Study by scanning tunneling microscopy of hydrogen adsorption and desorption on Si111 7 x 7 at room temperature and at high temperature

An overview is given on the use of scanning tunneling microscopy (STM) for investigation of the adsorption of hydrogen on Si(111)7 x 7 both at room temperature and at elevated temperature to finally obtain a hydrogen-saturated surface of Si(111). The initial stages are characterized by high reactivity of Si adatoms of the 7 x 7 structure. After adsorption of hydrogen on the more reactive sites in the beginning of the adsorption experiments a regular pattern, which is different for room and elevated temperature, is observed for the less reactive sites. In agreement with previous work, local 1 x 1 periodicity of the rest atom layer and the presence of di- and trihydride clusters is observed for hydrogen-saturated surface. STM has also been used to characterize surfaces from which the hydrogen atoms have been removed by thermal desorption. Finally, tip-induced desorption by large positive sample-bias voltages and by increasing the tunneling current will be described.     

Near-edge electronic structure in NbS2

The near-edge electronic and structural properties of 2H-NbS(2) were investigated using scanning tunneling microscopy (STM) and density-functional calculations. Geometry optimization of the near-edge structure using density-functional calculations was performed on [1010]- and [1010]-terminated layer edges. Ribbon model systems also included variation of the number of bound sulfur atoms at the edges. Atomic resolution STM data exhibit a pronounced electronic density of states at the outermost edge atomic sites but are otherwise bulk-like in the near-edge region. Optimized NbS2 ribbon structures confirm the STM results indicating that minimal reconstruction occurs and that the edge electronic structure exhibits a significant increase in local density of states compared to bulk. Simulated STM images using extended Hückel tight-binding calculations based on optimized ribbon structures successfully modeled the experimental STM results. The results indicate that the [1010] "Nb" edges are preferentially observed compared to the [1010] "S" edge possibly due to differences in stability.     

Spectroscopic evidence for the partial dissociation of H2O on ZnO(1010)

The interaction of water with the non-polar ZnO(1010) surface has been studied by high resolution electron energy loss spectroscopy (HREELS) and thermal desorption spectroscopy (TDS). Adsorption of water at room temperature leads to the partial dissociation of water molecules giving rise to a well defined (2x1) superstructure. This observation was confirmed by the HREELS data which show the water-induced O-H stretching modes at 396 and 460 meV (3193 and 3709 cm-1) as well as the peak at 456 meV (3677 cm-1) arising from the OH species. The large red shift of the loss at 396 meV indicates unusually strong hydrogen bonding interactions of water to both neighbouring adsorbate molecules and the surface O atoms which are responsible for the partial dissociation of water molecules on the perfect ZnO(1010) surface.     

The initiation and characterization of single bimolecular reactions with a scanning tunneling microscope

A scanning tunneling microscope (STM) operating at 9 K in ultrahigh vacuum was used to initiate a bimolecular reaction between isolated hydrogen sulfide and dicarbon molecules on the Cu(001) surface. The reaction products ethynyl (CCH) and sulfhydryl (SH) were identified by inelastic electron tunneling spectroscopy (STM-IETS) and by sequentially removing hydrogen atoms from an H2S molecule using energetic tunneling electrons. For comparison, the thermal diffusion and reaction of H2S and CC at 45 K and H2O and CC at 9 K were also observed.     

Pinning mass-selected Agn clusters on the TiO2(110)-1x1 surface via deposition at high kinetic energy

We present the first scanning tunneling microscopy (STM) study of the deposition of mass-selected silver clusters (Ag(n),n=1, 2, 3) on a rutile TiO(2)(110)-1x1 surface at room temperature under hard-landing conditions. Under hard-landing conditions, only small features are observed on the surface in all cases without sintering or surface damage. This suggests that the high impact energy of the clusters mainly dissipates as thermal energy in the substrate, resulting in the recovery of any initial impact-induced surface damage and the formation of bound clusters on the surface near the impact point. STM images indicate that Ag(1) binds on the bridging oxygen rows twice as often as on the Ti rows. Density-functional Theory (DFT) calculations are consistent with Ag(1) binding at either bridging oxygen vacancies or with two adjacent bridging oxygen atoms in the same bridging oxygen row. STM images of Ag(2) and Ag(3) depositions indicate almost exclusive binding centered on the Ti-atom rows. DFT calculations suggest that the Ag(2) and Ag(3) clusters are bound between two bridging oxygen rows, which is consistent with the STM observations.     

Low-temperature STM images of methyl-terminated Si(111) surfaces

Low-temperature scanning tunneling microscopy (STM) has been used to image CH(3)-terminated Si(111) surfaces that were prepared through a chlorination/alkylation procedure. The STM data revealed a well-ordered structure commensurate with the atop sites of an unreconstructed 1 x 1 overlayer on the silicon (111) surface. Images collected at 4.7 K revealed bright spots, separated by 0.18 +/- 0.01 nm, which are assigned to adjacent H atoms on the same methyl group. The C-H bonds in each methyl group were observed to be rotated by 7 +/- 3 degrees away from the center of an adjacent methyl group and toward an underlying Si atom. Hence, the predominant interaction that determines the surface structure arises from repulsions between hydrogen atoms on neighboring methyl groups, and secondary interactions unique to the surface are also evident.     

Coexistence of one- and two-dimensional supramolecular assemblies of terephthalic acid on Pd(111) due to self-limiting deprotonation

The adsorption of terephthalic acid [C(6)H(4)(COOH)(2), TPA] on a Pd(111) surface has been investigated by means of scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy, and near-edge x-ray absorption fine structure spectroscopy under ultrahigh vacuum conditions at room temperature. We find the coexistence of one- (1D) and two-dimensional (2D) molecular ordering. Our analysis indicates that the 1D phase consists of intact TPA chains stabilized by a dimerization of the self-complementary carboxyl groups, whereas in the 2D phase, consisting of deprotonated entities, the molecules form lateral ionic hydrogen bonds. The supramolecular growth dynamics and the resulting structures are explained by a self-limiting deprotonation process mediated by the catalytic activity of the Pd surface. Our models for the molecular ordering are supported by molecular mechanics calculations and a simulation of high resolution STM images.     

Cr掺杂ZnO(10(¯1)0)表面的原子结构和电子性质研究

多相催化中ZnO基催化剂广泛应用于甲醇合成、水汽变换和合成气转化等诸多领域.近期发展的ZnCrO_x-分子筛双功能催化剂(OX-ZEO)打破了传统合成气转化的ASF分布,能够高选择性地实现CO加氢转化为低碳烯烃.其中CO在ZnCrO_x表面活化被认为是OX-ZEO催化的关键基元过程,但是ZnCrO_x表面的活性位组成和结构目前仍然缺乏原子尺度上的理解,阻碍了人们对反应机理的研究.因此,本文构建了Cr掺杂ZnO(1010)单晶的模型催化剂,结合低温扫描隧道显微镜(LT-STM)和X射线光电子能谱(XPS),研究不同条件下Cr在ZnO(1010)表面生长的形貌结构,并重点考察了Cr掺杂对表面电子结构和CO吸附的影响.ZnO(101–0)是Zn-O混合终止的非极性面,也是ZnO最稳定的晶面.实验发现室温下沉积Cr在ZnO(1010)表面时,出现多种生长结构.STM显示低覆盖度(<0.1 ML)的沉积Cr在ZnO(1010)台阶面上出现单分散的亮点和暗点,分别为位于表面O原子链上的Cr原子和嵌入ZnO晶格替代Zn²⁺的Cr.XPS显示这些Cr原子与ZnO之间存在电荷转移,呈现出+3价.由于Cr在[0001]方向扩散能垒高于沿着[1210]方向扩散的能垒,能够观察到少量沿着[0001]台阶方向生长的长方形岛,归属为Cr岛.表面单分散Cr原子和Cr岛的密度都会随着Cr沉积量的增加而增多.当在200 K沉积Cr来抑制Cr的表面扩散行为,我们发现Cr主要在ZnO面上形成Cr团簇,均匀分散在表面;而在400 K沉积时,Cr则直接扩散进入ZnO晶格.STM和XPS结果都表明,600 K以上的高温处理能够促进Cr进入ZnO晶格,同时伴随Cr岛的分解,这说明表面负载的Cr原子在高温不能稳定存在;而Cr岛的再分散进入到近表层甚至体相,也表明了Cr和ZnO之间的强相互作用.这种强相互作用有利于Cr在ZnO表层进行原子级分散,形成具有催化活性的结构;与此同时,实验发现Cr扩散到近表层会导致表面能带向上弯曲,从而导致XPS芯能级向低结合能位移.在超高真空条件下,CO与Cr掺杂的ZnO表面作用较弱,室温下只观察到碳酸盐的形成.因此,通过对比不同条件下Cr在ZnO(1010)表面的生长结构,热稳定性以及相应的电子结构变化,发现Cr和ZnO存在强相互作用,在600 K以上Cr以Cr³⁺形式分散到ZnO晶格中.本文通过构建Cr/ZnO(1010)模型催化剂,并研究其原子结构与电子结构的演变,为进一步的分子尺度合成气转化机理研究开辟了道路.     

利用原位APXPS与STM研究H2在ZnO(10${\rm{\bar 1}}$0)表面的活化

Cu/ZnO/Al₂O₃是工业中最广泛使用的甲醇合成催化剂。然而该催化反应的活性位点和机理目前仍存争议。H₂作为反应物之一,研究其在ZnO表面的活化和解离对于弄清甲醇合成反应的催化机理具有重要的帮助。本工作利用近常压光电子能谱(APXPS)和扫描隧道显微镜(STM)原位研究了H₂在ZnO(10${\rm{\bar 1}}$0)表面上的活化和解离。APXPS结果表明：在0.3 mbar (1 mbar = 100 Pa)的H₂气氛中,室温下ZnO表面形成羟基(OH)吸附物种。STM实验发现通入H₂后ZnO表面发生了(1×1)到(2×1)的重构。上述结果和原子H在ZnO(10${\rm{\bar 1}}$0)表面的吸附结果一致。然而吸附H₂O可以导致同样的现象。因此,我们还开展了H₂O在ZnO(10${\rm{\bar 1}}$0)表面吸附的对比实验。结果表明：H₂气氛中ZnO表面发生0.3 eV的能带弯曲,而H₂O吸附实验中几乎观察不到能带弯曲发生。同时,热稳定性实验表明H₂气氛中ZnO表面的OH不同于H₂O解离吸附产生的OH,前者具有更高的脱附温度。因此,本工作的结果表明常温和常压下H₂在ZnO(10${\rm{\bar 1}}$0)表面发生解离吸附。这一结果和以往超高真空下未发现H₂在ZnO(10${\rm{\bar 1}}$0)表面上的解离不同,说明H₂的活化是一个压力依赖过程。     

Kinetics of the reduction of the Rh(111) surface oxide: linking spectroscopy and atomic-scale information

The reduction of the surface oxide on Rh(111) by H(2) was observed in situ by scanning tunneling microscopy (STM) and high-resolution core level spectroscopy (HRCLS). At room temperature, H(2) does not adsorb on the oxide, only in reduced areas. Reduction starts in very few sites, almost exclusively in stepped areas. One can also initiate the reduction process by deliberately creating defects with the STM tip allowing us to examine the reduction kinetics in detail. Depending on the size of the reduced area and the hydrogen pressure, two growth regimes were found. At low H(2) pressures or small reduced areas, the reduction rate is limited by hydrogen adsorption on the reduced area. For large reduced areas, the reduction rate is limited by the processes at the border of the reduced area. Since a near-random distribution of the reduction nuclei was found and the reduction process at defects starts at a random time, one can use Johnson-Mehl-Avrami-Kolmogoroff (JMAK) theory to describe the process of reduction. The microscopic data from STM agree well with spatially averaged data from HRCLS measurements.     

Chlorine adsorption on Au(111): chlorine overlayer or surface chloride?

We report the first scanning tunneling microscope (STM) investigation, combined with density functional theory calculations, to resolve controversy regarding the bonding and structure of chlorine adsorbed on Au(111). STM experiments are carried out at 120 K to overcome instability caused by mobile species upon chlorine adsorption at room temperature. Chlorine adsorption initially lifts the herringbone reconstruction. At low coverages (<0.33 ML), chlorine binds to the top of Au(111)-(1 x 1) surface and leads to formation of an overlayer with (square root(3) x square root(3))R30 degree structure at 0.33 ML. At higher coverages, packing chlorine into an overlayer structure is no longer favored. Gold atoms incorporate into a complex superlattice of a Au-Cl surface compound.     

Phosphine dissociation and diffusion on Si(001) observed at the atomic scale

A detailed atomic-resolution scanning tunneling microscopy (STM) and density functional theory study of the adsorption, dissociation, and surface diffusion of phosphine (PH(3)) on Si(001) is presented. Adsorbate coverages from approximately 0.01 monolayer to saturation are investigated, and adsorption is performed at room temperature and 120 K. It is shown that PH(3) dissociates upon adsorption to Si(001) at room temperature to produce both PH(2) + H and PH + 2H. These appear in atomic-resolution STM images as features asymmetric-about and centered-upon the dimer rows, respectively. The ratio of PH(2) to PH is a function of both dose rate and temperature, and the dissociation of PH(2) to PH occurs on a time scale of minutes at room temperature. Time-resolved in situ STM observations of these adsorbates show the surface diffusion of PH(2) adsorbates (mediated by its lone pair electrons) and the dissociation of PH(2) to PH. The surface diffusion of PH(2) results in the formation of hemihydride dimers on low-dosed Si(001) surfaces and the ordering of PH molecules along dimer rows at saturation coverages. The observations presented here have important implications for the fabrication of atomic-scale P dopant structures in Si, and the methodology is applicable to other emerging areas of nanotechnology, such as molecular electronics, where unambiguous molecular identification using STM is necessary.     

Room‐Temperature Synthesis of Covalent Organic Frameworks with a Boronic Ester Linkage at the Liquid/Solid Interface

With various prospected applications in the field of nanoelectronics and catalysis, on‐surface synthesis of single‐layer covalent organic frameworks (surface COFs) with designable structures and properties have attracted enormous interest. Herein, we report on a scanning tunneling microscopic investigation of the surface‐confined synthesis of a covalently bonded boronic ester network directly at the octanoic acid/ highly oriented pyrolytic graphite(HOPG) interface under room temperature. The dynamic reaction process was investigated in detail. STM results indicate that the surface networks undergo structural evolution from a hybrid covalent/noncovalent multiwall porous network to single‐wall hexagonal COF with the decrease of monomer concentration. Further experimental observation disclosed that the boronic ester‐linked system is sensitive to instantaneous voltage pulses and the stimulation of the STM tip. In addition, the ¹H NMR spectra has further confirmed that the surface and octanoic acid may play important roles in promoting the reaction between 4,4′‐phenylazobenzoyl diboronic acid (ABBA) and 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP) building units.     

Direct observation of C2 hydrocarbon-oxygen complexes on Ag(110) with a variable-low-temperature scanning tunneling microscope

A variable-low-temperature scanning tunneling microscope (STM) was used to observe oxygen (O2), ethylene (C2H4), and acetylene (C2H2) molecules on a Ag(110) surface and the various complexes that were formed between these two hydrocarbons and oxygen at 13 K. Ethylene molecule(s) were moved to the vicinity of O2 either by STM tunneling electrons at 13 K or thermally at 45 K to form (C2H4)x-O2 (x = 1-4) complexes stabilized by C-H...O hydrogen bonding. Acetylene-oxygen complexes involving one or two acetylene molecules were observed.     

Reaction of 5-40 eV ions with self-assembled monolayers

The reaction of 5-40 eV O(+) and Ne(+) ions with alkanethiolate and semifluorinated alkanethiolate self-assembled monolayers (SAMs) is studied under ultrahigh vacuum (UHV) conditions. Whereas Ne(+) simply sputters fragments from the surface, O(+) can also abstract surface atoms and break C-C bonds in both the hydrocarbon and fluorocarbon SAM chains. Isotopic labeling experiments reveal that O(+) initially abstracts hydrogen atoms from the outermost two carbon atoms on an alkanethiolate SAM chain. However, the position of the isotopic label quickly becomes scrambled along the chain as the SAM is damaged through continuous ion bombardment. Scanning tunneling microscopy (STM) monitors changes in the SAM conformational structure at various stages during 5 eV ion bombardment. STM images indicate that O(+) reacts less efficiently with dodecanethiolate molecules packed internally within a structural domain than it does with molecules adsorbed at domain boundaries or near defect sites. STM images recorded after Ne(+) bombardment suggest that Ne(+) attacks the SAM exclusively near the domain boundaries. Taken collectively, these experiments advance our understanding of the degradation pathways suffered by polymeric satellite materials in the low-earth orbit (LEO) space environment.     

Atomic Defects on the Surface of Quasi Two-Dimensional Layered Titanium Dichalcogenides: Stm Experiment and Quantum Chemical Simulation

The atomic surface structure of layered dichalcogenide 1T-TiSe₂ is studied by scanning tunneling microscopy (STM) at room temperature. In STM images, the ordered structures in the form of 6 ×6 ×6 triangles of Se atoms extending for 0.3 ±0.20 Å above the crystal surface are observed. The effect of a series of different atomic structural defects on the surface topology of titanium disulphide is modeled on the example of isostructural and isoelectronic 1T-TiS₂ system using the DFTB method. It is determined that a good agreement with the STM experiment is showed by the model of local 1T-TiS₂ packing defects, where the coordination of titanium atoms changes from the octahedral to the prismatic one. For these systems, the calculation results of the electronic structure and defect formation energy are also presented.     

H atom adsorption and diffusion on Si(110)-(1×1) and (2×1) surfaces

We present a periodic density-functional study of hydrogen adsorption and diffusion on the Si(110)-(1×1) and (2×1) surfaces, and identify a local reconstruction that stabilizes the clean Si(110)-(1×1) by 0.51 eV. Hydrogen saturates the dangling bonds of surface Si atoms on both reconstructions and the different structures can be identified from their simulated scanning tunneling microscopy/current image tunneling spectroscopy (STM/CITS) images. Hydrogen diffusion on both reconstructions will proceed preferentially along zigzag rows, in between two adjacent rows. The mobility of the hydrogen atom is higher on the (2×1) reconstruction. Diffusion of a hydrogen vacancy on a monohydride Si(110) surface will proceed along one zigzag row and is slightly more difficult (0.2 eV and 0.6 eV on (1×1) and (2×1), respectively) than hydrogen atom diffusion on the clean surface.     

Thermal behavior of MOCVD-grown Cu-clusters on ZnO(1010)

Scanning tunnelling microscopy (STM) and X-ray photoelectron spectroscopy (XPS, AES) were used to study MOCVD of Cu-clusters on the mixed terminated ZnO(1010) surface in comparison to MBE Cu-deposition. Both deposition methods result in the same Cu cluster morphology. After annealing to 670 K the amount of Cu visible above the oxide surface is found to decrease substantially, indicating a substantial diffusion of Cu atoms inside the ZnO-bulk. The spectroscopic data do not show any evidence for changes in the Cu oxidation state during thermal treatment up to 770 K.     

Correlation of reaction sites during the chlorine extraction by hydrogen atom from ClSi(100)-2x1

The Cl abstraction by gas-phase H atoms from a Cl-terminated Si(100) surface was investigated by scanning tunneling microscopy (STM), high-resolution core level photoemission spectroscopy, and computer simulation. The core level measurements indicate that some additional reactions occur besides the removal of Cl. The STM images show that the Cl-extracted sites disperse randomly in the initial phase of the reaction, but form small clusters as more Cl is removed, indicating a correlation between Cl-extracted sites. These results suggest that the hot-atom process may occur during the atom-adatom collision.     

Unusual process of water formation on RuO2(110) by hydrogen exposure at room temperature

The reduction mechanism of the RuO(2)(110) surface by molecular hydrogen exposure is unraveled to an unprecedented level by a combination of temperature programmed reaction, scanning tunneling microscopy, high-resolution core level shift spectroscopy, and density functional theory calculations. We demonstrate that even at room temperature hydrogen exposure to the RuO(2)(110) surface leads to the formation of water. In a two-step process, hydrogen saturates first the bridging oxygen atoms to form (O(br)-H) species and subsequently part of these O(br)-H groups move to the undercoordinated Ru atoms where they form adsorbed water. This latter process is driven by thermodynamics leaving vacancies in the bridging O rows.