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Rutile GeO$_2$ is a promising ultra-wide bandgap semiconductor for future power electronic devices whose alloy with the wide bandgap semiconductor rutile-SnO$_2$ enables bandgap engineering and the formation of heterostructure devices. The (Sn$_x$Ge$_{1-x}$)O$_2$ alloy system is in its infancy and molecular beam epitaxy (MBE) is a well-suited technique for its thin-film growth, yet presents challenges in controlling the alloy composition and growth rate. To understand and mitigate this challenge, the present study comprehensively investigates the kinetics and thermodynamics of suboxide incorporation into GeO$_2$, SnO$_2$, and (Sn$_x$Ge$_{1-x}$)O$_2$ during suboxide MBE, the latest development in oxide MBE using suboxide sources. We find suboxide MBE to simplify the growth kinetics, offering better control over growth rates than conventional MBE but without supporting cation-driven oxide layer etching. During binary growth, SnO incorporation is kinetically favored due to its higher oxidation efficiency and lower vapor pressure compared to those of GeO. In (Sn$_x$Ge$_{1-x}$)O$_2$ growth, however, the GeO incorporation is preferred and the SnO incorporation is suppressed, indicating a catalytic effect, where SnO promotes GeO incorporation through cation exchange. The origin of this cation exchange is likely thermodynamic yet calls for further theoretical studies. Our experimental study provides guidance for controlling the growth rate and alloy composition of (Sn$_x$Ge$_{1-x}$)O$_2$ in suboxide MBE, highlighting the impact of the substrate temperature and active oxygen flux besides that of the mere SnO:GeO flux stoichiometry. The results are likely transferable to further physical and chemical vapor deposition methods, such as conventional and hybrid MBE, pulsed laser deposition, mist- or metalorganic chemical vapor deposition.

Its piezo- and potentially ferroelectric properties make the metastable kappa polymorph of Ga$_2$O$_3$ an interesting material for multiple applications, while In-incorporation into any polymorphs of Ga$_2$O$_3$ allows to lower their bandgap. In this work, we provide a guideline to achieve single phase $\kappa$-, $\beta$-Ga$_2$O$_3$ as well as their (In$_x$Ga$_{1-x}$)$_2$O$_3$ alloys up to x = 0.14 and x = 0.17 respectively, using In-mediated metal exchange catalysis in plasma assisted molecular beam epitaxy (MEXCAT-MBE). The polymorph transition from $\kappa$ to $\beta$ is also addressed, highlighting the fundamental role played by the thermal stability of the $\kappa$-Ga$_2$O$_3$. Additionally, we also demonstrate the possibility to grow ($\bar{2}$01) $\beta$-Ga$_2$O$_3$ on top of $\alpha$-Al$_2$O$_3$ (0001) at temperatures at least 100 {\deg}C above those achievable with conventional non-catalyzed MBE, opening the road for increased crystal quality in heteroepitaxy. The role of the substrate, as well as strain and structural defects in the growth of $\kappa$-Ga$_2$O$_3$ is also investigated by growing simultaneously on three different materials: (i) $\alpha$-Al$_2$O$_3$ (0001), (ii) 20 nm of ($\bar{2}$01) $\beta$-Ga$_2$O$_3$ on $\alpha$-Al$_2$O$_3$ (0001) and (iii) ($\bar{2}$01) $\beta$-Ga$_2$O$_3$ single crystal., Comment: Main text: 7 pages, 4 figures; Supplementary: 6 pages, 9 figures

(La and Ga)-doped tin monoxide (stannous oxide, tin (II) oxide, SnO) thin films were grown by plasma-assisted and suboxide molecular beam epitaxy with dopant concentrations ranging from $\approx5\times10^{18}$cm$^{-3}$ to $2\times10^{21}$cm$^{-3}$. In this concentration range, the incorporation of Ga into SnO was limited by the formation of secondary phases observed at $1.2\times10^{21}$cm$^{-3}$ Ga, while the incorporation of La showed a lower solubility limit. Transport measurements on the doped samples reveal that Ga acts as an acceptor and La as a compensating donor. While Ga doping led to an increase of the hole concentration from $1\times10^{18}$cm$^{-3}-1\times10^{19}$cm$^{-3}$ for unintentionally (UID) SnO up to $5\times10^{19}$cm$^{-3}$, La-concentrations well in excess of the UID acceptor concentration resulted in semi-insulating films without detectable $n$-type conductivity. Ab-initio calculations qualitatively agree with our dopant assignment of Ga and La, and further predict In$_\text{Sn}$ to act as an acceptor as well as Al$_\text{Sn}$ and B$_\text{Sn}$ as donor. These results show the possibilities of controlling the hole concentration in $p$-type SnO, which can be useful for a range of optoelectronic and gas-sensing applications., Comment: 6 pages, 5 figures

Models for finite-rate-chemistry in underresolved flows still pose one of the main challenges for predictive simulations of complex configurations. The problem gets even more challenging if turbulence is involved. This work advances the recently developed PIESRGAN modeling approach to turbulent premixed combustion. For that, the physical information processed by the network and considered in the loss function are adjusted, the training process is smoothed, and especially effects from density changes are considered. The resulting model provides good results for a priori and a posteriori tests on direct numerical simulation data of a fully turbulent premixed flame kernel. The limits of the modeling approach are discussed. Finally, the model is employed to compute further realizations of the premixed flame kernel, which are analyzed with a scale-sensitive framework regarding their cycle-to-cycle variations. The work shows that the data-driven PIESRGAN subfilter model can very accurately reproduce direct numerical simulation data on much coarser meshes, which is hardly possible with classical subfilter models, and enables studying statistical processes more efficiently due to the smaller computing cost.

The oxidation-related issues in controlling Si doping from the Si source material in oxide molecular beam epitaxy (MBE) is addressed by using solid SiO as an alternative source material in a conventional effusion cell. Line-of-sight quadrupole mass spectrometry of the direct SiO-flux ($\Phi_{SiO}$) from the source at different temperatures ($T_{SiO}$) confirmed SiO molecules to sublime with an activation energy of 3.3eV. The $T_{SiO}$-dependent $\Phi_{SiO}$ was measured in vacuum before and after subjecting the source material to an O$_{2}$-background of $10^{-5}$ mbar (typical oxide MBE regime). The absence of a significant $\Phi_{SiO}$ difference indicates negligible source oxidation in molecular O$_{2}$. Mounted in an oxygen plasma-assisted MBE, Si-doped $\beta$-Ga2O3 layers were grown using this source. The $\Phi_{SiO}$ at the substrate was evaluated [from 2.9x10$^{9}$ cm$^{-2}$s$^{-1}$ ($T_{SiO}$=700{\deg}C) to 5.5x10$^{13}$ cm$^{-2}$s$^{-1}$ (T$_{SiO}$=1000{\deg}C)] and Si-concentration in the $\beta$-Ga2O3 layers measured by secondary ion mass spectrometry highlighting unprecedented control of continuous Si-doping for oxide MBE, i.e., $N_{Si}$ from 4x10$^{17}$ cm$^{-3}$ ($T_{SiO}$=700{\deg}C) up to 1.7x10$^{20}$ cm$^{-3}$ ($T_{SiO}$=900{\deg}C). For a homoepitaxial $\beta$-Ga2O3 layer an Hall charge carrier concentration of 3x10$^{19}$ cm$^{-3}$ in line with the provided $\Phi_{SiO}$ ($T_{SiO}$=800{\deg}C) is demonstrated. No SiO-incorporation difference was found between $\beta$-Ga2O3(010) layers homoepitaxially grown at 750{\deg}C and $\beta$-Ga2O3(-201) layers heteroepitaxially grown at 550{\deg}C. The presence of activated oxygen (plasma) resulted in partial source oxidation and related decrease of doping concentration (particularly at $T_{SiO}$<800{\deg}C) which has been tentatively explained with a simple model. Degassing the source at 1100{\deg}C reverted the oxidation.

Anisotropic, submicrometer sized particles are versatile systems providing interesting features in creating ordering in 2-dimensional systems. Combining hard ellipsoids with a soft shell further enhances the opportunities to trigger and control order and alignment. In this work, we report a rich 2D phase behavior and show how softness affects the ordering of anisotropic particles at fluid oil-water interfaces. Three different core-shell systems were synthesized such that they have the same elliptical hematite-silica core but differ with respect to thickness and stiffness of the soft microgel shell. Compression isotherms, the shape of individual core-shell microgel as well as their 2D order at a decane-water interface are investigated by means of the Langmuir-Blodgett technique combined with ex-situ Atomic Force Microscopy (AFM) imaging, as well as by Disspiative Particle Dynamics (DPD) simulations. We show how softness, size and anisotropy of the microgel shell affect the side-to-side vs. tip-to-tip ordering of anisotropic hybrid microgels as well as the alignment with respect to the direction of compression in the Langmuir trough. A large and soft microgel shell leads to an ordered structure with a tip-to-tip alignment directed perpendicular to the direction of compression. In contrast, a thin and harder microgel shell leads to side-to-side ordering orientated parallel to the compression direction. In addition, the thin and harder microgel shell induces clustering of the microgels in the dilute state indicating the presence of strong capillary interactions. Our findings highlight the relevance of softness for the complex ordering of anisotropic hybrid microgels at interfaces.

In this work we investigate the growth of $\beta$-Ga2O3 homoepitaxial layers on top of (100) oriented substrates via indium-assisted metal exchange catalyzed molecular beam epitaxy (MEXCAT-MBE) which have exhibited prohibitively low growth rates by non-catalyzed MBE in the past. We demonstrate that the proper tuning of the MEXCAT growth parameters and the choice of a proper substrate offcut allow for the deposition of thin films with high structural quality via step-flow growth mechanism at relatively high growth rates for $\beta$-Ga2O3 homoepitaxy (i.e., around 1.5 nm/min, $\approx$45% incorporation of the incoming Ga flux), making MBE growth on this orientation feasible. Moreover, through the employment of the investigated four different (100) substrate offcuts along the [00-1] direction (i.e., 0$^\circ$, 2$^\circ$, 4$^\circ$, 6$^\circ$) we give experimental evidence on the fundamental role of the (-201) step edges as nucleation sites for growth of (100)-oriented Ga2O3 films by MBE.

Holding promising applications in power electronics, the wide band gap material gallium oxide has emerged as a vital alternative to materials like GaN and SiC. The detailed study of phonon modes in $\beta$-Ga$_{2}$O$_{3}$ provides insights into fundamental material properties such as crystal structure and orientation and can contribute to the identification of dopants and point defects. We investigate the Raman active phonon modes of $\beta$-Ga$_{2}$O$_{3}$ in two different oxygen isotope compositions ($^{16}$O,$^{18}$O) by experiment and theory: By carrying out polarized micro-Raman spectroscopy measurements on the (010) and ($\bar{2}$01) planes, we determine the frequencies of all 15 Raman active phonons for both isotopologues. The measured frequencies are compared with the results of density functional perturbation theory (DFPT) calculations. In both cases, we observe a shift of Raman frequencies towards lower energies upon substitution of $^{16}$O with $^{18}$O. By quantifying the relative frequency shifts of the individual Raman modes, we identify the atomistic origin of all modes (Ga-Ga, Ga-O or O-O) and present the first experimental confirmation of the theoretically calculated energy contributions of O lattice sites to Raman modes. We find that oxygen substitution on the O$_{\mathrm{II}}$ site leads to an elevated relative frequency shift compared to O$_{\mathrm{I}}$ and O$_{\mathrm{III}}$ sites. This study presents a blueprint for the future identification of different point defects in Ga$_{2}$O$_{3}$ by Raman spectroscopy.

From experimental spark ignition (SI) engine studies, it is known that the slow-down of early flame kernel development caused by the ($\mathrm{Le}>1$)-property of common transportation-fuel/air mixtures tends to increase cycle-to-cycle variations (CCV). To improve the fundamental understanding of the complex phenomena inside the flame structure of developing flame kernels, an engine-relevant DNS database is investigated in this work. Conclusive analyses are enabled by considering equivalent flame kernels and turbulent planar flames computed with $\mathrm{Le}>1$ and $\mathrm{Le}=1$. In Part I of the present study (Falkenstein et al., Combust. Flame, 2019), a reduced representation of the local mixture state based on the parameters local enthalpy, local equivalence ratio, and H-radical mass fraction was proposed for the purpose of this analysis. Here, a coupling relation for the diffusion-controlled mixture parameter local enthalpy with local flame geometry and structure is derived, characterized by the key parameters $\kappa$ and ${\ |\nabla c \ t|/\ |\nabla c \ |_{\mathrm{lam}}}$. The analysis shows that the large positive global mean curvature intrinsic to the flame kernel configuration may detrimentally affect the local mixture state inside the reaction zone, particularly during the initial kernel development phase. External energy supply by spark ignition may effectively bridge over this critical stage, which causes the impact of global mean flame kernel curvature to be small under the present conditions compared to the overall effect of $\mathrm{Le}\neq1$. Once ignition effects have decayed, the mixture state inside the reaction zone locally exhibits an identical dependence on $\ |\nabla c \ |$ as in a strained laminar flame. This implies that differential diffusion effects under engine-typical Karlovitz numbers are not weakened by small-scale turbulent mixing.

Although experimental evidence for the correlation between early flame kernel development and cycle-to-cycle variations (CCV) in spark ignition (SI) engines was provided long ago, there is still a lack of fundamental understanding of early flame/turbulence interactions, and accurate models for full engine simulations do not exist. Since the flame kernel is initiated with small size, i.e. with large positive curvature, differential diffusion is expected to severely alter early flame growth in non-unity-Lewis-number (${\mathrm{Le}\neq1}$) mixtures as typically used in engines. In this work, a DNS database of developing iso-octane/air flame kernels and planar flames has been established with flame conditions representative for stoichiometric engine part-load operation. Differential diffusion effects on the global heat release rate are analyzed by relating the present findings to equivalent flames computed in the ${\mathrm{Le}=1}$ limit. It is shown that in the early kernel development phase, the normal propagation velocity is significantly reduced with detrimental consequences on the global burning rate of the flame kernel. Besides this impact on the overall mass burning rate, the initial production of flame surface area by the normal propagation term in the flame area balance equation is noticeably reduced. By using the optimal estimator concept, it is shown that strong fluctuations in local heat release rate inherent to ${\mathrm{Le}\neq1}$ flames in the thin reaction zones regime are mainly contained in the parameters local equivalence ratio, enthalpy, and H-radical mass fraction. Differential diffusion couples the evolution of these parameters to the unsteady flame geometry and structure, which is analyzed in Part II of the present study (Falkenstein et al., Combust. Flame, 2019).