Nanostructured Thin Films via Self‐Assembly of Block Copolymers

Thin films of incompatible block copolymers self‐assemble into highly regular supramolecular structures with characteristic dimensions in the 10–100 nm regime. There is increasing interest in controlling the resulting structures and utilizing them, for instance in the area of nanotechnology. So far, research has concentrated mainly on exploiting the melt structure of diblock copolymers. Recent work on block copolymer solutions and more complex co‐ and terpolymer architectures has revealed a rich variety of novel thin‐film structures, some of which exhibit high complexity and order. In addition, by use of mean field dynamic density functional theory along with well‐controlled experiments, the fundamentals of thin film structure formation have been elucidated. We highlight some aspects of these studies and point to future directions in this lively field of materials science.     

单分子膜诱导化学/电化学沉积纳米复合薄膜的研究进展

介绍了以单分子膜为基底，化学／电化学沉积纳米复合薄膜的发展现状，并对该方法的制备原理、工艺条件、膜结构、及其表征方法进行了阐述，还对发展方向进行了展望。     

Bromination of [60]Fullerene. I. High-Yield Synthesis of C60Brx (x=6, 8, 24)

The systematic study of the bromination of C₆₀ was performed under various experimental conditions. Application of some chloroarenes as reaction media resulted in the high-yield (70-96%) selective synthesis of C₆₀Br₆ and C₆₀Br₈. Direct bromination of fullerene yielded either C₆₀Br₈, C₆₀Br₁₄, or C₆₀Br₂₄ depending on the reaction time. Possible pathways of bromination of C₆₀Br₈ were analyzed using semiempirical (AM1) calculations, two most probable molecular structures are conjectured for the first isolated C₆₀Br₁₄.     

Multiple Charged Nitrogen Ion Beam Irradiation of Fullerene Thin Films

In this work, the results of structural modification of fullerene thin films bombarded by multiple charged nitrogen ions have been reported. The properties of as-deposited and irraditated fullerene thin films have been investigated by Raman and FTIR spectroscopy and AFM analysis. After irradiation by multiple charged nitrogen ions (N²⁺, N⁵⁺) new bondings in fullerene films have been formed and the amorphicity has been enhanced at higher doses. Raman and FTIR spectra showed structural changes of deposited films depending on the energy and implantation dose. AFM analysis showed that the ion beam had destroyed the surface ordering. At lower doses the surface order has been characterized by carbon clusters of 500 nm. At higher doses significantly smaller clusters have been formed (200 nm).     

Bromination of [60]Fullerene. II. Crystal and Molecular Structure of [60]Fullerene Bromides, C60Br6, C60Br8, and C60Br24

The crystal and molecular structures of the bromofullerene solvates C₆₀Br₆·0.5C₆H₅Cl·0.5Br₂, C₆₀Br₈·1.5(o-C₆H₄Cl₂), C₆₀Br₈·Br₂, C₆₀Br₈·0.5C₆H₅Br·0.5Br₂, and C₆₀Br₂₄·2Br₂ have been determined by single crystal X-ray diffraction. The molecular species C₆₀Br₆, C₆₀Br₈, and C₆₀Br₂₄ which have idealized C_s, C_2v , and T_h symmetries, respectively, have several different types of C-Br and C-C bonds. A comparison between different solvates of the same bromofullerenes revealed a larger stability of the packing modes for the C₆₀Br₆ and C₆₀Br₂₄ solvates, whereas the C₆₀Br₈ solvates showed different packing motifs dependent on the nature and amount of the solvent molecules.     

Multifunctional FeCo/TiN Multilayer Thin Films with Combined Magnetic and Protective Properties

Coatings with thicknesses ranging from a few nanometer up to several micrometer produced by physical vapor deposition (PVD) processes have been established in engineering technologies since the early 1980s. In particular, magnetron sputtered wear resistance coatings are industrially established and capable to enhance tool lifetimes significantly. However, in cases where optical inspection of a coating in use is not possible, an intrinsic sensor function of the film would be beneficial. Therefore, the development of wear resistant coatings with an integrated sensor functionality based on the insertion of a magnetoelastic ferromagnetic phase is suggested. In combination with appropriate read‐out electronics such a film system would be ready for online monitoring of the coatings' actual state (e.g., strain, temperature, volume loss). This paper focuses on the development of wear resistance coatings which simultaneously supply beneficial mechanical properties as well as ferromagnetic properties optimized for online non‐contact read‐out applications. Multilayer coatings obtained through alternate stacking of magnetron sputtered TiN and FeCo layers with a nominal total thickness of 1000 nm were produced as a model system meeting the above conditions. The bilayer period was varied down to 2.6 nm while the individual layer thickness ratio t_TiN/t_FeCo was determined by the deposition rates and maintained constant at a value of about 3/1. The films were vacuum annealed ex situ in a static magnetic field subsequent to the deposition. The constitution of the as‐deposited and annealed coatings as well as their mechanical (nanohardness, Young's modulus) and magnetic properties (magnetization hysteresis, frequency‐dependent permeability) are described. Finally, the suitability of the coatings for the use in remote‐interrogable wear sensor applications is briefly discussed.     

Ion irradiation hardening of C60 thin films

The nanoindentation technique is used to measure the hardness and the Young’s modulus of ion irradiated C₆₀ films, 70 nm thick, deposited on a Silicon substrate. An increase of hardness from 1.3 GPa for the pristine sample to 10 GPa after irradiation with 800 keV Bi⁺ and N²⁺ ions was observed. The Young’s modulus also increases from 60–150 GPa after the irradiation. The results are discussed in terms of the damage and amorphization produced as consequences of the electronic and nuclear energy transference due to the irradiation.     

Electrolytic and electrophoretic deposition of CeO2 films

Cerium oxide films of thickness 0.1–300 μm were deposited on Ni substrates via cathodic electrolytic and electrophoretic deposition. The films were studied by X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. Experimental results obtained by both deposition methods are compared. The influence of deposition parameters and additives on deposition yields and film morphologies is studied and discussed.