Au-induced nanofaceting and the stoichiometry of the Si(7 7 5)-Au surface

The Au-induced changes in the surface morphology of a Si(1 1 1) sample miscut 8° towards have been measured using room temperature scanning tunneling microscopy and low energy electron diffraction. Au coverages of less than 0.06 ML up to 0.43 ML have been investigated. In all cases Au adsorption produces dramatic changes in surface morphology. The Au-induced surface exhibits nanofacets with orientations that depend critically on the amount of Au deposited. Below 0.32 ML, the restructured surface always includes (7 7 5)-Au nanofacets suggesting that the (7 7 5)-Au facet is energetically preferred on this surface. The (7 7 5)-Au facet is oriented 8.5° from [1 1 1] towards and is characterized by 1-d chains spaced 21.3 Å apart that run along the direction. By maximizing the surface area of the (7 7 5) facets and optimizing the associated diffraction pattern we determine that the (7 7 5)-Au reconstruction is optimized at 0.24 ML and corresponds to a stoichiometry of 1.5 Au atoms per 1 × 1 unit cell. We believe that the local Au coverage on the (7 7 5) facet is 0.24 ML, and that the deficit/extra of Au at any particular coverage is accommodated by non-(7 7 5) facets. For example at 0.06 ML the regions of step bunching observed on the clean surface are eliminated and Au-induced (7 7 5) and Au-free (1 1 1)7 × 7 facets are already visible. Up to 0.18 ML the non-(7 7 5) facet is Au free. Beyond 0.32 ML, the (7 7 5)-Au reconstruction is no longer stable and the extra Au is accommodated by the formation of higher angle facets with smaller chain spacings.     

An AFM study of the processing of hydrogen passivated silicon(1 1 1) of a low miscut angle

We present atomic force microscopy (AFM) measurements from a passivated silicon crystal miscut by 0.1° and show the etching regime to be significantly different from surfaces with a larger miscut angle. A simple kinetic model is developed to explain the results and is used to derive the optimal etching conditions for nominally flat Si(1 1 1)–(1×1)H. We show that small changes in miscut angle can alter the kinetic steady state and promote the formation of deep etch pits, even on the least stable, miscut surface. Collisions of steps with these pits result in arrays of stable, self-aligned ‘etch hillocks' over micron dimensions. Following preparation, we use AFM to observe the initial growth of native oxide on the Si(1 1 1)–(1×1)H surface, and demonstrate that AFM is a sensitive probe to surface oxidation in the sub-monolayer regime.     

Step formation on hydrogen-etched 6H-SiC{0 0 0 1} surfaces

The formation of step bunches and/or facets on hydrogen-etched 6H-SiC(0 0 0 1) and () surfaces has been studied, using both nominally on-axis and intentionally miscut (i.e. vicinal) substrates. It is found that small miscuts on the (0 0 0 1) surface produce full unit-cell high steps, while half unit-cell high steps are observed on the () surface. The observed step normal direction is found to be for both surfaces. Hence, for intentionally miscut material, a miscut oriented towards this direction produces much better order in the step array compared to a miscut oriented towards a direction. For (0 0 0 1) vicinal surfaces that are miscut towards the direction, the formation of surface ripples is observed for 3° miscut and the development of small facets (nanofacets) is found for higher miscut angles. Much less faceting is observed on miscut () surfaces. Additionally, the (0 0 01) surface is found to have a much larger spatial anisotropy in step energies than the () surface.     

Two series of triple- and single-domain reconstructions induced by europium on vicinal Si(1 1 1) [ ]-miscut surface

The growth and properties of Eu-induced one-dimensional reconstructions on vicinal Si(1 1 1) surface miscut in the [ ] direction have been studied by low energy electron diffraction and scanning tunneling microscope in the submonolayer range. The focus has been attended to the formation of single-domain structures and the influence of preparation parameters on the domain orientation. We have found the critical conditions for the preparation of a variety of Eu-induced single-domain (n×2) and (n×1) structures. In addition, a new intermediate phase showing the 9×1 periodicity between 3×2 and 2×1 phases is detected.     

Faceting and Roughening of the Asymmetric Twin Grain Boundaries in Zinc

Faceting of grain boundaries (GBs) or surfaces can be considered as a phase transition when the original surface or GB dissociates onto flat segments whose energy is less than that of original surface or GB. Zn [1120] flat single crystals were grown using the modified Bridgman technique from Zn of 99.999 wt% purity. Individual elongated twin plates having very uniform thickness were produced with the aid of slight deformation of single crystals. Parallel elongated sides of the twin plate are formed by the coherent symmetric twin (1102)₁(1102)₂ grain boundary (STGB) facets. Due to its optical anisotropy, zinc allows one to study the shape of the GB with the aid of polarised light. The stationary shape of the slowly migrating tip of the twin plate has been studied in situ. The hot stage of optical microscope was used. The temperature interval from 592 to 692 K was investigated. Below 632 K the twin tip contains only one plane facet 1 which is nearly parallel to the (1102)₂ plane and has the angle of 84° with the coherent STGB. Above 632 K the second facet 2 appears at the tip of the twin plate. This facet is nearly parallel to the (1100)₁ plane and has the angle of 46° with the coherent STGB. Between 632 and 682 K both 84° and 46° facets coexist, and 84° facet gradually disappear with increasing temperature. Above 682 K only 46° facet is present in the twin tip. The indications of the GB roughening phase transition were also observed, namely the edges of the facets become smoother with increasing temperature. The GB phase diagram for the twin GBs in zinc containing the lines of two GB faceting phase transitions has been constructed. Schematic Wulff-Herring diagrams explaining these transitions are presented.     

Scaling and universality of roughening in thermal oxidation of Si(001)

By analyzing atomic force microscopy images, we derive a continuum equation that quantitatively explains the roughening at the Si(001)-SiO2 interface during thermal oxidation at the temperature at 1200 degrees C in an Ar atmosphere containing a small fraction of O2. We also show that there is a phase transition in the universality class from a disordered to step-terrace structure at the interface at oxidation temperatures between 1150 and 1380 degrees C with the miscut angle of the substrate as the scaling parameter.     

Thermal faceting of the rutile TiO2(001) surface

Temperature dependent faceting of rutile TiO₂ surfaces cut to the (001) plane has been reported [Tait and Kasowski, Phys. Rev. B20 (1979) 5178]. By comparing LEED data to beam positions calculated for various sets of facet planes, the facet planes have been identified. The first ordered structure observed on annealing ion bombarded surfaces is composed of {011} facets with the facet planes in a (2 × 1) reconstruction. The high temperature structure produced on annealing above 1300K is best described as {114} facets; however, there are deviations of the observed LEED pattern from that calculated for {114} facets, possibly because of the presence of related planes. LEED data have now been obtained on the behavior of (110), (100), (011), (114), and (001) surfaces in UHV. The observed stability of TiO₂ surfaces can be related to the Ti ion coordination numbers in the surface plane as derived from stoichiometric terminations of the rutile lattice.     

Oxygen-induced surface faceting of the threefold-symmetry surface of icosahedral AlPdMn quasicrystal

We have investigated the oxidation behavior of the threefold-symmetry surface of icosahedral AlPdMn quasicrystal by low-energy electron diffraction and Auger electron spectroscopy. Upon oxygen exposure at 740 K, the predominantly planar surface develops facets of an Al-oxide layer, each facet oriented along a high-symmetry direction of the icosahedral bulk structure. While the facets along the fivefold-symmetry directions are structurally well-ordered, the facets along the twofold- and threefold-symmetry directions are structureless. The results are compared with the oxide formation on the fivefold-symmetry surface of icosahedral AlPdMn quasicrystal.     

3D Crystal: How Flat its Flat Facets Are?

We investigate the hypothesis that the (random) crystal of the (–)-phase inside the (+)-phase of the 3D canonical Ising model has flat facets. We argue that it might need to be weakened, due to the possibility of formation of an extra monolayer on a facet. We then prove this weaker hypothesis for the Solid-On-Solid model.     

Initial oxidation of MgO-supported Rh nanoparticles studied by TEM

The formation of ultrathin oxide layers on the facets of MgO(0 0 1) supported Rh nanoparticles is revealed by high-resolution transmission electron microscopy (HRTEM) and spatially-resolved electron energy-loss spectroscopy (EELS). An O–Rh–O trilayer surface oxide has been observed on both {1 1 1} and (0 0 1) facets, which is confirmed by image simulation using the atomic model of a two-dimensional surface oxide obtained by density functional theory (DFT). The spacing between the oxide layer and the Rh {1 1 1} facet is however markedly smaller, indicating a variation of interface bonding in the case of nanoparticles. When the oxide layer is slightly thicker with two Rh planes, the structure of the surface oxide is different from corundum Rh₂O₃ bulk oxide, and the trilayer surface oxide persists as terminating layer. The spacing between the oxide layer and the Rh(1 1 1) facet is found to vary, being smaller in the middle of the oxide layer. It is also found that oxidation is more pronounced at the intersections of the nanoparticles’ facets.     

Monte Carlo study of the hetero-polytypical growth of cubic on hexagonal silicon carbide polytypes

In this article we use three dimensional kinetic Monte Carlo simulations on super-lattices to study the hetero-polytypical growth of cubic silicon carbide polytype (3C-SiC) on misoriented hexagonal (4H and 6H) substrates. We analyze the quality of the 3C-SiC film varying the polytype, the miscut angle and the initial surface morphology of the substrate. We find that the use of 6H misoriented (4°–10° off) substrates, with step bunched surfaces, can strongly improve the quality of the cubic epitaxial film whereas the 3C/4H growth is affected by the generation of dislocations, due to the incommensurable periodicity of the 3C (3) and the 4H (4) polytypes. For these reasons, a proper pre-growth treatment of 6H misoriented substrates can be the key for the growth of high quality, twin free, 3C-SiC films.     

Grain-boundary faceting at a = 3, [110]/{112} grain boundary in a cubic zirconia bicrystal

The atomic structure of a = 3, [110]/{112} grain boundary in a yttria-stabilized cubic zirconia bicrystal has been investigated by high-resolution transmission electron microscopy (HRTEM). It was found that the grain boundary migrated to form periodic facets, although the bicrystal was initially joined so as to have the symmetric boundary plane of {112}. The faceted boundary planes were indexed as {111}/{115}. The structure of the {111}/{115} grain boundary was composed of an alternate array of two types of structure unit: {112}- and {111}-type structure units. HRTEM observations combined with lattice statics calculations verified that both crystals were relatively shifted by (α/4)[110] along the rotation axis to form a stable grain-boundary structure. A weak-beam dark-field image revealed that there was a periodic array of dislocations along the grain boundary. The grain-boundary dislocations were considered to be introduced by the slight misorientation from the perfect = 3 orientation. The fact that the periodicity of the facets corresponded to that of the grain-boundary dislocations must indicate that the introduction of the grain-boundary dislocations is closely related to the periodicity of the facets. An atomic flipping model has been proposed for the facet growth from the initial = 3, {112} grain boundary.     

Si(111)衬底切偏角对GaN基LED外延膜的影响

利用金属有机化学气相沉积(MOCVD)方法在具有偏角(0°~0.9°)的Si(111)衬底上生长了GaN薄膜。采用高分辨X射线衍射(HRXRD)对Si衬底的偏角进行了精确的测量,利用HRXRD、原子力显微镜(AFM)以及光致发光(PL)对外延薄膜的晶体质量、量子阱中In组分、表面形貌及光学特性进行了研究。结果表明,Si(111)衬底偏角对量子阱中的In组分、 GaN外延膜的表面形貌、晶体质量以及光学性能具有重大影响。为了获得高质量的GaN外延薄膜,衬底偏角必须控制在小于0.5°的范围内。超出该范围,GaN薄膜的晶体质量、表面形貌及光学性能都明显下降。     

Instabilities and coarsening of stressed crystal surfaces in aqueous solution

Strong pattern formation occurs on polished miscut surfaces of sodium chlorate (NaClO3) single crystals that are uniaxially stressed perpendicular to the step edge direction and placed in a saturated aqueous solution. The wavelength lambda of the stress-induced surface instability increased continuously in experiments up to 9 days after placed in the solution. There were three successive regimes of coarsening: (i) one-dimensional step bunching with lambda approximately t(1/4) until an undulation transition was reached, (ii) a two-dimensional coarsening mechanism with lambda approximately t(1/2), and a gradual transition to (iii) Ostwald ripening-like coarsening with lambda approximately t(1/3). The coarsening of the surface patterns towards a stable, flat surface implies the spontaneous formation of a stress-free skin on the surface of the stressed solid.     

Atomic structures on faceted W(111) surfaces induced by ultrathin films of Pd

The faceting of Pd/W(111) surfaces has been studied using a Scanning tunneling microscope (STM). Three-sided pyramidal facets having {211} faces with dimensions ranging from 3 to 15 nm can be induced by ultrathin Pd films (≥ 1 monolayer), upon annealing to 700 K or higher. From atomic-resolution STM-images of these surfaces, we obtain direct confirmation of the {211} structure on individual facets of the 3-sided pyramids. In addition, the atomic structure of the facet edges indicates that edge energy may play a role in faceting. When the as-deposited coverage of Pd is greater than the critical value ( 1 monolayer) for inducing faceting, the extra Pd atoms diffuse to form 3-dimensional clusters, some with discernible crystalline structures, upon annealing.     

Blue emission from InGaN/GaN hexagonal pyramid structures

Cathodoluminescence (CL) from InGaN grown on GaN hexagonal pyramid structures has been investigated. The facet structure can be controlled by the growth temperature and reactor pressure. GaN pyramid structures surrounded with facets were grown at 1020 C at a pressure of 500 Torr by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE). The indium mole fraction in the InGaN film depends on the facet structure. The thickness of the InGaN and the peak wavelength and intensity of the CL from the InGaN gradually increased from the bottom to the top of the facets.     

Atomistic and lattice model of a grain boundary defaceting phase transition

Recent calculations have shown that grain boundary (GB) stress is too small to stabilize finite GB facets, suggesting that the existing theory of GB defaceting phase transitions is incomplete. We perform molecular dynamics calculations, which show a reversible phase transition at approximately 400 K with a concerted shuffle of two atoms at the facet junction as the elementary excitation. Based on this excitation we formulate an appropriate lattice model, perform Monte Carlo simulations, and establish an analytical relationship between the elementary excitation energy and the transition temperature.     

Spontaneous pattern formation with incoherent white light

We present the first experimental observation of modulation instability and spontaneous pattern formation with incoherent white light emitted from an incandescent light bulb. We show experimentally that modulation instability of white light propagating in a noninstantaneous self-focusing medium is a collective effect, where the entire temporal spectrum of the light beam becomes unstable at the same threshold value and collectively forms a pattern with a single periodicity. We experimentally demonstrate that the temporal spectrum of the evolving perturbation self-adjusts to match the collective pattern formation phenomenon.     

合成氨钌催化剂的晶体和形貌敏感性

哈伯-博施法合成氨反应是高温高压的耗能过程,因此降低该过程的能量消耗及开发温和条件下合成氨反应催化剂具有重要意义. 金属钌是合成氨反应中最有前途的催化剂之一,一直备受广泛关注. 确定金属钌催化剂的结构敏感性并提高其比质量活性是多相催化中亟待解决的重要问题. 氮气(N₂)活化是合成氨反应中的关键步骤. 本文通过第一性原理理论计算和微观动力学模拟方法系统研究了具有六方密排和面心立方晶体结构的钌催化剂上N₂活化过程和N₂解离反应速率. 理论计算研究表明,在六方密排Ru形貌中,{2130}晶面具有最高的N₂解离活性,其次是{0001}台阶面,它们比六方密排Ru其他表面上N₂解离反应速率高3个数量级以上;在面心立方Ru形貌中,{211}和{311}表面上N₂解离活性最高. 这些结果都表明台阶面/台阶位对氮气活化至关重要. 虽然六方密排Ru {2130}晶面具有最低的N₂解离能垒,然而由于面心立方Ru上可以暴露更高密度的活性位点,使得面心立方Ru比六方密排Ru具有更高的N₂转化速率. 本研究深入理解了N₂解离过程中,金属Ru 催化剂形貌和晶相结构敏感性,这为设计和优化高活性的合成氨Ru催化剂提供了理论基础.