Mechanism study of femtosecond laser induced selective metallization (FLISM) on glass surfaces

We investigate the mechanism of selective metallization on glass surfaces with the assistance of femtosecond laser irradiation followed by electroless plating. Irradiation of femtosecond laser makes it possible to selectively deposit copper microstructures in the irradiated area on glass surfaces coated with silver nitrate films. The energy-dispersive X-ray (EDX) analyses reveal that silver atoms are produced on the surface of grooves formed by laser ablation, which serve as catalysis seeds for subsequent electroless copper plating. (C) 2008 Elsevier B.V. All rights reserved.

Vibrational pooling and constrained equilibration on surfaces

In this thesis, we provide a statistical theory for the vibrational pooling and fluorescence time dependence observed in infrared laser excitation of CO on an NaCl surface. The pooling is seen in experiment and in computer simulations. In the theory, we assume a rapid equilibration of the quanta in the substrate and minimize the free energy subject to the constraint at any time t of a fixed number of vibrational quanta N(t). At low incident intensity, the distribution is limited to one- quantum exchanges with the solid and so the Debye frequency of the solid plays a key role in limiting the range of this one-quantum domain. The resulting inverted vibrational equilibrium population depends only on fundamental parameters of the oscillator (ω_e and ω_eχ_e) and the surface (ω_D and T). Possible applications and relation to the Treanor gas phase treatment are discussed. Unlike the solid phase system, the gas phase system has no Debye-constraining maximum. We discuss the possible distributions for arbitrary N-conserving diatom-surface pairs, and include application to H:Si(111) as an example.

Computations are presented to describe and analyze the high levels of infrared laser-induced vibrational excitation of a monolayer of absorbed ¹³CO on a NaCl(100) surface. The calculations confirm that, for situations where the Debye frequency limited n domain restriction approximately holds, the vibrational state population deviates from a Boltzmann population linearly in n. Nonetheless, the full kinetic calculation is necessary to capture the result in detail.

We discuss the one-to-one relationship between N and γ and the examine the state space of the new distribution function for varied γ. We derive the Free Energy, F = NγkT − kTln(∑P_n), and effective chemical potential, μn ≈ γkT, for the vibrational pool. We also find the anti correlation of neighbor vibrations leads to an emergent correlation that appears to extend further than nearest neighbor.

Structure, chemistry, and energetics of organic and inorganic adsorbates on Ga-rich GaAs and GaP(001) surfaces

The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.

First, we investigate epitaxial Zn₃P₂ films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn₃P₂/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn₃P₂ and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.

Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.

Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.

The autocorrelation of speckles in deep Fresnel diffraction region and characterizations of random self-affine fractal surfaces

This paper studies the correlation properties of the speckles in the deep Fresnel diffraction region produced by the scattering of rough self-affine fractal surfaces. The autocorrelation function of the speckle intensities is formulated by the combination of the light scattering theory of Kirchhoff approximation and the principles of speckle statistics. We propose a method for extracting the three surface parameters, i.e. the roughness w, the lateral correlation length xi and the roughness exponent alpha, from the autocorrelation functions of speckles. This method is verified by simulating the speckle intensities and calculating the speckle autocorrelation function. We also find the phenomenon that for rough surfaces with alpha = 1, the structure of the speckles resembles that of the surface heights, which results from the effect of the peak and the valley parts of the surface, acting as micro-lenses converging and diverging the light waves.

The accuracy of Kirchhoff's approximation in describing the far field speckles produced by random self-affine fractal surfaces

Based on the rigorous formulation of integral equations for the propagations of light waves at the medium interface, we carry out the numerical solutions of the random light field scattered from self-affine fractal surface samples. The light intensities produced by the same surface samples are also calculated in Kirchhoff's approximation, and their comparisons with the corresponding rigorous results show directly the degree of the accuracy of the approximation. It is indicated that Kirchhoff's approximation is of good accuracy for random surfaces with small roughness value w and large roughness exponent alpha. For random surfaces with larger w and smaller alpha, the approximation results in considerable errors, and detailed calculations show that the inaccuracy comes from the simplification that the transmitted light field is proportional to the incident field and from the neglect of light field derivative at the interface.

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.

Selective metallization on insulator surfaces with femtosecond laser pulses

We report selective metallization on surfaces of insulators ( glass slides and lithium niobate crystal) based on femtosecond laser modification combined with electroless plating. The process is mainly composed of four steps: (1) formation of silver nitrate thin films on the surfaces of glass or crystal substrates; (2) generation of silver particles in the irradiated area by femtosecond laser direct writing; (3) removal of unirradiated silver nitrate films; and (4) selective electroless plating in the modified area. We discuss the mechanism of selective metallization on the insulators. Moreover, we investigate the electrical and adhesive properties of the copper microstructures patterned on the insulator surfaces, showing great potential of integrating electrical functions into lab-on-a-chip devices. (C) 2007 Optical Society of America.