Rapidly Infrared-Assisted Cooperatively Self-Assembled Highly Ordered Multiscale Porous Materials

In this paper, cooperative self-assembly (CSA) of colloidal spheres with different sizes was studied. It was found that a complicated jamming effect makes it difficult to achieve an optimal self-assembling condition for construction of a well-ordered stacking of colloidal spheres in a relatively short growth time by CSA. Through the use of a characteristic infrared (IR) technique to significantly accelerate local evaporation on the growing interface without changing the bulk growing environment, a concise three-parameter (temperature, pressure, and IR intensity) CSA method to effectively overcome the jamming effect has been developed. Mono- and multiscale inverse opals in a large range of lattice scales can be prepared within a growth time (15-30 min) that is remarkably shorter than the growth times of several hours for previous methods. Scanning electron microscopy images and transmittance spectra demonstrated the superior crystalline and optical qualities of the resulting materials. More importantly, the new method enables optimal conditions for CSA without limitations on sizes and materials of multiple colloids. This strategy not only makes a meaningful advance in the applicability and universality of colloidal crystals and ordered porous materials but also can be an inspiration to the self-assembly systems widely used in many other fields, such as nanotechnology and molecular bioengineering.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.

Molecular Antennas and Photoactive Nanomaterials based on Energy Transfer Processes

110 p.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Photoluminescence investigation of InAs bimodal self-assembled quantum dots state filling

Self-assembled InAs quantum dots were prepared on GaAS(100)) substrate in a solid source molecular beam epitaxy system The distribution and topographic images of uncapped dots were studied by atomic force microscope. The statistical result shows that the quantum dots are bimodal distribution. The photoluminescence spectrum results shows that the intensity of small size quantum dots dominated, which may be due to: (1) the state density of large quantum dots lower than that of small quantum dots; (2) the carriers capture rate of large size quantum dots is small relative to that of small ones; (3) there is a large strain barrier between large quantum dots and capping layer, and the large strain is likely to produce the defect and dislocation, resulting in a probability carriers transferring from large quantum dots to small dots that is very small with temperature increasing.

InAs nanostructure grown with different growth rate in InAlAs matrix on InP (001) substrate

InAs self-organized nanostructures in In0.52Al0.48As matrix have been grown on InP (001) substrates by molecular beam epitaxy. The morphologies of the nanostructures are found to be strongly dependent on the growth rate of the InAs layer. By increasing the growth rate from 0.005 to 0.35 ML/s, the morphology of the nanostructure changes from wire to elongated dot and then changes back to wire again. Polarized photoluminescence of the InAs quantum wires and quantum dots are performed at 77 K, which are characterized by strong optical anisotropies. (C) 2003 Elsevier B.V. All rights reserved.

Effect of the InAlAs and InGaAs combination strain-reducing layer on 1.3 mu m emission self-assembled InAs/GaAs quantum dots

Self-assembled InAs quantum dots (QDs) with differing deposition thicknesses covered by InxAl1-xAs (x = 0.2, 0.3) and In0.2Ga0.8As combination strain-reducing layers (CSRLs) were grown by molecular beam epitaxy. Their structural and optical properties were investigated by atomic force microscopy and photoluminescence spectroscopy, respectively. The emission peak position of InAs QDs capped by CSRL can reach 1.34 mum at room temperature with a relatively larger energy splitting of 93 meV between the ground and first excited states.

Raman scattering of folded acoustic phonons in self-assembled Si/Ge dot superlattices

Self-assembled Si/Ge dot multilayers with small, uncorrelated dots fabricated by molecular beam epitaxy in the Stranski-Krastanov growth mode are studied by Raman scattering of folded longitudinal acoustic (FLA) modes. The FLA Raman spectra are analyzed and modeled with respect to mode frequencies and the spectral envelope of mode intensities. The deduced average superlattice properties are consistent with results from atomic force microscopy. The simple Rytov model used for Si/Ge layer structures reproduces very well the frequencies of the FLA modes up to 150 cm(-1). The nonlinearity of phonon dispersion curves in bulk Si for large momenta, however, becomes important for modeling the higher frequencies of observed FLA modes up to 22nd order. The effective dot layer width and an activation energy for thermal intermixing of 2.1+/-0.2 eV are determined from the spectral envelopes of FLA mode intensities of as-grown and annealed Si/Ge dot multilayers. (C) 2004 American Institute of Physics.

Structural and optical properties of InAs/In0.52Al0.48As self-assembled quantum wires on InP(001)

Six-stacked InAs/In0.52Al0.48As self-assembled quantum wires (QWRs) on InP(001) by molecular-beam epitaxy (MBE) have been studied by high-resolution transmission electron microscopy (HRTEM) and polarized PL measurements. We obtained the chemical lattice fringe (CLF) image of InAs self-assembled QWRs embedded in the In0.52Al0.48As matrix by the interference between the (002)-diffracted beam and the transmitted beam in the image plane of the objective lens. The results show that the InAs QWRs were bounded by (113), (001) and (114) facets. Both the size and strain distribution in QWRs were determined. It was found that with the growth of successive periods, the height and height fluctuation of InAs QWRs decreased from the bottom period to the upper one. Some suggestions are put forward for further improving the uniformity of the stacked InAs QWRs. (c) 2005 Elsevier B.V. All rights reserved.

Artificial nanograting woven by self-assembled nanowires

We report on a new simple route to realize a high resolution nanograting. By adopting an InAlGaAs matrix and strain-compensated technique, we have proved that a uniform self-assembled InAs nanowire array can be fabricated by molecular beam epitaxy (MBE). A nanograting woven by self-assembled semiconductor nanowires shows a conspicuous diffraction feature. The good agreement between the theoretical and experimental values of diffraction peak positions indicates that a uniform nanowire array is a promising nanograting. This simple one-step MBE growth method will open exciting opportunities for the field of clever optics design.

Realization of highly uniform self-assembled InAs quantum wires by the strain compensating technique

Self-assembled InAs quantum wires (QWRs) on InP(001) substrate have been grown by molecular-beam epitaxy, using a strain compensating technique. Atom force microscope, Transmission electron microscopy, and high-resolution x-ray diffraction are used to characterize their structural properties. We proposed that, by carefully adjusting composition of InAlGaAs buffer layer and strain compensating spacer layers, stacked QWRs with high uniformity could be achieved. In addition, the formation mechanism and vertical anti-correlation of QWRs are also discussed. (c) 2005 American Institute of Physics.

Rapid thermal annealing effects on structural and optical properties of self-assembled InAs/GaAs quantum dots capped by InAlAs/InGaAs layers

Effects of rapid thermal annealing on the optical and structural properties of self-assembled InAs/GaAs quantum dots capped by the InAlAs/InGaAs combination layers are studied by photoluminescence and transmission electron microscopy. The photoluminescence measurement shows that the photoluminescence peak of the sample after 850 degrees C rapid thermal annealing is blue shifted with 370meV and the excitation peak intensity increases by a factor of about 2.7 after the rapid thermal annealing, which indicates that the InAs quantum dots have experienced an abnormal transformation during the annealing. The transmission electron microscopy shows that the quantum dots disappear and a new InAlGaAs single quantum well structure forms after the rapid thermal annealing treatment. The transformation mechanism is discussed. These abnormal optical properties are attributed to the structural transformation of these quantum dots into a single quantum well.

Changing planar thin film growth into self-assembled island formation by adjusting experimental conditions

Illustrated in this paper are two examples of altering planar growth into self-assembled island formation by adapting experimental conditions. Partial oxidation, undersaturated solution and high temperature change Frank-Van der Merwe (FM) growth of Al0.3Ga0.7As in liquid phase epitaxy (LPE) into isolated island deposition. Low growth speed, high temperature and in situ annealing in molecular beam epitaxy (MBE) cause the origination of InAs/GaAs quantum dots (QDs) to happen while the film is still below critical thickness in Stranski-Krastanow (SK) mode. Sample morphologies are characterized by scanning electron microscopy (SEM) or atomic force microscopy (AFM). It is suggested that such achievements are of value not only to fundamental researches but also to spheres of device applications as well. (c) 2004 Elsevier B.V. All rights reserved.

Effect of layer thickness of immiscible alloy In0.52Al0.48As on the morphology of InAs nanostructure grown on In0.52Al0.48As/InP(001)

Thickness effect of immiscible alloy InAlAs as matrix layer on the morphology of InAs nanostructure grown on InAlAs/InP (0 0 1) by solid-source molecular-beam epitaxy has been studied. Experiments demonstrate that InAs nanostructure grown on thin InAlAs matrix layer forms randomly distributed quantum dot, whereas, grown on thick InAlAs matrix layer forms one-dimension ordered mixture of quantum wire and quantum dot. This drastic modification in the nanostructure morphology is attributed to the generation of composition modulation in the immiscible InAlAs alloy with the increase of the layer thickness. (C) 2004 Elsevier B.V. All rights reserved.

Evolution of InAs/GaAs(001) islands during the two- to three-dimensional growth mode transition in molecular-beam epitaxy

A detailed observation was made using atomic force microscopy on the two- to three-dimensional (2D-3D) growth mode transition in the molecular-beam epitaxy of InAs/GaAs(001). The evolution of the 3D InAs islands during the 2D-3D mode transition was divided into two successive phases. The first phase may be explained in terms of a critical phenomenon of the second-order phase transition.