Electrochemical and Electronic Charge Transport Properties of Ni-Doped LiMn₂O₄ Spinel Obtained from Polyol-Mediated Synthesis.

LiNiMnO₄ (LNMO) spinel has been extensively investigated as one of the most promising high-voltage cathode candidates for lithium-ion batteries. The electrochemical performance of LNMO, especially its rate performance, seems to be governed by its crystallographic structure, which is strongly influenced by the preparation methods. Conventionally, LNMO materials are prepared via solid-state reactions, which typically lead to microscaled particles with only limited control over the particle size and morphology.

Directed Self-Assembly and Infrared Reflection Absorption Spectroscopy Analysis of Amphiphilic and Zwitterionic Janus Gold Nanoparticles.

Here, we report an approach to use infrared reflection absorption spectroscopy (IRRAS) for the unambiguous proof of the presence as well as the spatial distribution of organic ligands on the Janus gold nanoparticle (AuNP) surface. For this purpose we synthesized amphiphilic and zwitterionic Janus AuNPs and immobilized these on pretreated gold surfaces by directed self-assembly, exploiting hydrophilic/hydrophobic or electrostatic interactions, respectively. Thus, we obtained macroscopic two-dimensional arrays of Janus AuNPs exhibiting a specific orientation.

Differential adsorption of gold nanoparticles to gold/palladium and platinum surfaces.

Integration of molecule-capped gold nanoparticles (AuNP) into nanoelectronic devices requires detailed knowledge about the AuNP-electrode interface. Here, we report the pH-dependent adsorption of amine or carboxylic acid-terminated gold nanoparticles on platinum or gold/palladium (30% Pd) alloy, respectively. We synthesized amine-terminated AuNP, applying a new solid phase supported approach, as well as AuNP exhibiting carboxylic acid as terminal groups.

Electronic transport properties of individual 4,4'-bis(mercaptoalkyl)-biphenyl derivatives measured in STM-based break junctions.

Electronic transport measurements of single, systematically varied 4,4'-bis(mercaptoalkyl)-biphenyl derivatives (MABP) are performed in a controlled test-device. The molecules are composed of a central biphenyl unit (BP) carrying two mercaptoalkyl substituents with different chain lengths (m, n = number of CH(2)-units), in the para-position of the BP unit. The total length of both spacers is m + n = 10.

On the application potential of gold nanoparticles in nanoelectronics and biomedicine.

Ligand-stabilized gold nanoparticles (AuNPs) are of high interest to research dedicated to future technologies such as nanoelectronics or biomedical applications. This research interest arises from the unique size-dependent properties such as surface plasmon resonance or Coulomb charging effects. It is shown here how the unique properties of individual AuNPs and AuNP assemblies can be used to create new functional materials for applications in a technical or biological environment.

Field-emission resonances at tip/alpha,omega-mercaptoalkyl ferrocene/Au interfaces studied by STM.

The electrical properties of alpha,omega-mercaptoalkyl ferrocenes with different alkyl chain lengths embedded in a self-assembled host matrix of alkanethiols on Au(111) are studied by scanning tunneling microscopy and spectroscopy. Based on current-distance spectroscopy, as well as on the evaluation of Fowler-Nordheim tunneling current oscillations, the apparent barrier height of ferrocene is determined independently by two methods. The electronic coupling of the ferrocene moiety to the Au(111) substrate is shown to depend on the length of the alkane-spacer chain.

Striped phase of mercaptoalkylferrocenes on Au(111) with a potential for nanoscale surface patterning.

The molecular structure of submonolayer-coverage phases of 3-(thioacetyl)-propanoylferrocene and 5-ferrocenylpentanethiol in mixed layers with alkanethiols on Au(111) was resolved by scanning tunneling microscopy. The ferrocenes formed a striped surface phase, similar to the lying-down structures of alkanethiols, resulting in equally spaced rows of the ferrocene moieties. The obtained nanoscale lattice of functional groups on the surface offers an interesting potential for the patterning of small, periodic structures with precise distance control via a hydrocarbon spacer.

Scanning tunneling microscopy and spectroscopy studies of 4-methyl- 4'-(n-mercaptoalkyl)biphenyls on Au(111)-(1x1).

4-methyl-4'-(n-mercaptoalkyl)biphenyl (CH3-C6H4-C6H4-(CH2)n-SH, n=3-6, BPn) monolayers assembled on Au(111)-(1x1) in 1,3,5,-trimethylbenzene (TMB) at various temperatures are studied by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). High resolution STM images reveal that BP3 and BP5 form a (sqrt 3x2sqrt 3) repeating motif superimposed on a temperature-dependent Moire pattern. BP4 and BP6 adlayers are characterized by a coexisting (2sqrt 3x5sqrt 3) majority phase and a temperature-dependent (3xpsqrt 3) minority phase.

Dilithiation of Bis(benzene)molybdenum and subsequent isolation of a molybdenum-containing paracyclophane.

The homoleptic sandwich complex bis(benzene)molybdenum, [Mo(eta6-C6H6)2], was successfully dilithiated by employing an excess of BuLi in the presence of N,N,N',N'-tetramethylethylenediamine (up to 6 equiv each) at slightly elevated temperatures furnishing the highly reactive, ring metalated species [Mo(eta6-C6H5Li)2].tmeda in high yields. Alternatively, this compound was synthesized upon prolonged sonication with 5 equiv of tBuLi/tmeda without heating.

STM study of mixed alkanethiol/biphenylthiol self-assembled monolayers on Au(111).

A method is presented for depositing mixed self-assembled monolayers (SAMs) of dodecanethiol (C12) and 4'-methyl-1,1'-biphenyl-4-butane (H3C-C6H4-C6H4-(CH2)4-SH, BP4) by insertion of BP4 into a closely packed SAM of dodecanethiol on Au(111). Insertion takes place at defect sites such as domain boundaries or etch pits in the gold surface that are characteristic of C12 monolayers on gold. With a lower probability, insertion also occurs beside defect sites inside dodecanethiol domains.