Structural transformations of Cu(110) surface induced by adsorption of molecular chlorine

Andryushechkin, B. V.; Cherkez, V.; Павлова, Т. В.; Zhidomirov, G. M.; Eltsov, K. N.

doi:10.1016/j.susc.2012.10.005

Cited by 25 publications

(32 citation statements)

References 38 publications

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“…8 Among the low index copper surfaces the Cu(110) has been found to facet especially easily. For example, adsorption of molecular chlorine on Cu(110) leads to formation of (210) facets, 6 adsorption of larger molecules of formate and benzoate induces step bunching resulting in formation of (11 13 1) facets, 9 and electrochemical annealing of bromide covered Cu(110) results in formation of (100) facets. 10 In all the mentioned cases the structural changes were linked to sufficient surface mobility of the substrate atoms (often achieved by thermal activation) and adsorbate−substrate interaction.…”

Section: ■ Introductionmentioning

confidence: 99%

Faceting Transition at the Oxide–Metal Interface: (13 13 1) Facets on Cu(110) Induced by Carpet-Like Ceria Overlayer

et al. 2015

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Structural transitions affect electronic structure of materials and consequently their catalytic properties. We report the observation of faceting of a low index metal surface at an oxide− metal interface in a catalytically relevant system of ceria on Cu(110). We observe formation of (13 13 1) facets on the Cu(110) surface covered by ceria upon annealing above 500°C. The faceting transition occurs in spite of a weak adsorbate−substrate interaction, which manifests itself in ceria adopting a carpet-like growth mode. We rationalize the surface faceting under such conditions by oxide overlayer-induced modification of the roughening temperature of Cu(110). We describe the carpet-like ceria film in terms of elasticity theory and show that the specific structure of the ceria supported on Cu(13 13 1) can lead to a periodic modulation of the electronic structure of the ceria−copper interface. The reported structural transition indicates that surface faceting of metal can occur at the oxide−metal interface at relatively low temperatures with possible consequences for the catalytic properties of the interface. The oxide overlayer induced faceting transition can be expected to occur for other oxide−metal combinations and, as such, has perspective applications in preparation of functional oxide−metal nanostructures.

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Section: ■ Introductionmentioning

confidence: 99%

Faceting Transition at the Oxide–Metal Interface: (13 13 1) Facets on Cu(110) Induced by Carpet-Like Ceria Overlayer

et al. 2015

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“…Thermodynamically, attachment of the strongest binding edge to the step is most probable, and this prescribes the 2D layer orientation; if the steps on the vicinal plane were all exactly parallel, then all emerging 2D domains were also oriented alike, with a prospect to eventually fuse into a large monocrystal. However, the steps are generally known to be parallel only roughly, on average (to maintain the overall miscut direction), but can be quite meandering (Figure b) and even change in time and wander at high temperature. − This makes an impression that the tightly docked emerging islands should also vary in orientation (Figure b, dashed triangle), which would preclude the overall monocrystallinity, unless some other factors realign the isles. One can see that, even if some epitaxy with the terrace takes place, it is unable to restore the order.…”

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confidence: 99%

How the Complementarity at Vicinal Steps Enables Growth of 2D Monocrystals

2019

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Large 2D monocrystals are highly sought after yet hard to achieve; unlike graphene, most dichalcogenides and h-BN possess low symmetry, which allows for nucleation of mutually inverted pieces, merging into polycrystals replete with grain boundaries. On vicinal substrate surfaces such growing pieces were observed to orient alike, and very recently this effect apparently enabled the growth of large single crystal h-BN. Addressing the compelling questions of how such a growth process can operate and what the key mechanisms are is crucial in guiding the substrate selection for optimal synthesis of perhaps many materials. To this end, the basic crystallography and atomistic-modeling theory presented here reveal (i) how the undulations of the ever-wandering steps do not, surprisingly, disturb the orientations of the attached 2D-nuclei, whose direction remains robust owing to complementarity between the meandering step and h-BN counterpart if their kinks have similar size of negligible misfit, δk < 0.1 Å. (ii) Stronger chemical affinity of metal to the N atoms at the zigzag edge of h-BN singles out its particular orientation, without evidence of any epitaxy, at the edge or to the surface. (iii) The monocrystal integrity requires unhindered growth spillover across the steps and the seamless healing of the residual fissures, caused by the very same steps necessary for coorientation. Molecular dynamics simulations show this happening for the steps not taller than the BN bond, s < 1.44 Å. These criteria point to [−1 1 2] steps on the Cu (110) surface, in accord with experimental results (Wang et al. Towards the growth of single-crystal boron nitride monolayer on Cu. arXiv:1811.06688 Cond. Mat. Mtrl. Sci., 2018), while other possibilities can also be predicted.

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“…In ref , we have discussed by means of EC-STM the step-wise transformation of the Cu(110) surface from the pristine state, showing the 1 × 1 structure of the uppermost copper surface atoms, toward a faceted surface because of the increasing anodic potentials and chloride adsorption. The latter facets were also observed upon Cl – deposition in UHV . At intermediate potentials, we have observed groove- or chain-like structures oriented along [11̅0] .…”

Section: Introductionmentioning

confidence: 54%

“…Atomically resolved EC-STM images are unfortunately still missing, and a precise structure analysis is thus difficult. The fact that is worth mentioning in this connection is the reported weak bound strength of the Cl-ions. , Andryushechkin, et al have discussed a “complete loss of atomic resolution in STM” while studying sub-monolayer Cl coverages on Cu(110) in UHV as well.…”

Section: Resultsmentioning

confidence: 99%

Chloride-Induced Surface States in Cu(110)/Liquid Interfaces

et al. 2020

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While surface states (SSs) have been widely exploited under ultrahigh vacuum conditions, their appearance and role in metal–electrolyte interfaces are still a controversial debate. The existence of SSs, similar to those shown here, permits control and tunability of electronic properties of functional metal–electrolyte interfaces. Resonant excitations among them could enhance, for example, photocatalytic reactions or permit further investigations of the surface chemistry of such reactions with surface resonance Raman spectroscopy. On the one hand, SSs and other properties are readily adjustable via an applied electrical potential, that is, by promoting changes in the chemical potential favoring adsorption of ionic species. On the other hand, the presence of the electrolyte induces additional scattering and screening effects, so that the electron charge distributions can differ considerably in the presence of high electric fields as compared to the respective surfaces in vacuum. Hence, a straightforward comparison is challenging. In this work, we report on a systematic study, by means of electrochemical impedance spectroscopy (EIS) jointly with in situ reflectance anisotropy spectroscopy (RAS), which aimed to assess the evolution of surface properties and SSs occurring at Cu(110) in contact with an HCl solution. Thereafter, by modeling the RAS response and in comparison with electrochemical scanning tunneling microscopy measurements, specific surface structures have been identified and ascribed to the optical response. In a specific potential range, three additional resonances are detected in RAS that can be explained by two-dimensional confined SSs. This work renders both in situ RAS and EIS as useful tools to study and tune SSs in a systematic way by applied electrical potentials, thereby stabilizing thermodynamically preferred surface structures.

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Structural transformations of Cu(110) surface induced by adsorption of molecular chlorine

Cited by 25 publications

References 38 publications

Faceting Transition at the Oxide–Metal Interface: (13 13 1) Facets on Cu(110) Induced by Carpet-Like Ceria Overlayer

Faceting Transition at the Oxide–Metal Interface: (13 13 1) Facets on Cu(110) Induced by Carpet-Like Ceria Overlayer

How the Complementarity at Vicinal Steps Enables Growth of 2D Monocrystals

Chloride-Induced Surface States in Cu(110)/Liquid Interfaces

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