Peculiar Structural Phase of a Single-Atom-Thick Layer of Antimony.

Using molecular beam epitaxy, a new structural phase of a single atom thick antimony layer has been synthesized on the W(110) surface. Scanning tunneling microscopy measurements reveal an atomically resolved structure with a perfectly flat surface and unusually large unit cell. The structure forms a well-ordered continuous film with a lateral size in the range of several millimeters, as revealed by low energy electron microscopy and diffraction experiments. The results of density functional theory calculations confirm the formation of a new phase of single-atom-thick antimony film without the buckling characteristic for the known phases of antimonene. The presented results demonstrate a substrate-tuned approach in the preparation of new structural phases of 2D materials.

Temperature-Dependent Growth and Evolution of Silicene on Au Ultrathin Films-LEEM and LEED Studies.

The formation and evolution of silicene on ultrathin Au films have been investigated with low energy electron microscopy and diffraction. Careful control of the annealing rate and temperature of Au films epitaxially grown on the Si(111) surface allows for the preparation of a large scale, of the order of cm2, silicene sheets. Depending on the final temperature, three stages of silicene evolution can be distinguished: (i) the growth of the low buckled phase, (ii) the formation of a layered heterostructure of the low buckled and planar phases of silicene and (iii) the gradual destruction of the silicene. Each stage is characterized by its unique surface morphology and characteristic diffraction patterns. The present study gives an overview of structures formed on the surface of ultrathin Au films and morphology changes between room temperature and the temperature at which the formation of Au droplets on the Si(111) surface occurs.

Tuning Ferromagnetism in a Single Layer of Fe above Room Temperature.

The crystallographic and magnetic properties of an Fe monolayer (ML) grown on 2 ML Au/W(110) substrate are studied with spin-polarized low-energy electron microscopy, density functional theory, and relativistic screened Korringa-Kohn-Rostoker calculations. The single layer of iron atoms possesses hexagonal symmetry and reveals a ferromagnetic order at room temperature. We experimentally demonstrate the possibility of tuning the Curie temperature and the magnitude of magnetization of the Fe monolayer by capping with Au. Taking into account several structural models, the calculation results mostly show ferromagnetic states with enhanced magnetic moments of Fe atoms compared to their bulk value and a further increase in their value after covering with Au. The theoretically calculated Curie temperatures are in fair agreement with those obtained in the experiments. The calculations, furthermore, found evidence for the presence of frustrated isotropic Fe-Fe exchange interactions, and a discussion of the structural effects on the magnetic properties is provided herein.

Self-Assembly Properties of Solution Processable, Electroactive Alkoxy, and Alkylthienylene Derivatives of Fused Benzoacridines: A Scanning Tunneling Microscopy Study.

Self-organization in mono- and bilayers on HOPG of two groups of benz[5,6]acridino[2,1,9,8-klmna]acridine derivatives, namely, 8,16-dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines with an increasing alkoxy substituent length and 8,16-bis(3- or 4- or 5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines, i.e., three positional isomers of the same benzoacridine, is investigated by scanning tunneling microscopy. The layers were deposited from a solution of the adsorbate (in hexane or dichloromethane) and imaged ex situ at molecular resolution. In all cases, the resulting two-dimensional (2D) supramolecular organization is governed by the interactions between large, fused heteroaromatic cores that form densely packed rows separated by areas covered by substituents. In 8,16-dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines, the alkoxy substituents, separating the rows of densely packed cores, are interdigitated. An increasing substituent length leads to an intuitively expected increase in this 2D unit cell parameter that corresponds to the orientation of the substituent in the monolayer. In the case of 8,16-bis(3- or 4- or 5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine positional isomers, the self-assembly processes are more complex. Although the determined 2D unit cell is in all cases essentially the same, the role of alkylthienylene substituents in layer formation is distinctly different. Thus, the formation of monolayers and bilayers is very sensitive to isomerism. 8,16-Bis(5-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine is capable of forming the most stable monolayer and the most labile bilayer. In the case of 8,16-bis(3-octylthiophen-2-yl)benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine, an inverse phenomenon is observed leading to the most labile monolayer and the most stable bilayer. These differences are rationalized in terms of dissimilar molecular geometries of the studied isomers and different interdigitation patterns in their 2D supramolecular structures.

Supramolecular organization of liquid-crystal dimers - bis-cyanobiphenyl alkanes on HOPG by scanning tunneling microscopy.

2D supramolecular organization of a series of six cyanobiphenyls bimesogens deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM). The adsorbates are 1,ω-bis(4-cyanobiphenyl-4'-yl)alkanes (CBnCB) with different lengths of their flexible alkyl spacer (containing from 7 to 12 methylene groups). Microscopic investigations at the molecular resolution allow for detailed analysis of the effect of the alkyl spacer length on the type and the extent of the resulting 2D organization. It was demonstrated that bimesogens with shorter spacers (7 and 8 methylene units) organize in a similar manner characterized by the formation of two types of differently ordered monolayers: dense packed, wherein the molecules are oriented in one direction and ordered into parallel rows (layer structure), or less densely packed where they are organized into a chiral windmill-like structure. For derivatives with longer spacers (ranging from 9 to 12 methylene units) the additional effect of parity of carbon atoms in the spacer (even versus odd) is observed. In this range of the spacer lengths even membered bimesogens are also organized in a typical layer structure. However, odd-membered dimers exhibit a much more complex 2D supramolecular organization with a larger unit cell and a helical arrangement of the molecules. Careful comparison of this structure with the 3D structural data derived from the X-ray diffraction investigations of single crystals indicates that for these bimesogens a clear correlation exists between the observed complex 2D supramolecular organization in the monolayer and the organization in one of the crystallographic planes of the 3D nematic twist-bent phase.

Gold-capped silicon for ultrasensitive SERS-biosensing: Towards human biofluids analysis.

Surface-enhanced Raman spectroscopy (SERS) has been widely used in a variety of biomedical, analytical, forensic and environmental investigations due to its chemical specificity, label-free nature combined with high sensitivity. Here, we report a simple method for the fabrication of reproducible and reliable, well-defined, stable SERS substrates with uniform and giant Raman enhancement suitable for routine trace chemical analysis and detection of biological compounds in complex biological fluids. We prepared porous silicone (PS) surface by a galvanostatic anodic etch of crystalline silicon wafers. The electrochemical process generates a specific layer of PS: the thickness and porosity of a given layer is controlled by the current density, the duration of the etch cycle, and the composition of the etchant solution. These substrates presented high sensitivity to p-mercaptobenzoic acid (p-MBA) at a low concentration of 10-6M and the enhancement factor of over 108 was achieved. Such high enhancement is attributed to semiconducting silicon-induced and stabilized hot spots. The uniform distribution of SERS-active 'hot-spots' on the Au/Si surface results in high reproducibility towards detecting p-MBA at 40 different, randomly selected positions on a single substrate (RSD=6.7%) and on twenty different SERS substrates prepared under identical conditions (RSD=8%). Designed substrates allow the ultrahigh sensitive and specific detection of human such biofluids as blood, urine and cerebrospinal fluid (CSF) in a reliable, label-free, and reproducible manner. The SERS spectra of these fluids are rich in patient-specific information and can be useful in many analytical and biomedical applications. We have shown that our developed SERS substrates allow the nanomolar detection of neopterin (bacterial infections' marker) in cerebrospinal fluid samples. In order to test the performance of our SERS method in term of low detection limit (LOD), the calibration curve i.e. plot of SERS intensity of the marker band at 695cm-1 versus the concentration of neopterin in CSF was constructed and used to calculate the neopterin concentration in clinical samples. The level of neopterin was significantly higher in CSF samples infected by Neisseria meningitidis, (54nmol/L), compared to normal (control) group, (4.3nmol/L). The high sensitivity, selectivity and stability of obtained SERS-active substrates combined with simple, low-cost, and easy method of producing offer a promising tool for SERS-based analysis in clinical trials.

Star-Shaped Conjugated Molecules with Oxa- or Thiadiazole Bithiophene Side Arms.

Star-shaped conjugated molecules, consisting of a benzene central unit symmetrically trisubstituted with either oxa- or thiadiazole bithiophene groups, were synthesized as promising molecules and building blocks for application in (opto)electronics and electrochromic devices. Their optical (Eg (opt)) as well as electrochemical (Eg (electro)) band gaps depended on the type of the side arm and the number of solubilizing alkyl substituents. Oxadiazole derivatives showed Eg (opt) slightly below 3 eV and by 0.2 eV larger than those determined for thiadiazole-based compounds. The presence of alkyl substituents in the arms additionally lowered the band gap. The obtained compounds were efficient electroluminophores in guest/host-type light-emitting diodes. They also showed a strong tendency to self-organize in monolayers deposited on graphite, as evidenced by scanning tunneling microscopy. The structural studies by X-ray scattering revealed the formation of supramolecular columnar stacks in which the molecules were organized. Differences in macroscopic alignment in the specimen indicated variations in the self-assembly mechanism between the molecules. The compounds as trifunctional monomers were electrochemically polymerized to yield the corresponding polymer network. As shown by UV/Vis-NIR spectroelectrochemical studies, these networks exhibited reversible electrochromic behavior both in the oxidation and in the reduction modes.

Soluble Flavanthrone Derivatives: Synthesis, Characterization, and Application to Organic Light-Emitting Diodes.

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine-8,16-dione, an old and almost-forgotten vat dye, by reduction of its carbonyl groups and subsequent O-alkylation, yields solution-processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and -3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16-dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridine (FC-8), the most promising compound, was solved. It crystallizes in space group P1‾ and forms π-stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC-8 have a strong tendency to self-organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16-Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8-klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4'-bis(N-carbazolyl)-1,1'-biphenyl host in guest/host-type organic light-emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m(-12) , a luminance efficiency of about 3 cd A(-1) , and external quantum efficiencies exceeding 0.9 %.

Self-assembly properties of semiconducting donor-acceptor-donor bithienyl derivatives of tetrazine and thiadiazole-effect of the electron accepting central ring.

Scanning tunneling microscopy was used to study the effect of the electron-accepting unit and the alkyl substituent's position on the type and extent of 2D supramolecular organization of penta-ring donor-acceptor-donor (DAD) semiconductors, consisting of either tetrazine or thiadiazole central acceptor ring symmetrically attached to two bithienyl groups. Microscopic observations of monomolecular layers on HOPG of four alkyl derivatives of the studied adsorbates indicate significant differences in their 2D organizations. Ordered monolayers of thiadiazole derivatives are relatively loose and, independent of the position of alkyl substituents, characterized by large intermolecular separation of acceptor units in the adjacent molecules located in the face-to-face configuration. The 2D supramolecular architecture in both derivatives of thiadiazole is very sensitive to the alkyl substituent's position. Significantly different behavior is observed for derivatives of tetrazine (which is a stronger electron acceptor). Stronger intermolecular DA interactions in these adsorbates generate an intermolecular shift in the monolayer, which is a dominant factor determining the 2D structural organization. As a consequence of this molecular arrangement, tetrazine groups (A segments) face thiophene rings (D segments) of the neighboring molecules. Monolayers of tetrazine derivatives are therefore much more densely packed and characterized by similar π-stacking of molecules independently of the position of alkyl substituents. Moreover, a comparative study of 3D supramolecular organization, deduced from the X-ray diffraction patterns, is also presented clearly confirming the polymorphism of the studied adsorbates.

Effect of molecular mass on supramolecular organisation of poly(4,4''-dioctyl-2,2':5',2''-terthiophene).

The effect of the chain length on the type and extent of the 2D supramolecular organization in poly(4,4''-dioctyl-2,2':5',2''-terthiophene) (PDOTT) monomolecular layers deposited on highly oriented pyrolytic graphite (HOPG) is studied by scanning tunneling microscopy (STM) and analyzed in terms of molecular modeling. The strictly monodispersed fractions of increasing molecular mass used in this study were obtained by chromatographic fractionation of the crude product of 4,4''-dioctyl-2,2':5',2''-terthiophene oxidative polymerization. STM investigations of PDOTT layers, deposited on HOPG from poly- and monodispersed fractions, show that polydispersity can be considered as a key factor seriously limiting supramolecular ordering. This is a consequence of significant differences in the type of supramolecular order observed for molecules of different chain length. It has been demonstrated that shorter molecules (consisting of 6 and 9 thiophene units) form well-defined two-dimensional islands, while the interactions between longer molecules (consisting of 12 and 15 thiophene units) become anisotropic. Consequently, for higher molecular mass fractions, the supramolecular organization is one-dimensional and consists of more or less separated rows of ordered macromolecules. In this case an increase of the chain length leads to amplification of the intermolecular interactions proceeding via interdigitation of the alkyl substituents of adjacent molecules. Polydispersed fractions show much less ordered organization because of the incompatibility of the supramolecular structures of molecules of different molecular masses. This finding is of crucial importance for the application of polythiophene derivatives in organic and molecular electronics since ordered supramolecular organization constitutes the condition sine qua non of good electrical transport properties.