Cyano‐Functionalized Triarylamines on Au(111): Competing Intermolecular versus Molecule/Substrate Interactions

The self‐assembly of cyano‐substituted triarylamine derivatives on Au(111) is studied with scanning tunneling microscopy and density functional theory calculations. Two different phases, each stabilized by at least two different cyano bonding motifs are observed. In the first phase, each molecule is involved in dipolar coupling and hydrogen bonding, while in the second phase, dipolar coupling, hydrogen bonding and metal‐ligand interactions are present. Interestingly, the metal–ligand bond is already observed for deposition of the molecules with the sample kept at room temperature leaving the herringbone reconstruction unaffected. It is proposed that for establishing this bond, the Au atoms are slightly displaced out of the surface to bind to the cyano ligands. Despite the intact herringbone reconstruction, the Au substrate is found to considerably interact with the cyano ligands affecting the conformation and adsorption geometry, as well as leading to correlation effects on the molecular orientation.     

Hydrogen‐Bonded Molecular Networks of Melamine and Cyanuric Acid on Thin Films of NaCl on Au(111)

Self‐assembly of organized molecular structures on insulators is technologically very relevant, but in general rather challenging to achieve due to the comparatively weak molecule–substrate interactions. Here the self‐assembly of a bimolecular hydrogen‐bonded network formed by melamine (M) and cyanuric acid (CA) on ultrathin NaCl films grown on a Au(111) surface is reported. Using scanning tunneling microscopy under ultrahigh‐vacuum conditions it is demonstrated that it is possible to exploit strong intermolecular forces in the M–CA system, resulting from complementary triple hydrogen bonds, to grow 2D bimolecular networks on an ultrathin NaCl film that are stable at a relatively high temperature of ≈160 K and at a coverage below saturation of the first molecular monolayer. These hydrogen‐bonded structures on NaCl are identical to the self‐assembled structures observed for the M–CA system on Au(111), which indicates that the molecular self‐assembly is not significantly affected by the isolating NaCl substrate.     

Control of self-assembled 2D nanostructures by methylation of guanine

Methylation of DNA nucleobases is an important control mechanism in biology applied, for example, in the regulation of gene expression. The effect of methylation on the intermolecular interactions between guanine molecules is studied through an interplay between scanning tunneling microscopy (STM) and density functional theory with empirical dispersion correction (DFT-D). The present STM and DFT-D results show that methylation of guanine can have subtle effects on the hydrogen-bond strength with a strong dependence on the position of methylation. It is demonstrated that the methylation of DNA nucleobases is a precise means to tune intermolecular interactions and consequently enables very specific recognition of DNA methylation by enzymes. This scheme is used to generate four different types of artificial 2D nanostructures from methylated guanine. For instance, a 2D guanine windmill motif that is stabilized by cooperative hydrogen bonding is revealed. It forms by self-assembly on a graphite surface under ambient conditions at the liquid-solid interface when the hydrogen-bonding donor at the N1 site of guanine is blocked by a methyl group.     

Direct Imaging of the Induced‐Fit Effect in Molecular Self‐Assembly

Molecular recognition is a crucial driving force for molecular self‐assembly. In many cases molecules arrange in the lowest energy configuration following a lock‐and‐key principle. When molecular flexibility comes into play, the induced‐fit effect may govern the self‐assembly. Here, the self‐assembly of dicyanovinyl‐hexathiophene (DCV6T) molecules, a prototype specie for highly efficient organic solar cells, on Au(111) by using low‐temperature scanning tunneling microscopy and atomic force microscopy is investigated. DCV6T molecules assemble on the surface forming either islands or chains. In the islands the molecules are straight—the lowest energy configuration in gas phase—and expose the dicyano moieties to form hydrogen bonds with neighbor molecules. In contrast, the structure of DCV6T molecules in the chain assemblies deviates significantly from their gas‐phase analogues. The seemingly energetically unfavorable bent geometry is enforced by hydrogen‐bonding intermolecular interactions. Density functional theory calculations of molecular dimers quantitatively demonstrate that the deformation of individual molecules optimizes the intermolecular bonding structure. The intermolecular bonding energy thus drives the chain structure formation, which is an expression of the induced‐fit effect.     

氧化铟纳米立方块的合成及其自组装膜

以乙酰丙酮铟为前驱体,在不同的有机溶剂中进行溶剂热反应,得到棱角规则清晰、尺寸可控的立方相氧化铟纳米立方块,通过X射线粉末衍射（XRD）、透射电子显微镜（TEM）等对产品进行详细表征,采用层层自组装技术,将氧化铟纳米立方块自组装戍厚度可控的薄膜,UV-vis吸收光谱强度的线性增长为多层膜组装提供了证据,且对氧化铟纳米立方块及其自组装薄膜的光致发光光谱进行了测试。     

Large-Scale Synthesis of Strain-Tunable Semiconducting Antimonene on Copper Oxide

Controlled synthesis of 2D structures on nonmetallic substrate is challenging, yet an attractive approach for the integration of 2D systems into current semiconductor technologies. Herein, the direct synthesis of high-quality 2D antimony, or antimonene, on dielectric copper oxide substrate by molecular beam epitaxy is reported. Delicate scanning tunneling microscopy imaging on the evolution intermediates reveals a segregation growth process on Cu₃O₂/Cu(111), from ordered dimer chains to packed dot arrays, and finally to monolayer antimonene. First-principles calculations demonstrate the strain-modulated band structures in antimonene, which interacts weakly with the oxide surface so that its semiconducting nature is preserved, in perfect agreement with spectroscopic measurements. This work paves the way for large-scale growth and processing of antimonene for practical implementation.     

2D self-assembly of oligo(p-phenylene vinylene) derivatives: from dimers to chiral rosettes

Enantiomerically pure oligo(p-phenylene vinylene) diaminotriazine derivatives and a short structurally related achiral diaminotriazine derivative, all having a rigid backbone in common, are studied to self-assemble at the solution-graphite interface by scanning tunneling microscopy. As a function of the length of the backbone, different two-dimensional motifs are formed (dimers and rosettes) that are rationalized in terms of the balance between different intermolecular interactions, in this case, intermolecular hydrogen bonding and the packing requirements of the alkyl chains on a graphite surface. In addition, the effect of molecular chirality on monolayer chirality is investigated, revealing molecular size-dependent expressions of the monolayer chirality.     

用密度泛函理论研究汞在CeO_2(111)表面的吸附

采用密度泛函理论计算了Hg、HgCl、HgCl_2在CeO_2(111)表面的吸附构型、吸附能和态密度。结果表明,Hg在CeO_2(111)表面属于弱化学吸附。HgCl与CeO_2(111)表面为强化学吸附,是反应的重要中间体。HgCl_2在CeO_2(111)表面是物理吸附,易发生解离,脱除。氯对于汞的吸附和氧化产生较强的影响,这与实验结果相一致。基于计算结果,得到汞在CeO_2(111)表面的反应机理。     

The Itinerant 2D Electron Gas of the Indium Oxide (111) Surface: Implications for Carbon‐ and Energy‐Conversion Applications

Transparent conducting oxides (TCO) have integral and emerging roles in photovoltaic, thermoelectric energy conversion, and more recently, photocatalytic systems. The functional properties of TCOs, and thus their role in these applications, are often mediated by the bulk electronic band structure but are also strongly influenced by the electronic structure of the native surface 2D electron gas (2DEG), particularly under operating conditions. This study investigates the 2DEG, and its response to changes in chemistry, at the (111) surface of the model TCO In₂O₃, through angle resolved and core level X‐ray photoemission spectroscopy. It is found that the itinerant charge carriers of the 2DEG reside in two quantum well subbands penetrating up to 65 Å below the surface. The charge carrier concentration of this 2DEG, and thus the high surface n‐type conductivity, emerges from donor‐type oxygen vacancies of surface character and proves to be remarkably robust against surface absorbents and contamination. The optical transparency, however, may rely on the presence of ubiquitous surface adsorbed oxygen groups and hydrogen defect states that passivate localized oxygen vacancy states in the bandgap of In₂O₃.     

Ceria Nanocrystals Exposing Wide (100) Facets: Structure and Polarity Compensation

Compact CeO₂(111) films grown on Ru(0001) can be transformed into well‐shaped nanoparticles by annealing them in an oxygen‐poor environment. With increasing temperature, the particles undergo a distinct shape evolution that finally leads to crystallites exposing wide (100) facets. The atomic structure of the (100) termination is determined with a combination of high‐resolution scanning tunneling microscopy and density functional theory. Two surface reconstructions are identified that are compatible with the need to compensate for the intrinsic dipole of the (100) plane and with a substantial reduction of the oxide material. Our study provides insights into the rarely explored (100) surface of ceria, which can be considered as model system for studying chemical processes on the polar termination of reducible oxides.     

Electron‐Induced Dynamics of Heptathioether β‐Cyclodextrin Molecules

Variable‐temperature scanning tunneling microscopy (STM) and spectroscopy (STS) measurements are performed on heptathioether β‐cyclodextrin (β‐CD) self‐assembled monolayers (SAMs) on Au. The β‐CD molecules exhibit very rich dynamical behavior, which is not apparent in ensemble‐averaged studies. The dynamics are reflected in the tunneling current–time traces, which are recorded with the STM feedback loop disabled. The dynamics are temperature independent, but increase with increasing tunneling current and sample bias, thus indicating that the conformational changes of the β‐CD molecules are induced by electrons that tunnel inelastically. Even for sample biases as low as 10 mV, well‐defined levels are observed in the tunneling current–time traces. These jumps are attributed to the excitations of the molecular vibration of the macrocyclic β‐CD molecule. The results are of great importance for a proper understanding of transport measurements in SAMs.     

Triphenylene‐Derived Electron Acceptors and Donors on Ag(111): Formation of Intermolecular Charge‐Transfer Complexes with Common Unoccupied Molecular States

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes.     

In2O3薄膜及纳米颗粒制备进展

主要介绍了In2O2薄膜及其纳米颗粒的制备方法和特点,并比较了它们的优缺点。