Vibrational entropy-driven dealloying of Mo(1 0 0) and W(1 0 0) surface alloys

The formation and stability of Cu, Ag and Au-induced c(2 × 2) alloys at the Mo(1 0 0) and W(1 0 0) surfaces have been investigated with low-energy electron microscopy and diffraction. The ordered alloys transform to disordered overlayer structures at elevated temperature. Comparison of the transformation temperatures with energetics obtained from first principles calculations reveals the vibrational entropic contribution to the system free energy that defines alloy thermal stability. Effective Debye temperatures for metal adatoms are determined that exhibit the expected mass and bond strength dependence.     

Morphological evidence for surface pre-melting on Si(1 1 1)

We present what we believe to be the first morphological evidence for the occurrence of surface pre-melting on the Si(1 1 1) surface. Our results complement the extensive previous evidence from diffraction and ion scattering techniques for the presence of pre-melted (liquid-like) layers on Si(1 1 1) below the bulk melting temperature and also suggest how atomic steps are involved in the initiation of such layers. Our results are based on atomic force microscopy studies of morphologies that are preserved when surfaces are annealed in a range of high temperatures and then rapidly cooled to room temperature for observation. A unique feature of the experiments is the use of specially prepared atomically flat or very low step density surfaces; this allows us to see how the liquid-like morphologies are associated with the steps and also allows the high temperature structures to survive the cooling process without being absorbed into the steps which normally would exist on a surface vicinal to (1 1 1). Quenched-in structures ascribed to pre-melting also act as sinks for diffusing ‘excess’ adatoms generated by the (1 × 1) to (7 × 7) transition and this leads to the formation of dendritic islands.     

Height and roughness distributions in thin films with Kardar-Parisi-Zhang scaling

We study height and roughness distributions of films grown with discrete Kardar-Parisi-Zhang (KPZ) models in a small time regime which is expected to parallel the typical experimental conditions. Those distributions are measured with square windows of sizes 8 ? r ? 128 gliding through a much larger surface. Results for models with weak finite-size corrections indicate that the absolute value of the skewness and the value of the kurtosis of height distributions converge to 0.2 ? ∣S∣ ? 0.3 and 0 ? Q ? 0.5, respectively. Despite the low accuracy of these results, they give additional support to a recent claim of KPZ scaling in oligomer films. However, there are significant finite-size effects in the scaled height distributions of models with large local slopes, such as ballistic deposition, which suggests that comparison of height distributions must not be used to rule out KPZ scaling. On the other hand, roughness distributions of the same models show good data collapse, with negligible dependence on time and window size. The estimates of skewness and kurtosis for roughness distributions are 1.7 ? S ? 2 and 3 ? Q ? 7. A stretched exponential tail was found, which seems to be a particular feature of KPZ systems in 2 + 1 dimensions. Moreover, the KPZ roughness distributions cannot be fitted by those of 1/f^α noise. This study suggests that the roughness distribution is the best option to test KPZ scaling in the growth regime, and provides quantitative data for future comparison with other models or experiments.     

A phenomenological explanation for the buckling of surface alloys

A phenomenological model, in which the interactions between the nearest-neighbor (NN) atoms are described as bondings but not hard sphere contacts, is proposed to explain the unexpected reduced buckling in surface alloy systems. In the model, the forces acting on an adsorbate atom from its NN substrate atoms in different layers may be either repulsive or attractive, depending on whether the bond between the adsorbate atom and its NN substrate atoms is compressed or stretched. It is found that the forces on the adsorbate atom from its NN substrate atoms in the sub-surface layer play a more important role for the buckling of surface alloy than those from its NN substrate atoms in the surface layer do. The bucklings expected by the model are significantly smaller than those predicted by the simple hard sphere model and are in good agreement with the experiments when the equilibrium bond length of the NN adsorbate-substrate atom pairs is taken as the sum of the corresponding metal radii.     

Atomic structure of the Si(5 5 12)-2 × 1 surface

Based on the results of scanning tunneling microscopy studies of the reconstructed Si(5 5 12)-2 × 1 surface, its atomic structure has been found. It turns out that Si(5 5 12)-2 × 1 consists of four one-dimensional structures: honeycomb (H) chain, π-bonded H′ (π) chain, dimer-adatom (D/A) row, and tetramer (T) row. Its period is composed of three subunits, i.e., (i) (3 3 7) unit with a D/A row [D(3 3 7)], (ii) (3 3 7) unit with a T row [T(3 3 7)], and (iii) (2 2 5) unit with both a D/A and a T row. Two kinds of adjacent subunits, T(3 3 7)/D(3 3 7) and D(3 3 7)/(2 2 5), are divided by H chains with 2× periodicity due to buckling, while one kind of adjacent subunits, T(3 3 7)/(2 2 5), is divided by a π chain with 1× periodicity. Two chain structures, H and π chains, commute with each other depending upon the external stresses perpendicular to the chain, which is the same for two row structures, D/A and T rows. It can be concluded that the wide and planar reconstruction of Si(5 5 12)-2 × 1 is originates from the stress balance among two commutable chains and two commutable rows.     

Study of Si(0 0 1)4 × 2-Ga structure by scanning tunneling microscopy and ab initio calculation

We have studied Si(0 0 1)-Ga surface structures formed at Ga coverages of slightly above 0.50 monolayer (ML) at 250 °C by scanning tunneling microscopy (STM). 4 × 2-, 5 × 2-, and 6 × 2-Ga structures were observed in a local area on the surface. The 4 × 2-Ga structure consists of three protrusions, as observed in filled- and empty-state STM images. The characters of these structures are clearly different from those of other Si(0 0 1)-Ga structures. We also performed an ab initio calculation of the energetics for several possible models for the 4 × 2-Ga structure, and clarified that the three-orthogonal-Ga-dimer model is the most stable. Also, the results of comparing the simulated STM images and observation images at various bias voltages indicate that this structural model is the most favorable.     

Imine‐linked porous organic polymers showing mesoporous microspheres architectures with tunable surface roughness

Different kinds of porous organic polymers (POPs) bearing 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BDP) fluorophores have been developed to generate singlet oxygen upon light illumination. Herein, four imine‐linked POPs were prepared by copolymerization of amine and aldehyde with different ratios of di‐aldehyde A1 and A2. The POPs were investigated by a combination of techniques such as solid ¹³C NMR, FTIR, and nitrogen absorption–desorption isotherms and electronic microscopy. The results demonstrated that these POPs were prone to form hierarchical porous architectures. Scanning electron microscopy and transmission electron microscopy images revealed that the spherical morphologies showed different roughness, that is, BDP‐POPs with more BDP aldehyde A2 presented rougher surface. Finally, these POPs were used to generate singlet oxygen (¹O₂) monitored by 1,3‐diphenylisobenzofuran and bioimaging in HeLa cells. Our results indicated that the ability to generate ¹O₂ is dependent on the amount of BDP. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 319–327     

Skew-Gaussian random field

In this article, we introduce the concept of skewness to the Gaussian random field theory by defining a new two-dimensional non-Gaussian random field called skew-Gaussian random field. We derive the expected Euler characteristic of its excursion set. Moreover, an approximation to the size distribution of one connected component is derived. As an illustration, we present a simulation study to compare the approximation mechanism with the exact one.     

Effects of guest microparticles on the swelling behavior of polyacrylamide gels

We report the effects of guest particles on the swelling properties of bulk polyacrylamide gels. The guest particles were the spheres of poly(N‐isopropylacrylamide) gel with submicrometer diameter, which were synthesized by an emulsion‐polymerized reaction in water. Polyacrylamide gels were prepared by a free radical polymerization reaction, immobilizing the gel microparticles with different concentrations at gelation. The macroscopic swelling ratio of this hybrid gel in a cylindrical shape was measured as functions of temperature and acetone concentration. The presence of guest particles was found to strongly affect the swelling behavior in the bulk gels when the concentration of incorporated particles exceeded a threshold. The experimental results indicated that the macroscopic volume in response to the temperature change should be determined by the guest particles above the threshold. On the other hand, the hybrid gel could not evidently shrink by adding acetone when the concentration of guest particles exceeded the threshold. To make clear the distribution of guest particles in the bulk networks, the fractured surfaces of dried gels were imaged by tapping mode atomic force microscopy. The guest particles were found to aggregate in the bulk homogeneous networks to form microdomains with densely connected structure, which became larger with increasing particle concentration. The roles of bulk networks as well as guest particles on the swelling behavior of hybrid gels were qualitatively discussed on the basis of the incorporated structure of guest particles, depending on the concentration of guest particles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1696–1704, 2005