptionally low values, as compared both with bulk and thin-film SiGe alloys of the same average concentration, by simply changing the thicknesses of the constituent layers. Ab initio calculations reveal that partial interdiffusion of Ge into the Si spacers, which naturally results from Ge segregation during growth, plays a determinant role, lowering the thermal conductivity below what could be achieved without interdiffusion (perfect superlattice), or with total interdiffus…
Many of the purported virtues of Multi-Principal Element Alloys (MPEAs), such as corrosion, high-temperature oxidation and irradiation resistance, are highly sensitive to vacancy diffusivity. Similarly, solute interdiffusion is governed by vacancy diffusion -- it is often unclear whether MPEAs are truly stable, or effectively stabilized by slow interdiffusion. The considerable composition space afforded to these alloys makes optimizing for desired properties a daunting task; theoretical and computational tools are necessary to guide alloy development. For diffusion, such tools depend on both a…
The diffusion kinetics in a CoCrFeMnNi high entropy alloy is investigated by a combined radiotracer--interdiffusion experiment applied to a pseudo-binary Co$_{15}$Cr$_{20}$Fe$_{20}$Mn$_{20}$Ni$_{25}$ / Co$_{25}$Cr$_{20}$Fe$_{20}$Mn$_{20}$Ni$_{15}$ couple. As a result, the composition-dependent tracer diffusion coefficients of Co, Cr, Fe and Mn are determined. The elements are characterized by significantly different diffusion rates, with Mn being the fastest element and Co being the slowest one. The elements having originally equiatomic concentration through the diffusion couple are found to r…
Using the first-principles non-equilibrium Green's function technique with supercell disorder averaging, we study the influence of interfacial intermixing on the spin-orbit torque in Co$\mid$Pt bilayers. Intermixing is modeled by inserting one or more monolayers of a disordered CoPt alloy between Co and Pt. Dampinglike torque is moderately enhanced by interfacial intermixing, while the fieldlike torque, which is small for abrupt interfaces, is strongly enhanced and becomes comparable to the dampinglike torque. The enhancement of the fieldlike torque is attributed to the interface between Co an…
Femtosecond laser excitation of a Co/Pt bilayer results in the efficient emission of picosecond THz pulses. Two known mechanisms for generating THz emission are spin-polarized currents through a Co/Pt interface, resulting in helicity-independent electric currents in the Pt layer due to the inverse spin-Hall effect and helicity-dependent electric currents at the Co/Pt interface due to the inverse spin-orbit torque effect. Here we explore how roughness, crystal structure and intermixing at the Co/Pt interface affect the efficiency of the THz emission. In particular, we varied the roughness of th…
The Al-Ga intermixing at Al(Ga)N/GaN interfaces in nanowires and the chemical inhomogeneity in AlxGa1-xN/AlN nanodisks (NDs) are attributed to the strain relaxation process. This interpretation is supported by the three-dimensional strain distribution calculated by minimizing the elastic energy in the structure. The alloy inhomogeneity increases with Al content, leading to enhanced carrier localization signatures in their optical characteristics i.e. red shift of the emission, s-shaped temperature dependence and linewidth broadening. Despite these alloy fluctuations, the emission energy of AlG…
Transport phenomena are studied for a binary (AB) alloy on a rigid square lattice with nearest-neighbor attraction between unlike particles, assuming a small concentration $c_v$ of vacancies $V$ being present, to which $A(B)$ particles can jump with rates $Γ_A (Γ_B)$ in the case where the nearest neighbor attractive energy $ε_{AB}$ is negligible in comparison with the thermal energy $k_BT$ in the system. This model exhibits a continuous order-disorder transition for concentrations $c_A,c_B=1-c_A-c_V$ in the range $c_{A,1}^{crit}\leq c_A \leq c_{A,2}^{crit}$, with $c_{A,1}^{crit}=(1-m^*-c_V)/2$…
Barrier-channel intermixing and 2-dimensional electron gas degradation in Al-rich Al(Ga)N/AlGaN high electron mobility transistor heterostructures
Tyndall National Institute, University College Cork（廷德尔国家研究所，科克大学）；James Watt School of Engineering, University of Glasgow（詹姆斯·瓦特工程学院，格拉斯哥大学）；School of Physics, University College Cork（物理学院，科克大学）；School of Engineering, University College Cork（工程学院，科克大学）
The temporal interface microstructure and diffusion in the diffusion couples with the mutual interactions of temperature gradient, concentration difference and initial aging time of the alloys were studied by phase-field simulation, the diffusion couples are produced by the initial aged spinodal alloys with different compositions. Temporal composition evolution and volume fraction of the separated phase indicates the element diffusion direction through the interface under the temperature gradient. The increased temperature gradient induces a wide single-phase region at two sides of the interfa…
Germanium-Tin (GeSn) alloys have emerged as a promising material for future optoelectronics, energy harvesting and nanoelectronics owing to their direct bandgap and compatibility with existing Si-based electronics. Yet, their metastability poses significant challenges calling for in-depth investigations of their thermal behavior. With this perspective, this work addresses the interdiffusion processes throughout thermal annealing of pseudomorphic GeSn binary and SiGeSn ternary alloys. In both systems, the initially pseudomorphic layers are relaxed upon annealing exclusively via thermally induce…
In the present work, it is shown that the surface preparation method used on two Ni-based superalloys prior to aluminizing chemical vapor deposition (CVD) is one of the most important factors determining the oxidation resistance of aluminized Ni-based superalloys. It was found that grit blasting the substrate surface negatively affects the oxidation resistance of the aluminized coatings. For grit blasted and aluminized IN 625, a thicker outer NiAl coating was formed compared to that of IN 738. In contrast, no effect on NiAl coating thickness was found for grit blasted and aluminized IN 738. Ho…
Application of transition metal dichalcogenides (TMDC) in photonic, optoelectronic or valleytronic devices requires the growth of continuous monolayers, heterostructures and alloys of different materials in a single process. We present a facile pulsed thermal deposition method which provides precise control over layer thickness and stoichiometry of two-dimensional systems. The versatility of the method is demonstrated on ternary monolayers of Mo$_{1-x}$W$_{x}$S$_{2}$ and on heterostructures combining metallic TaS$_{2}$ and semiconducting MoS$_{2}$ layers. The fabricated ternary monolayers cove…
Power semiconductor device architectures require the inclusion of a diffusion barrier to suppress, or at best prevent the interdiffusion between the copper metallisation interconnects and the surrounding silicon substructure. The binary pseudo-alloy of titanium-tungsten (TiW), with $>$70~at.\% W, is a well established copper diffusion barrier but is prone to degradation via the out-diffusion of titanium when exposed to high temperatures ($\geq$400$^\circ$C). Here, the thermal stability of physical vapour deposited (PVD) TiW/Cu bilayer thin films in Si/SiO\textsubscript{2}(50~nm)/TiW(300~nm)/Cu…
Cross-sectional helium irradiation reveals interface-controlled bubble evolution in Cr/CrAlSiN multilayer coatings on zirconium alloys
Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences（中国科学院宁波材料技术与工程研究所）；Ningbo University of Technology（宁波工程学院）；Harbin Engineering University（哈尔滨工程大学）；Southwest University of Science and Technology（西南科技大学）；Czech Technical University in Prague（布拉格捷克理工大学）；Qianwan Institute of CNITECH（国创中心千湾研究院）；Advanced Energy Science and Technology Guangdong Laboratory（先进能源科学与技术广东省实验室）；University of Chinese Academy of Sciences（中国科学院大学）；University of Southampton（南安普顿大学）
The growth and microstructural properties of ternary monolayers of two-dimensional hexagonal materials are examined, including both individual two-dimensional crystalline grains and in-plane heterostructures, multijunctions, or superlattices. The study is conducted through the development of a ternary phase field crystal model incorporating sublattice ordering and the coupling among the three atomic components. The results demonstrate that a transition of compositional pattern or modulation in this type of two-dimensional ternary crystals, from phase separation to geometrically frustrated latt…
