Field-effect transistors based on self-organized molecular nanostripes

Charge transport properties in organic semiconductors depend strongly on molecular order. Here we demonstrate field-effect transistors where drain current flows through a precisely defined array of nanostripes made of crystalline and highly ordered molecules. The molecular stripes are fabricated across the channel of the transistor by a stamp-assisted deposition of the molecular semiconductors from a solution. As the solvent evaporates, the capillary forces drive the solution to form menisci under the stamp protrusions. The solute precipitates only in the regions where the solution is confined by the menisci once the critical concentration is reached and self-organizes into molecularly ordered stripes 100-200 nm wide and a few monolayers high. The charge mobility measured along the stripes is 2 orders of magnitude larger than the values measured for spin-coated thin films.

Orientation dependent electrocatalysis using self-assembled molecular films

Surface orientation of self-assembled molecular films of 2,9,6,23-tetraamino cobalt phthalocyanine on gold and silver is shown to determine the nature and the products of the electrocatalytic reduction of oxygen.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.

Propriedades luminescentes de polioxometalato contendo európio(III) correlacionadas à sua conformação em sólido estendido e em filmes auto-organizados de Langmuir e Langmuir-Blodgett

Pós-graduação em Química - IQ

Control of self-organized low-dimensional morphology in Poly(styrene-b-4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene-b-4vinylpyridine) (PS-b-P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (phi(PS)) in the mixture. It was found that when hPS was added into symmetric PS-b-P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With phi(PS) increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in phi(PS) is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated.

Self-organized superlattices along the [001] growth direction in In0.52Al0.48As layers grown on nominally (001) InP substrates by molecular beam epitaxy

Horizontal self-organized superlattice structures consisting of alternating In-rich and Al-rich layers formed naturally during solid-source molecular beam epitaxy (MBE) growth of In0.52Al0.48As on exactly (001) InP substrates, with In and At fluxes unchanged. The growth temperatures were changed from 490 to 510 degrees C, the most commonly used growth temperature for In0.52Al0.48As alloy. No self-organized superlattices (SLs) were observed at the growth temperature 490 degrees C, and self-organized SLs were observed in InAlAs layers at growth temperatures ranging from 498 to 510 degrees C. The results show that the period of the SLs is very highly regular, with the value of similar to 6 nm, and the composition of In or Al varies approximately sinusoidally along the [001] growth direction. The theoretical simulation results confirm that the In composition modulation amplitude is less than 0.02 relative the In composition of the In0.52Al0.48As lattice matched with the InP substrate. The influence of InAs self-organized quantum wires on the spontaneously formed InxAl1-xAs/InyAl1-yAs SLs was also studied and the formation of self-organized InxAl1-xAs/InyAl1-yAs SLs was attributed to the strain-mediated surface segregation process during MBE growth of In0.52Al0.48As alloy. (C) 2005 Published by Elsevier Ltd.

Cr-doped InAs self-organized diluted magnetic quantum dots with room-temperature ferromagnetism

Cr-doped InAs self-organized diluted magnetic quantum dots (QDs) are grown by low-temperature molecular-beam epitaxy, Magnetic measurements reveal that the Curie temperature of all the InAs:Cr QDs layers with Cr/In flux ratio changing from 0.026 to 0.18 is beyond 400 K. High-resolution cross sectional transmission electron microscopy images indicate that InAs:Cr QDs are of the zincblende structure. Possible origins responsible for the high Curie temperature are discussed.

Optical and electrical characterizations of ZnSe self-organized quantum dots grown by molecular beam epitaxy

Optical and electrical properties of ZnSe self-organized quantum dots were investigated using photoluminescence, capacitance-voltage, and deep level transient Fourier spectroscopy techniques. The temperature dependence of photoluminescence was employed to clarify the mechanism of photoluminescence thermal quenching processes in ZnSe quantum dots. A theoretic fit on considering a two-step quenching processes well explained the experimental data. The apparent carrier concentration profile obtained from capacitance-voltage measurements exhibits an accumulation peak at the depth of about 100nm below the sample surface, which is in good agreement with the location of the quantum dot layer. The electronic ground state of ZnSe quantum dots is determined to be about 0.11 eV below the conduction band of ZnS, which is similar to that obtained by simulating the thermal quenching of ZnSe photoluminescence.

Lateral ordered InGaAs self-organized quantum dots grown on (311) GaAs by conventional molecular beam epitaxy

Self-assembled InxGa1-xAs quantum dots (QDs) on (311) and (100) GaAs surfaces have been grown by conventional solid source molecular beam epitaxy. Spontaneously ordering alignment of InxGa1-xAs QDs with lower In content around 0.3 has been observed on As-terminated (B type) surfaces. The direction of alignment orientation of the QDs formation differs from the direction of misorientation of the (311) B surface, and is strongly dependent upon the In content x. The ordering alignment becomes significantly deteriorated as the In content is increased to above 0.5 or as the QDs are formed on (100) and (311) Ga-terminated (A type) substrates.

Nanoscale effects and applications of self-organized nanostructured thin films

A nanostructured thin film is a thin material layer, usually supported by a (solid) substrate, which possesses subdomains with characteristic nanoscale dimensions (10 ~ 100 nm) that are differentiated by their material properties. Such films have captured vast research interest because the dimensions and the morphology of the nanostructure introduce new possibilities to manipulating chemical and physical properties not found in bulk materials. Block copolymer (BCP) self-assembly, and anodization to form nanoporous anodic aluminium oxide (AAO), are two different methods for generating nanostructures by self-organization. Using poly(styrene-block-methyl methacrylate) (PS-b-PMMA) nanopatterned thin films, it is demonstrated that these polymer nanopatterns can be used to study the influence of nanoscale features on protein-surface interactions. Moreover, a method for the directed assembly of adsorbed protein nanoarrays, based on the nanoscale juxtaposition of the BCP surface domains, is also demonstrated. Studies on protein-nanopattern interactions may inform the design of biomaterials, biosensors, and relevant cell-surface experiments that make use of nanoscale structures. In addition, PS-b-PMMA and AAO thin films are also demonstrated for use as optical waveguides at visible wavelengths. Due to the sub-wavelength nature of the nanostructures, scattering losses are minimized, and the optical response is amenable to analysis with effective medium theory (EMT). Optical waveguide measurements and EMT analysis of the films’ optical anisotropy enabled the in situ characterization of the PS-b-PMMA nanostructure, and a variety of surface processes within the nanoporous AAO involving (bio)macromolecules at high sensitivity.

Plasma-assisted self-organized growth of uniform carbon nanocone arrays

The self-organized growth of uniform carbon nanocone arrays using low-temperature non-equilibrium Ar + H 2 + CH 4 plasma-enhanced chemical vapor deposition (PECVD) is studied. The experiment shows that size-, shape-, and position-uniform carbon nanocone arrays can develop even from non-uniformly fragmented discontinuous nickel catalyst films. A three-stage scenario is proposed where the primary nanocones grow on large catalyst particles during the first stage, and the secondary nanocones are formed between the primary ones at the second stage. Finally, plasma-related effects lead to preferential growth of the secondary nanocones and eventually a uniform nanopattern is formed. This does not happen in a CVD process with the same gas feedstock and surface temperature. The proposed three-stage growth scenario is supported by the numerical experiment which generates nanocone arrays very similar to the experimentally synthesized nanopatterns. The self-organization process is explained in terms of re-distribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array. Our results suggest that plasma-related self-organization effects can significantly reduce the non-uniformity of carbon nanostructure arrays which commonly arises from imperfections in fragmented Ni-based catalyst films.

Defects around self-organized InAs quantum dots measured by slow positron beam

Self-organized InAs quantum dots (QDs) have been fabricated by molecular beam epitaxy. The authors try to use a slow positron beam to detect defects in and around self-organized QDs, and point defects are observed in GaAs cap layer above QDs. For the self-organized InAs QDs without strain-reducing layer, it is free of defects. However, by introducing a strain-reducing layer, the density of point defects around larger sized InAs QDs increased. The above results suggest that low energy positron beam measurements may be a good approach to detect depth profiles of defects in QD materials. (c) 2007 American Institute of Physics.

Self-organized hexagonal ordering of quantum dot arrays

We report a structure of (In, Ga)As/GaAs quantum dots which are vertically correlated and laterally aligned in a hexagonal way thus forming three-dimensionally ordered arrays. The growth pathway is based on a mechanism of self-assembly by strain-mediated multilayer vertical stacking on a planar GaAs(100) substrate, rather than molecular-beam epitaxy on a prepatterned substrate. The strain energy of lateral island-island interaction is minimum for the arrangement of hexagonal ordering. However, realization of hexagonal ordering not only depends on a complicated trade-off between lateral and vertical island-island interaction but is also related to a delicate and narrow growth kinetics window.

High uniformity of self-organized InAs quantum wires on InAlAs buffers grown on misoriented InP(001)

Highly uniform InAs quantum wires (QWRs) have been obtained on the In0.5Al0.5As buffer layer grown on the InP substrate 8 degrees off (001) towards (111) by molecular-beam epitaxy. The quasi-periodic composition modulation was spontaneously formed in the In0.5Al0.5As buffer layer on this misoriented InP (001). The width and period of the In-rich bands are about 10 and 40 nm, respectively. The periodic In-rich bands play a major role in the sequent InAs QWRs growth and the InAs QWRs are well positioned atop In-rich bands. The photoluminescence (PL) measurements showed a significant reduction in full width at half maximum and enhanced PL efficiency for InAs QWRs on misoriented InP(001) as compared to that on normal InP(001). (c) 2006 American Institute of Physics.

Self-organized InAs quantum wires on GaAs (331)A substrates

Self-organized InAs quantum wires (QWRs) were fabricated on the step edges of the GaAs (331)A surface by molecular beam epitaxy. The lateral size of InAs QWRs was saturated by the terrace width (i.e., 90 nm) while the size along the step lines increased with the increasing thicknesses of the InAs layers, up to 1100 nm. The height of InAs QWRs varied from 7.9 nm to 13 nm. The evolution of the morphology of InAs QWRs was attributed to the diffusion anisotropy of In adatoms.