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No description available.

Four different trivalent and tetravalent metal phthalocyanine systems (chlorogallium, chloroindium, vanadyl, and titanyl phthalocyanines) were used singly to prepare thin films (0.05-2.0 micron thickness) on gold, optically transparent substrates. The photoelectronic properties of these electrodes could be modified either by altering the growth conditions (i.e. rate of sublimation, cleanliness of substrate) or by dosing the thin films with either hydrogen or oxygen at elevated temperatures (150°C). The properties of these thin films were monitored by electron microscopy, UV-visible spectrophotometry, X-ray and Ultra-violet surface spectroscopies, and a variety of electrochemical and photoelectrochemical techniques. All four systems behaved in a manner similar to a p-type semiconductor when prepared at rapid rates (10-20 A/min) on gold substrates. In the dark, for contacting redox couples with Eᵒ’ values negative of +0.6V, the phthalocyanine electrodes showed negligible dark currents. Upon illumination, the photoelectrodes only produced positive photopotentials. Chlorogallium phthalocyanine thin films could be made to produce both positive and negative photopotentials when grown at slow rates (1-5 A/min) on clean, gold substrates. These chlorogallium phthalocyanine electrodes regained the properties of a p-type semiconductor after being dosed with oxygen for 48 hours at 150°C. X-ray Photoelectron Spectroscopy confirmed the presence of a high concentration of oxygen at the surface of all of the p-type phthalocyanine electrodes. The oxygen may accept electron density from the phthalocyanine macrocycle to cause the Fermi level to move down in energy toward its valence band edge. Dosing the film with hydrogen caused the electrode to exhibit its original intrinsic characteristics. This variability in electrical properties as a function of gas dopant may lead to the development of a sensitive gas sensing device. Ultra-violet Photoelectron Spectroscopy, as well as molecular orbital calculations, were applied to the chlorogallium phthalocyanine system to determine the molecular orbital contributions to its valence and conduction bands. Photoelectrochemical cells made from electrodes of chlorogallium and vanadyl phthalocyanines exhibited power conversion efficiencies in excess of 0.1%. The vanadyl and titanyl phthalocyanine electrodes were also effective catalysts for the photoreduction of H⁺ to H₂.

The development of materials for optical thin film application is essential to progress in fields such as optical data storage and signal processing. Samarium sulfide (SmS) thin films were prepared by reactive evaporation of samarium in hydrogen sulfide (H₂S). These displayed optical switching properties despite the presence of large amounts of carbon and oxygen. They are therefore potentially useful for data storage. The semiconductor to metal phase transition was characterized by x-ray diffraction and spectrophotometry. The observed optical response was modelled by a Bruggeman effective medium calculation. Success with this analysis suggests it as a means for predicting performance in subsequent applications. Zinc sulfide (ZnS) thin films were prepared by molecular beam epitaxy (MBE). Implimentation of an H₂S treated silicon surface provided good chemical bond match in addition to a good lattice match. Atomic layer epitaxy was unsuccessfully explored as a means to grow ZnS from zinc and H₂S reactants, therefore other reactants are proposed. Both the MBE and ALE work is directed at the long term goals of producing p-type ZnS, which is suitable for semiconductor lasing at short wavelengths, and high quality SmS thin films.

This work concerns the vacuum deposition of novel thin films that exhibit nonlinear optical effects due to their unusual microstructure. We discuss four different materials: 1) Tilted columns of aluminum-oxide 2) Gold particles in aluminum-oxide 3) Cadmium sulpho-selenide particles in aluminum-oxide 4) Silver particles in zinc-sulphide. We begin with a description of the vacuum system and some the techniques used to characterize the optical and structural properties of the films. This leads to our study of second-harmonic generation (SHG) in aluminum-oxide thin films deposited at an angle to the evaporant source. We show that SHG is very sensitive to the non-isotropic microstructure that results from such a deposition. and the behavior of the SHG signal with sample orientation provides insight to the symmetry properties of the microstructure. In a related study we show that AU/Al₂O₃ composite films produce a large SHG signal. We investigate the dependence of the strength of the SHG signal with fill-fraction of gold and show that it increases quadratically. in agreement with theory. The third material we discuss is cadmium sulpho-selenide doped aluminumoxide. We describe attempts at nucleating semiconductor crystallites in a variety of hosts through a process of co-deposition and subsequent annealing. We also deposit alternate layers of CdS-Se and Al₂O₃ with the semiconductor layer thin enough that interspersed crystallites form. This results in suspended. isolated crystallites similar to the doped-glass materials of interest to nonlinear optics. A waveguide of a CdS/Al₂O₃ "sandwich" demonstrates optical nonlinearity through a power-dependent prism coupling experiment, and the degree of nonlinearity is much greater than undoped glass, though less than doped glass. The final section of the dissertation is a theoretical description of nonlinear optical behavior in a novel composite material consisting of metal particles in a nonlinear dielectric host. We assume the enhanced field around the resonating particles drives the host locally nonlinear through either a Kerr-type or thermal nonlinearity. We calculate the change in optical properties of the medium due to this effect and show that for a system of silver in zinc-sulphide the nonlinearity can be significant.

Materials in the form of thin films that have been deposited from the vapor phase are significantly different from similar bulk materials, both optically and mechanically, because of their columnar structure and consequent porosity. Their porosity have been verified in different ways. The effects of the pores on optical and mechanical performance and, in particular, the influence of water adsorption, have also been demonstrated. Three techniques used for investigating optical instabilities in thin films are given. They all involve sharp resonances. The resonances are associated either with surface plasmons, metal-dielectric narrowband filters, or all dielectric narrowband filters. These resonances are very sensitive functions of layer properties and hence can be used to detect and measure changes in the layers, particularly those that are induced by adsorption of moisture. Moisture adsorption in thin films is a complex process that occurs unevenly in patches. Using resonance techniques, the adsorption isotherms of change in refractive index, of growth rate in patch size, and of peak wavelength shift, which are all important in characterizing the porosity of films, have been measured. Some effects that locally increase film porosity and create central pores that permit water to penetrate into multilayer structures have been investigated. Based on these results, some suggestions for preventing water adsorption in films are then made. Moisture penetration into thin film structures is the major source of optical coating instability and it is therefore very important that the mechanisms of penetration by understood. Some deductions of the mechanisms are made from the experimental results.

We consider in this work the contribution of anisotropic microstructure to polarization effects in thin films. The microstructure is pictured by a simple model as composed of identical columns with elliptical cross section elongated in a direction perpendicular to that of the vapor incidence. The asymmetry in columnar structure that results from oblique deposition is identified as the common source for the significant dichroism and birefringence observed in metal and dielectric films, respectively. A four-dimensional theory for multilayer systems is presented that starts from first principles, unifies previous treatments for particular cases of film anisotropy, and properly handles the most general case of elliptically polarized mode propagation. In this framework and from a set of polarimetric measurements, a simple method is devised, with explicit consideration of the anisotropic microstructure, for the determination of the physical thickness and principal refractive indices of a single dielectric film. A sequence of transmittance measurements is performed with a zirconium oxide film deposited at 65° and, substrate role and instrumental errors considered, good agreement is obtained between theory and experiment. Spectrophotometer data for a narrowband filter with 21 layers deposited at 30° is shown to confirm theoretical predictions of peak positions with Angstrom resolution. A hypothetical metal film is discussed that reproduces the essential features observed in the optical behavior of an aluminum film deposited at 85°. Potential applications and suggestions for future work are included.

The incentive for conducting Degenerate Four Wave Mixing (DFWM) within guided wave devices is two-fold: (1) By coupling the optical beams into guided wave devices, the optical power densities can be increased orders of magnitude due to the tight confinement of the beams. Such an increase in power density means a concomitant increase in conversion efficiency of the signal beam. (2) The potential signal processing applications of DFWM (logic gates, switching, correlation/convolution), particularly for ultra-fast serial processing, would be better exploited, and adjoined to existing integrated circuit technology, by such an integrated optic/guided wave approach. In this dissertation we describe experiments and present data confirming the presence of DFWM within a planar glass thin film with carbon disulphide as the nonlinear cover medium. Optical pulses from a Q-switched, frequency doubled Nd:YAG laser are coupled into the glass film. The nonlinear polarization required to produce the desired conjugate signal is generated within the CS₂ by the evanescent tails of the guided input beams as they probe the nonlinear cover medium. The signals measured agree well with theory, but because they were so small in magnitude, signal-to noise ratios were small due to stray background radiation scattering from beamsplitters and other associated optics. Additionally, recent studies (Jain & Lind, 1983) indicate nonlinear responses in semiconductor (CdS/Se) doped glasses, commercially available as color glass filters, that are orders of magnitude higher than corresponding nonlinearities within CS₂, in addition to possessing subnanosecond response times. We have performed experiments upon such glasses in an effort to fabricate nonlinear optical waveguides within them via ion-exchange techniques. We have successfully fabricated single mode planar guides, but they are currently too lossy to allow demonstration of any guided wave nonlinearities. Also, we describe experiments in which we have measured (bulk) DFWM grating lifetimes with greater precision than previously reported. Results indicate a fast (20 to 50 pico-seconds, depending on the particular glass) electronic response, superimposed upon, but clearly distinguishable from, a slower (10's of nanoseconds) thermal response.

No description available.