Adsorption of Acetonitrile on Si(111)-(7 × 7).

The adsorption of acetonitrile (CH3CN) on Si(111)-(7 × 7) at a room temperature has been investigated using scanning tunneling microscopy (STM) and first-principles calculations. The site-specific information on adsorption enables us to understand the site-by-site and step-by-step adsorption mechanism. From theoretical simulations, the most stable configuration of CH3CN on Si(111)-(7 × 7) is found to be a molecularly chemisorbed CH3CN with the carbon and nitrogen atoms of CN bonded to the rest atom and adatom on the Si surface, respectively. Some chemisorption-induced features in the STM topographic image are assigned based on the theoretical calculations.

Intertwined Solitons and Impurities in a Quasi-One-Dimensional Charge-Density-Wave System: In/Si(111).

Recent studies on a quasi-one-dimensional (quasi-1D) charge-density-wave (CDW) system, In atomic wires on Si(111), have brought intriguing issues on topological solitons in quasi-1D systems: the existence of few-atom-sized solitons, chirality of solitons, and the realization of logic exploiting the chirality switching. Using scanning tunneling microscopy and first-principles calculations, we show that the previously reported "short" phase-flip defects are In adatoms and thus have nonsolitonic nature, resolving the controversy over the existence of highly localized solitons. The observed "long" phase-flip and phase-slip defects are genuine solitons with and without chirality, respectively. While achiral solitons (phase-slip defects) can exist on the pristine CDW (8×2) surface, chiral solitons (phase-flip defects) cannot due to their breakage of 8×2 ordering. The chiral solitons can exist only when they are trapped by In adatoms and constitute a part of a closed-loop domain wall. The intertwinement of chiral solitons and In adatoms implies the limitations of the previously proposed logic utilizing soliton chirality, but it provides an opportunity to realize this by controlling the In-adatom defect.

Observation of Restored Topological Surface States in Magnetically Doped Topological Insulator.

The introduction of ferromagnetic order in topological insulators in general breaks the time-reversal symmetry and a gap is opened in topological surface bands. Various studies have focused on gap-opened magnetic topological insulators, because such modified band structures provide a promising platform for observing exotic quantum physics. However, the role of antiferromagnetic order in topological insulators is still controversial. In this report, we demonstrate that it is possible to restore the topological surface states by effectively reducing the antiferromagnetic ordering in Gd-substituted Bi2Te3. We successfully control the magnetic impurities via thermal treatments in ultra-high vacuum condition and observe apparent restoration of topological surface band dispersions. The microscopic mechanism of atomic rearrangements and the restoration process of topological surface states are unraveled by the combination of scanning tunneling microscopy measurements and density functional theory calculations. This work provides an effective way to control the magnetic impurities which is strongly correlated with topological surface states.

Thermal stability of mullite RMn2O5 (R = Bi, Y, Pr, Sm or Gd): combined density functional theory and experimental study.

Understanding and effectively predicting the thermal stability of ternary transition metal oxides with heavy elements using first principle simulations are vital for understanding performance of advanced materials. In this work, we have investigated the thermal stability of mullite RMn2O5 (R = Bi, Pr, Sm, or Gd) structures by constructing temperature phase diagrams using an efficient mixed generalized gradient approximation (GGA) and the GGA + U method. Simulation predicted stability regions without corrections on heavy elements show a 4-200 K underestimation compared to our experimental results. We have found the number of d/f electrons in the heavy elements shows a linear relationship with the prediction deviation. Further correction on the strongly correlated electrons in heavy elements could significantly reduce the prediction deviations. Our corrected simulation results demonstrate that further correction of R-site elements in RMn2O5 could effectively reduce the underestimation of the density functional theory-predicted decomposition temperature to within 30 K. Therefore, it could produce an accurate thermal stability prediction for complex ternary transition metal oxide compounds with heavy elements.

Magnetic Transition to Antiferromagnetic Phase in Gadolinium Substituted Topological Insulator Bi2Te3.

There are many interests to achieve long-range magnetic order in topological insulators of Bi2Se3 or Bi2Te3 by doping magnetic transition metals such as Fe and Mn. The transition metals act as not only magnetic dopants but also electric dopants because they are usually divalent. However, if the doping elements are rare-earth metals such as Gd, which are trivalent, only magnetic moments can be introduced. We fabricated single crystals of Bi2-xGdxTe3 (0 ≤ × ≤ 0.2), in which we observed magnetic phase change from paramagnetic (PM) to antiferromagnetic (AFM) phase by increasing x. This PM-to-AFM phase transition agrees with the density functional theory calculations showing a weak and short-ranged Gd-Gd AFM coupling via the intervening Te ions. The critical point corresponding to the magnetic phase transition is x = 0.09, where large linear magnetoresistance and highly anisotropic Shubnikov-de Haas oscillations are observed. These results are discussed with two-dimensional properties of topological surface state electrons.

Optical and electronic properties of hydrogenated silicon nanoclusters and nitrogen passivated silicon nanoclusters: a density functional theory study.

Silicon nanoclusters have become significant research interest due to their potential application to optoelectronic devices in visible range. We investigate the electronic and optical properties of hydrogenated and nitrogen-passivated silicon nanoclusters using density functional theory calculations. The energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of nanoclusters have varying sizes. They are systematically studied using the conventional local density approximation, the generalized gradient approximation, and the time-dependent density functional theory calculations with hybrid functional. The HOMO-LUMO gap is found to decrease monotonically as the size of nanocluster increases. Introducing one and two nitrogen passivants to a Si29H36 nanocluster, we find that the HOMO-LUMO gap decreases as the number of nitrogen passivants increases. It suggests that multi-nitrogen passivants may enable light emission in visible range from smaller clusters.

Adsorption states of the self-assembly of NH(3) molecules on the Si(001) surface.

Adsorption states of the self-assembly of NH(3) molecules on the Si(001) surface are investigated using density-functional theory calculations. H-bond interactions between incoming and adsorbed NH(3) molecules produce a strong attractive potential field for the incoming molecules. Induced by the H bonds, physisorption states are formed on the adsorbed NH(3). Molecular adsorption states are formed on a buckled-down Si atom near the adsorbed NH(3). Various physisorption, molecular and dissociative adsorption configurations are discussed.

Interplay of hydrogen-bond and coordinate covalent-bond interactions in self-assembly of NH3 molecules on the Si(001) surface.

An exchange of hydrogen-bond and coordinate covalent-bond (dative-bond) interactions is found to play a critical role in the self-assembly of NH3 molecules on the Si(001) surface. An NH3 molecule in the height of approximately 3-10 A above the surface is attracted toward the preadsorbed NH2 moiety through the long-range H-bond interaction. Within approximately 3 A, the H-bond interaction becomes repulsive, and instead the dative bond with the buckled-down Si atom governs the adsorption process. The interplay of the two interactions induces the clustering and the zigzag feature of the dissociatively adsorbed NH3 molecules on the Si(001) surface.

Extrinsic nature of point defects on the Si(001) surface: dissociated water molecules.

Point defects on a Si(001)-(2 x 1) surface were examined by scanning tunneling microscopy and ab initio pseudopotential calculations. The residual water molecules in the ultrahigh vacuum chamber are found to be the sole origin of the type-C defects. Most of the apparent dimer vacancies in the filled-state images were found to show a distinct U-shaped triple-dimer footprint in the empty-state images, which also originate from water adsorption. These two defects were identified as a single dissociated water molecule forming Si-OH and Si-H bonds in the interdimer (type-C defect) and the on-dimer (dimer-vacancy-like or U-shape defect) configurations.

Two-dimensional carbon incorporation into Si(001): C amount and structure of Si(001)-c(4 x 4).

The C amount and the structure of the Si(001)-c(4 x 4) surface is studied using scanning tunneling microscopy (STM) and ab initio calculations. The c(4 x 4) phase is found to contain 1/8 monolayer C (1 C atom in each primitive unit cell). From the C amount and the symmetry of high-resolution STM images, it is inferred that the C atoms substitute the fourth-layer site below the dimer row. We construct a structure model relying on ab initio energetics and STM simulations. Each C atom induces an on-site dimer vacancy and two adjacent rotated dimers on the same dimer row. The c(4 x 4) phase constitutes the subsurface Si(0.875)C(0.125) delta layer with two-dimensionally ordered C atoms.

Dynamic pathway model for the formation of C(60).

We present a dynamic pathway model for the formation of C(60) using the action-derived molecular dynamics simulations. We propose candidate precursors for dynamic pathway models in which carbons spontaneously aggregate due to favorable energetics and kinetics. Various planar polycyclic models are in a disadvantageous state where they cannot be trapped in the forward reaction due to their high excess internal energies. Our simulation results show that precursors either in the shape of tangled polycyclics or in the shape of open cages are kinetically favored over precursors in the shape of planar hexagonal graphite fragments. Calculated activation energies for the probable precursor models are in good agreement with experiment. Existence of chains in the models of tangled polycyclics and open cages is beneficially for the formation of C(60) molecule. Chains attached to the precursor model are energetically favorable and display lithe movements along the dynamic pathway.

Facile fabrication of 2-dimensional arrays of sub-10 nm single crystalline Si nanopillars using nanoparticle masks.

A simple procedure for the fabrication of sub-10 nm scale Si nanopillars in a 2-D array using reactive ion etching with 8 nm Co nanoparticles as etch masks is demonstrated. The obtained Si nanopillars are single crystalline tapered pillar structures of 5 nm (top) x 8 nm (bottom) with a density of approximately 4 x 10(10) pillars cm(-2) on the substrate, similar to the density of Co nanoparticles distributed before the ion etching process. The uniform spatial distribution of the Si nanopillars can also be patterned into desired positions. Our fabrication method is straightforward and requires mild process conditions, which can be extended to patterned 2-D arrays of various Si nanostructures.

Initial stage of carbon incorporation into si(001) and one-dimensional ordering of embedded carbon.

We investigate the initial stage of the C incorporation into Si(001) using thermal dissociation of C2H2. The scanning tunneling microscopy shows that C-induced dimer vacancies (DVs) with depressed adjacent dimers are generated on the surface and aligned in the dimer direction, forming the 2xn structure. The ab initio pseudopotential calculations reveal that, with the presence of a DV in the surface, the alpha site in the fourth subsurface layer directly below the DV is the most favorable for the incorporated C atoms. The embedded C atoms align one dimensionally due to the interaction which is attractive in neighboring dimer rows but repulsive in the same dimer row.