Bond Partners Research Articles

The Synergistic Influence of the Hydrophobic and Hydrophilic Ends on the Primary Dielectric Relaxation Rate of Methanol

The primary dielectric relaxation process of monoalcohols typically exhibits characteristic Debye behavior, and the factors influencing its rate have become a research focus in recent years. It is generally believed that the hydrophilic end (i.e., the hydroxyl group) of alcohol molecules plays a major role in the primary dielectric relaxation process through hydrogen bonding networks, while the hydrophobic end mainly exerts an indirect effect by influencing the formation of intermolecular hydrogen bonds. This study systematically investigates the factors influencing the primary dielectric relaxation process of methanol using molecular dynamics simulations. As the simplest alcohol molecule, studying methanol can provide insights into the common characteristics of monohydroxy alcohols and even alcohols in general. The well-known "wait-and-switch" model currently emphasizes the impact of hydrogen bond partner concentration on the primary dielectric relaxation rate of the system. In this study, we systematically investigated the factors influencing the primary dielectric relaxation rate of methanol by independently adjusting the O-H bond length (<i>d<sub>oh</sub></i>), the C-O bond length (<i>d<sub>oc</sub></i>), and the methyl diameter (<i>σ<sub>methyl</sub></i>) of methanol molecules, and provided significant extensions to the "wait-and-switch" model:1) By adjusting <i>doh</i>, we found that a stronger total hydrogen bond energy (<i>U<sub>HB</sub></i>) in the system enhances the correlation of molecular motion, slowing down the reorientation rate of molecules and, consequently, the primary dielectric relaxation process of the system. 2) By adjusting <i>d<sub>co</sub></i>, we discovered that a longer hydrophobic end not only slows down the primary dielectric relaxation process by stabilizing the intermolecular hydrogen bond network but also directly reduces the rate of this process. 3) By adjusting <i>σ<sub>methyl</sub></i>, we found that an excessively small <i>σ<sub>methyl</sub></i> is detrimental to the stability of the hydrogen bond network, while an excessively large <i>σ<sub>methyl</sub></i> hinders the formation of hydrogen bonds. Both cases negatively affect the correlation of molecular motion. The primary dielectric relaxation process of the system is slowest when <i>σ<sub>methyl</sub></i> is at a moderate level. It was ultimately found that factors such as <i>U<sub>HB</sub></i> and the volume of the correlated motion (<i>V<sub>CM</sub></i>), along with the concentration of hydrogen bond partners in the system, collectively form the key elements influencing the primary dielectric relaxation rate of the system. Our results can reasonably explain experimental phenomena that the original "wait-and-switch" model could not account for. This study contributes to a deeper understanding of the relaxation processes of alcohol molecules and their physical origins.

From propensities to patterns to principles in protein folding.

As proposed here, β-turns play an essential role in protein self-assembly. This compact, four-residue motif affects protein conformation dramatically by reversing the overall chain direction. Turns are the "hinges" in globular proteins. This new proposal broadens a previous hypothesis that globular proteins solve the folding problem in part by filtering conformers with unsatisfied backbone hydrogen bonds, thereby preorganizing the folding population. Recapitulating that hypothesis: unsatisfied conformers would be dramatically destabilizing, shifting the U(nfolded) ⇌ N(ative) equilibrium far to the left. If even a single backbone polar group is satisfied by solvent when unfolded but buried and unsatisfied when folded, that energy penalty alone, approximately +5 kcal/mol, would rival almost the entire free energy of protein stabilization at room temperature. Consequently, globular proteins are built on scaffolds of hydrogen-bonded α-helices and/or strands of β-sheet, motifs that can be extended indefinitely, with intra-segment hydrogen bond partners for their backbone polar groups and without steric clash. Scaffolds foster a protein-wide hydrogen-bonded network, and, of thermodynamic necessity, they self-assemble cooperatively. Unlike elements of repetitive secondary structure, α-helices and β-sheet, a four-residue β-turn has only a single hydrogen bond (from i + 3 → i), not a cooperatively formed assembly of hydrogen bonds. As such, turns can form autonomously and are poised to initiate assembly of scaffold elements by bringing them together in an orientation and registration that promotes cooperative "zipping". The overall effect of this self-assembly mechanism is to induce substantial preorganization in the thermodynamically accessible folding population and, concomitantly, to reduce the folding entropy.

Improving the accuracy of GIPAW chemical shielding calculations with cluster and fragment corrections

Ab initio methods for predicting NMR parameters in the solid state are an essential tool for assigning experimental spectra and play an increasingly important role in structural characterizations. Recently, a molecular correction (MC) technique has been developed which combines the strengths of plane-wave methods (GIPAW) with single molecule calculations employing Gaussian basis sets. The GIPAW + MC method relies on a periodic calculation performed at a lower level of theory to model the crystalline environment. The GIPAW result is then corrected using a single molecule calculation performed at a higher level of theory. The success of the GIPAW + MC method in predicting a range of NMR parameters is a result of the highly local character of the tensors underlying the NMR observable. However, in applications involving strong intermolecular interactions we find that expanding the region treated at the higher level of theory more accurately captures local many-body contributions to the N15 NMR chemical shielding (CS) tensor. We propose alternative corrections to GIPAW which capture interactions between adjacent molecules at a higher level of theory using either fragment or cluster-based calculations. Benchmark calculations performed on N15 and C13 data sets show that these advanced GIPAW-corrected calculations improve the accuracy of chemical shielding tensor predictions relative to existing methods. Specifically, cluster-based N15 corrections show a 24% and 17% reduction in RMS error relative to GIPAW and GIPAW + MC calculations, respectively. Comparing the benchmark data sets using multiple computational models demonstrates that N15 CS tensor calculations are significantly more sensitive to intermolecular interactions relative to C13. However, fragment and cluster-based corrections that include direct hydrogen bond partners are sufficient for optimizing the accuracy of GIPAW-corrected methods. Finally, GIPAW-corrected methods are applied to the particularly challenging NMR spectral assignment of guanosine dihydrate which contains two guanosine molecules in the asymmetric unit.

The Long-Term Efficacy of "Social Buffering" in Artificial Social Agents: Contextual Affective Perception Matters.

In dynamic (social) environments, an affective state of “stress” can be adaptive and promote agent wellbeing, but maladaptive if not appropriately regulated. The presence of (and interactions with) affect-based social support has been hypothesised to provide mechanisms to regulate stress (the “social buffering” hypothesis), though the precise, underlying mechanisms are still unclear. However, the hormone oxytocin has been implicated in mediating these effects in at least two ways: by improving social appraisals and reducing the short-term release of stress hormones (i.e., cortisol), and adapting an agent’s long-term stress tolerance. These effects likely facilitate an agent’s long-term adaptive ability by grounding their physiological and behavioural adaptation in the (affective) social environment, though these effects also appear to be context-dependent. In this paper, we investigate whether two of the hypothesised hormonal mechanisms that underpin the “social buffering” phenomenon affect the long-term wellbeing of (artificial) social agents who share affective social bonds, across numerous social and physical environmental contexts. Building on previous findings, we hypothesise that “social buffering” effects can improve the long-term wellbeing of agents who share affective social bonds in dynamic environments, through regular prosocial interactions with social bond partners. We model some of the effects associated with oxytocin and cortisol that underpin these hypothesised mechanisms in our biologically-inspired, socially-adaptive agent model, and conduct our investigation in a small society of artificial agents whose goal is to survive in challenging environments. Our results find that, while stress can be adaptive and regulated through affective social support, long-term behavioural and physiological adaptation is determined by the contextual perception of affective social bonds, which is influenced by early-stage interactions between affective social bond partners as well as the degree of the physical and social challenges. We also show how these low-level effects associated with oxytocin and cortisol can be used as “biomarkers” of social support and environmental stress. For socially-situated artificial agents, we suggest that these “social buffering” mechanisms can adapt the (adaptive) stress mechanisms, but that the long-term efficacy of this adaptation is related to the temporal dynamics of social interactions and the contextual perception of the affective social and physical environments.

Male chimpanzees communicate to mediate competition and cooperation during feeding

An ongoing debate in animal behaviour research is whether food calls function to cooperatively inform others or provide the caller with competitive advantages. When feeding, chimpanzees, Pan troglodytes, produce two types of call: context-specific, close-range ‘rough grunts’ and context-general, long-range ‘pant hoots’. We investigated this dual signalling behaviour by wild male chimpanzees that were either actively joining others or passively being joined in food trees, considering the effects of the audience composition and the type of food encountered. For arriving individuals, we found that pant hoot production was best explained by the absence of socially important individuals (i.e. social bond partners and/or high-ranking males), suggesting that callers were cooperatively informing them about food availability, probably to strengthen social relationships. In contrast, rough grunts were mostly produced by low-ranking individuals, suggesting they were part of competitive interactions to avoid aggression. For individuals already in a tree, we found that both rough grunt and pant hoot production were most common in low-ranking individuals reacting to the arrival of high-ranking males and there was no significant effect of the presence, or absence, of social bond partners. We discuss these patterns and conclude that, when chimpanzees enter a food tree, their vocal behaviour functions to mediate both cooperative and competitive interactions.

Kinetic Monte Carlo method for epitaxial 3C-SiC (0001) growth on vicinal surfaces

A kinetic Monte Carlo model has been developed to predict island nucleation and step flow growth on vicinal surface during epitaxial growth of 3C-SiC. In the model, the crystal lattice is represented by a structured mesh which retains fixed atom positions and bond partners of the 3C-SiC crystal lattice. The events considered in the model are the deposition, evaporation and diffusion of atoms, and the attachment and detachment of adsorbed atoms. Both the incorporation energy barrier and Ehrlich-Schwoebel (ES) barrier are taken into account in the model when an adatom migrates to a step or island. The growth parameters such as growth temperature, coverages and terrace width can be selected freely, and the cross process of step flow growth and island nucleation can be simulated. The simulation results show that lower growth temperatures lead to a larger number of islands forming on the vicinal surfaces. There is also an observed coupling between island nucleation and steps at higher temperature. For smaller coverages, the islands and step patterns grow independently, and the steps and islands begin eventually to coalesce over the time. Furthermore, a decrease in terrace width leads to adatoms preferentially attaching to steps and the system to go to a step flow growth system. The results are consistent with predictions for the case of the epitaxial growth on vicinal surfaces.

Group-level cooperation in chimpanzees is shaped by strong social ties

Humans maintain extensive social ties of varying preferences, providing a range of opportunities for beneficial cooperative exchange that may promote collective action and our unique capacity for large-scale cooperation. Similarly, non-human animals maintain differentiated social relationships that promote dyadic cooperative exchange, but their link to cooperative collective action is little known. Here, we investigate the influence of social relationship properties on male and female chimpanzee participations in a costly form of group action, intergroup encounters. We find that intergroup encounter participation increases with a greater number of other participants as well as when participants are maternal kin or social bond partners, and that these effects are independent from one another and from the likelihood to associate with certain partners. Together, strong social relationships between kin and non-kin facilitate group-level cooperation in one of our closest living relatives, suggesting that social bonds may be integral to the evolution of cooperation in our own species.

Kin bias and male pair-bond status shape male-male relationships in a multilevel primate society

Male-male social relationships in group-living mammals vary from fierce competition to the formation of opportunistic coalitions or the development of long-lasting bonds. We investigated male-male relationships in Guinea baboons (Papio papio), a species characterized by male-male tolerance and affiliation. Guinea baboons live in a multi-level society, with units of one reproductively active “primary” male, 1–6 females, and offspring at the core level. Together with “bachelor” males, several units form a party, and 2–3 parties constitute a gang. We aimed to clarify to which degree male relationship patterns varied with relatedness and pair-bond status, i.e., whether males had primary or bachelor status. Data were collected from 24 males in two parties of Guinea baboons near Simenti in the Niokolo-Koba National Park in Senegal. Males maintained differentiated and equitable affiliative relationships (“strong bonds”) with other males that were stable over a 4-year period, irrespective of their pair-bond status. Remarkably, most bachelor males maintained strong bonds with multiple primary males, indicating that bachelor males play an important role in the cohesion of the parties. A clear male dominance hierarchy could not be established due to the high degree of uncertainty in individual rank scores, yet bachelor males were more likely to be found at the low end of the dominance hierarchy. Average relatedness was significantly higher between strongly bonded males, suggesting that kin biases contribute to the social preferences of males. Long-term data will be needed to test how male bonds affect male tenure and ultimately reproductive success.Significance statementMales living in social groups may employ different strategies to increase their reproductive success, from fierce fighting to opportunistic alliance formation or the development of long-term bonds. To shed light on the factors that shape male strategies, we investigated male-male social relationships in the multilevel society of Guinea baboons (Papio papio) where “primary” males are associated with a small number of females and their offspring in “units” while other males are “bachelors.” Strong bonds occurred among and between primary and bachelor males and strongly bonded males were, on average, more closely related. Bachelor males typically had multiple bond partners and thus play an important role in the fabric of Guinea baboon societies. Across primate species, neither dispersal patterns nor social organization clearly map onto the presence of strong bonds in males, suggesting multiple routes to the evolution of male bonds.

Social relationships among adult male chimpanzees (Pan troglodytes schweinfurthii): variation in the strength and quality of social bonds

Socioecological environments that promote frequent interaction and social tolerance have favored the evolution of strong and equitable social bonds, which facilitate cooperation and confer fitness benefits. In most species, kinship is the primary predictor of bond strength and quality, but it does not adequately explain partner choice among adult male chimpanzees. Instead, most bonds and cooperative interactions occur among unrelated individuals, likely because of a lack of brothers among available partners. To identify what factors drive partner choice when kinship does not, we investigated the strength and quality of social bonds among adult male chimpanzees (N = 26) at Gombe National Park, Tanzania. Maternal brothers, when present, formed stronger bonds than other dyads, and maternal brothers who were close in age or rank formed the strongest bonds. Among dyads that were not maternal brothers, however, the strength of social bonds was not associated with either age difference or rank difference. Additionally, dyads with stronger bonds groomed more equitably than other dyads, as did maternal brothers and dyads close in rank. Bonds were stable, community-wide, for 2 years on average, while lasting up to 13 years. Overall, there remains no clear-cut explanation for partner choice among male chimpanzees. Demographic constraints limit the impact of kinship, and the effects of age and rank difference are small or nonexistent, suggesting that bond strength results from a more complex process than a simple accounting of basic characteristics. Instead, dyads may possess some distinct quality that engenders strength and stability, such as compatible personalities. Strong social ties are associated with increased fitness in several species, including humans, baboons, feral horses, and dolphins. Although close kin typically form the strongest bonds, kinship explains only a limited number of bonds (and associated cooperation) among adult male chimpanzees. To identify what factors influence partner choice when kinship does not, we examined social bonds among adult male chimpanzees at Gombe National Park, Tanzania. Males formed strong, stable bonds and groomed more equitably with strong bond partners. Nevertheless, kinship, age difference, and rank difference did not fully explain male partner choice. These results contrast with findings in other species, where stronger and more equitable bonds are typically formed by kin as well as those that are close in age and rank. Instead, male chimpanzee dyads may possess some distinct quality that promotes strength and stability, such as compatible personalities.

Oxytocin increases after affiliative interactions in male Barbary macaques

Mammals living in stable social groups often mitigate the costs of group living through the formation of social bonds and cooperative relationships. The neuropeptide hormone oxytocin (OT) is proposed to promote both bonding and cooperation although only a limited number of studies have investigated this under natural conditions. Our aim was to assess the role of OT in bonding and cooperation in male Barbary macaques (Macaca sylvanus). First, we tested for an effect of affiliation - grooming and triadic male-infant-male interactions - with bond and non-bond partners on urinary OT levels. Second, we tested whether grooming interactions (and thus increased OT levels) increase a male's general propensity to cooperate in polyadic conflicts. We collected >4000 h of behavioral data on 14 adult males and measured OT levels from 139 urine samples collected after affiliation and non-social control periods. Urinary OT levels were higher after grooming with any partner. By contrast, OT levels after male-infant-male interactions with any partner or with bond partners were not different from controls but were higher after interactions with non-bond partners. Previous grooming did not increase the likelihood of males to support others in conflicts. Collectively, our results support research indicating that OT is involved in the regulation of adult affiliative relationships. However, our male-infant-male interaction results contradict previous studies suggesting that it is affiliation with bond rather than non-bond partners that trigger the release of OT. Alternatively, OT levels were elevated prior to male-infant-male interactions thus facilitating interaction between non-bond partners. The lack of an association of grooming and subsequent support speaks against an OT linked increase in the general propensity to cooperate.

Urea's match in the hydrogen-bond network? A high pressure THz study

We present results of the measurement of the low frequency spectrum of solvated urea. The study revealed a blue shift of the intramolecular mode of urea centered at 150 cm−1 of Δν= 17 cm−1 upon increasing the pressure up to 10 kbar. The blue shift scaled linearly with the increase in density and was attributed to a stiffening of the water-urea intermolecular potential. We deduced an increase in the number of affected water molecules from 1 to 2 up to 5–7, which corresponds to the sterical coordination number of urea. The increase in hydration number can be explained by an suppression of the NH2 inversion and the hydrogen bond switching around the NH2 group. Pressure induced sterical constraints are proposed to hinder the rapid switching of hydrogen bond partners and make the water around urea less bulk-like than under ambient conditions.

Anisotropic structure and dynamics of water under static electric fields.

We study the structure and dynamics of water subject to a range of static external electric fields, using molecular dynamics simulations. In particular, we monitor the changes in hydrogen bond kinetics, reorientation dynamics, and translational motions of water molecules. We find that water molecules translate and rotate slower in electric fields because the tendency to reinstate the aligned orientation reduces the probability of finding a new hydrogen bond partner and hence increases the probability of reforming already ruptured bonds. Furthermore, dipolar alignment of water molecules with the field results in structural and dynamic anisotropies even though the angularly averaged metrics indicate only minor structural changes. Through comparison of selected nonpolarizable and polarizable water models, we find that the electric field effects are stronger in polarizable water models, where field-enhanced dipole moments and thus more stable hydrogen bonds lead to slower switching of hydrogen bond partners and reduced translational mobility, compared to a nonpolarizable water model.

Counterion Effects on Aggregate Structure of 12-Hydroxystearate Salts in Hexane: A Quantum Mechanical and Molecular Dynamics Simulation Study.

Salts of 12-hydroxystearate are important organogelators and grease thickeners, but a structural rationale for their rheological properties remains elusive. We use quantum mechanical calculations and molecular dynamics (MD) simulations to analyze aggregate structures for (1) ( R)-12-hydroxystearic acid (( R)-12HSA), (2) lithium ( R)-12-hydroxystearate (( R)-Li12HS), and (3) sodium ( R)-12-hydroxystearate (( R)-Na12HS). First, quantum mechanical calculations were used to establish the structure and complexation energies of dimers of acetic acid, lithium acetate, and sodium acetate. The expected acetic acid dimer is predicted, and both the lithium acetate and sodium acetate dimer formed a C2 h-symmetric structure. All dimers were sufficiently stable to allow modeling them as pseudocovalent complexes in all-atom, explicit solvent MD. After microsecond-long MD, all systems produced strong ringlike ordered nuclei. The C2 h lithium salt molecules produced aggregates that had the most efficient packing at the head group and a higher frequency of hydroxyl hydrogen bonding compared to the sodium salt. This ordering propensity explains the high melting temperature of ( R)-Li12HS. Also, the higher frequency of hydrogen bonding leads to fewer solvent-exposed hydrogen bond partners. This explains why lithium is a common counterion in high-temperature and water-resistant greases.

Chimpanzee quiet hoo variants differ according to context.

In comparative studies of evolution of communication, the function and use of animal quiet calls have typically been understudied, despite that these signals are presumably under selection like other vocalizations, such as alarm calls. Here, we examine vocalization diversification of chimpanzee quiet ‘hoos’ produced in three contexts—travel, rest and alert—and potential pressures promoting diversification. Previous playback and observational studies have suggested that the overarching function of chimpanzee hoos is to stay in contact with others, particularly bond partners. We conducted an acoustic analysis of hoos using audio recordings from wild chimpanzees (Pan troglodytes schweinfurthii) of Budongo Forest, Uganda. We identified three acoustically distinguishable, context-specific hoo variants. Each call variant requires specific responses from receivers to avoid breaking up the social unit. We propose that callers may achieve coordination by using acoustically distinguishable calls, advertising their own behavioural intentions. We conclude that natural selection has acted towards acoustically diversifying an inconspicuous, quiet vocalization, the chimpanzee hoo. This evolutionary process may have been favoured by the fact that signallers and recipients share the same goal, to maintain social cohesion, particularly among those who regularly cooperate, suggesting that call diversification has been favoured by the demands of cooperative activities.

A Convergent Synthesis of Functionalized Alkenyl Halides through Cobalt(III)‐Catalyzed Three‐Component C−H Bond Addition

AbstractA CoIII‐catalyzed three‐component coupling of C(sp2)−H bonds, alkynes, and halogenating agents to give alkenyl halides is reported. This transformation proceeds with high regio‐ and diastereoselectivity, and is effective for a broad range of aryl and alkyl terminal alkynes. Diverse C−H bond partners also exhibit good reactivity for a range of heteroaryl and aryl systems as well as synthetically useful secondary and tertiary amide, urea, and pyrazole directing groups. This multicomponent transformation is also compatible with allenes in place of alkynes to furnish tetrasubstituted alkenyl halides, showcasing the first halo‐arylation of allenes.

A Convergent Synthesis of Functionalized Alkenyl Halides through Cobalt(III)-Catalyzed Three-Component C-H Bond Addition.

A CoIII -catalyzed three-component coupling of C(sp2 )-H bonds, alkynes, and halogenating agents to give alkenyl halides is reported. This transformation proceeds with high regio- and diastereoselectivity, and is effective for a broad range of aryl and alkyl terminal alkynes. Diverse C-H bond partners also exhibit good reactivity for a range of heteroaryl and aryl systems as well as synthetically useful secondary and tertiary amide, urea, and pyrazole directing groups. This multicomponent transformation is also compatible with allenes in place of alkynes to furnish tetrasubstituted alkenyl halides, showcasing the first halo-arylation of allenes.

The Role of Oxytocin in Social Buffering: What Do Primate Studies Add?

The ability to maintain close social bonds impacts on reproductive success, longevity, stress and health in social mammals, including humans (Silk et al., Curr Biol 20(15):1359-1361, 2010; Crockford et al., Horm Behav 53(1):254-265, 2008; Wittig et al., Horm Behav 54(1):170-177, 2008; Archie et al., Proc R Soc B 281(1793):20141261, 2014; Cameron et al., Proc Natl Acad Sci U S A 106:13850-13853, 2009; Schülke et al., Curr Biol 20:2207-2210, 2010; Silk et al., Science 302:1231-1234, 2003; Holt-Lunstad et al., PLoS Med 7(7):e1000316, 2010). Close social bonds provide an important social support system, at least in part by acting as a buffer against the deleterious effects of chronic exposure to stressors (Young et al., Proc Natl Acad Sci U S A 51:18195-18200, 2014; Heinrichs et al., Biol Psychiatry 54:1389-1398, 2003). There is accumulating evidence that individuals that provide predictable affiliation or support to others (bond partners) may moderate the perception of the stressor as well as of the physiological stress response. The neuropeptide, oxytocin, may mediate social buffering by down-regulating HPA activity and thus reducing the stress response. However, much within this process remains unclear, such as whether oxytocin is always released when exposed to a stressor, whether more oxytocin is released if there is social support, what aspect of stress or social support triggers oxytocin release and whether social support in the absence of a stressor also impacts oxytocin release and HPA activity, during everyday life. We review the literature that addresses each of these questions in an attempt to clarify where future research effort will be helpful. A better understanding of these dynamics is likely to have implications for enhancing social and health gains from human social relationships.

Social support reduces stress hormone levels in wild chimpanzees across stressful events and everyday affiliations.

Stress is a major cause of poor health and mortality in humans and other social mammals. Close social bonds buffer stress, however much of the underlying physiological mechanism remains unknown. Here, we test two key hypotheses: bond partner effects occur only during stress (social buffering) or generally throughout daily life (main effects). We assess urinary glucocorticoids (uGC) in wild chimpanzees, with or without their bond partners, after a natural stressor, resting or everyday affiliation. Chimpanzees in the presence of, or interacting with, bond partners rather than others have lowered uGC levels across all three contexts. These results support the main effects hypothesis and indicate that hypothalamic-pituitary-adrenocortical (HPA) axis regulation is mediated by daily engagement with bond partners both within and out of stressful contexts. Regular social support with bond partners could lead to better health through daily ‘micro-management' of the HPA axis, a finding with potential medical implications for humans.

Effect of nucleation on instability of step meandering during step-flow growth on vicinal 3C-SiC (0001) surfaces

A three-dimensional kinetic Monte Carlo (KMC) model has been developed to study the step instability caused by nucleation during the step-flow growth of 3C-SiC. In the model, a lattice mesh was established to fix the position of atoms and bond partners based on the crystal lattice of 3C-SiC. The events considered in the model were adsorption and diffusion of adatoms on the terraces, attachment, detachment and interlayer transport of adatoms at the step edges, and nucleation of adatoms. Then the effects of nucleation on the instability of step meandering and the coalescence of both islands and steps were simulated by the model. The results showed that the instability of step meandering caused by nucleation was affected by the growth temperature. And the effects of nucleation on the instability was also analyzed. Moreover, the surface roughness as a function of time for different temperatures was discussed. Finally, a phase diagram was presented to predict in which conditions the effects of nucleation on step meandering become significant and the three different regimes, the step-flow (SF), 2D nucleation (2DN), and 3D layer by layer (3DLBL) were determined.

(Invited) MEMS Capping By Anodic Bonding of Evaporated Glass Thin Films

Anodic bonding is a widely used MEMS process to join silicon and glass wafers. It has been utilized for many years in a large variety of devices and is valued for its possibility to create highly reliable and strong bonds at rather robust process parameters – e.g. not demanding extremely perfect surface conditions as in fusion bonding. However, the limitation in the choice of bond partners (typically borosilicate glass like Pyrex or Borofloat33 to silicon) and the rather harsh processing conditions (temperatures around 400°C and typical voltages of 600-1000V) has restricted the use of this process. Extensive research has been done over the years to adapt the process conditions in order to enable anodic bonding at lower temperatures and voltages and reach a higher compatibility of the process. The quality of the anodic bond is characterized by the charge (alkaline ion content) moved in the glass substrate and the ability of the glass to form covalent bonds with the silicon wafer. It can be observed that the bonding result is mainly an interaction on three process parameters: temperature, voltage, and process time with a clear dependence on the surface roughness of the bond partners. In bulk anodic wafer bonding it is not p ossible to reduce all three of these parameters and receive a satisfactory result. In order to enhance the compatibility of the anodic bonding process, the limitation of bulk silicon glass bonding needs to be overcome. Work has been reported on replacing the bulk glass wafers by thinner glass structures e.g. formed on a silicon wafer by polishing a previously anodically bonded glass substrate to a thickness of 20-50µm to achieve a kind of glass film. Other approaches include sputtering of borosilicate glass and the evaporation of this glass type, which is the focus of this contribution. On part of the silicon wafer, anodic bonding has be verified to work with different metalization layers, esp. aluminum coatings. Our contribution gives an overview on the possibilities of bonding with evaporated glass thin films to silicon and aluminum structures, and it applications in e.g. MEMS capping or pressure sensors. We investigate the influence of the process parameters of the glass deposition on the bonding result and present concepts for enhancing the compatibility of the anodic bonding process using evaporated glass thin films.