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Paley, Mark S.

Publications and source records attributed to Paley, Mark S..

35 records · Page 2

Nonlinear Optical Properties and Applications of Polydiacetylene

Recently, we have demonstrated a picosecond all-optical switch, which also functions as a partial all-optical NAND logic gate using a novel polydiacetylene that is synthesized in our laboratory. The nonlinear optical properties of the polydiacetylene material are measured using the Z-scan technique. A theoretical model based on a three level system is investigated and the rate equations of the system are solved. The theoretical calculations are proven to match nicely with the experimental results. The absorption cross-sections for both the first and higher excited states are estimated. The analyses also show that the material suffers a photochemical change beyond a certain level of the laser power and its physical properties suffer radical changes. These changes are the cause for the partial NAND gate function and the switching mechanism.

Abdeldayem, Hossin

Polydiacetylene Films Prepared in Microgravity

A diffusive/kinetic rate equation was developed for the growth of polydiacetylene films from solution and compared with a microgravity experiment. The model takes into account both the kinetics of thin film growth and the diffusive transport limitations inherent to microgravity. In order to apply this model, measurements of the density and the ultraviolet extinction coefficient of the films, as well as of the diffusion coefficient of the monomer/solvent system, were made. The thin films grown in microgravity were predicted by the model to grow to a thickness of 0.148 micron, versus 0.150 micron for the ground control films. The flight films grew to 0.102 micron.

Carswell, William E.

Gravitational Effects on the Morphology and Kinetics of Photodeposition of Polydiacetylene Thin Films From Monomer Solutions

The goal of this proposed work is to study gravitational effects on the photodeposition of polydiacetylene thin films from monomer solutions onto transparent substrates. Polydiacetylenes have been an extensively studied class of organic polymers because they exhibit many unusual and interesting properties, including electrical conductivity and optical nonlinearity. Their long polymeric chains render polydiacetylenes readily conducive to thin film formation, which is necessary for many applications. These applications require thin polydiacetylene films possessing uniform thicknesses, high purity, minimal inhomogeneities and defects (such as scattering centers), etc. Also, understanding and controlling the microstructure and morphology of the films is important for optimizing their electronic and optical properties. The lack of techniques for processing polydiacetylenes into such films has been the primary limitation to their commercial use. We have recently discovered a novel method for the formation of polydiacetylene thin films using photo-deposition from monomer solutions onto transparent substrates with UV light. This technique is very simple to carry out, and can yield films with superior quality to those produced by conventional methods. Furthermore, these films exhibit good third-order properties and are capable of waveguiding. We have been actively studying the chemistry of diacetylene polymerization in solution and the photo-deposition of polydiacetylene thin films from solution. It is well-known that gravitational factors such as buoyancy-driven convection and sedimentation can affect chemical and mass transport processes in solution. One important aspect of polydiacetylene thin film photodeposition in solution, relevant to microgravity science, is that heat generated by absorption of UV radiation induces thermal density gradients that under the influence of gravity, can cause fluid flows (buoyancy-driven convection). Additionally, changes in the chemical composition of the solution during polymerization may cause solutal convection. These fluid flows affect transport of material to and from the film surface and thereby affect the kinetics of the growth process. This manifests itself in the morphology of the resulting films; films grown under the influence of convection tend to have less uniform thicknesses, and can possess greater inhomogeneities and defects. Specifically, polydiacetylene films photodeposited from solution, when viewed under a microscope, exhibit very small particles of solid polymer which get transported by convection from the bulk solution to the surface of the growing film and become embedded. Even when carried out under conditions designed to minimize unstable density gradients (i.e., irradiating the solution from the top), some fluid flow still takes place (particles remain present in the films). It is also possible that defect nucleation may be occurring within the films or on the surface of the substrate; this, too, can be affected by convection (as is the case with crystal growth). Hence films grown in 1-g will, at best, still possess some defects. The objective of this proposal is to investigate, both in 1-g and in low-g, the effects of gravitational factors (primarily convection) on the dynamics of these processes, and on the quality, morphology, and properties of the films obtained.

Paley, Mark S.

Observation of Individual Fluorine Atom from Highly Oriented Poly (tetrafluoroethylene) Films by Atomic Force Microscopy

Direct observation of the film thickness, molecular structure and individual fluorine atoms from highly oriented poly(tetrafluoroethylene) (PTFE) films were achieved using atomic force microscopy (AFM). A thin PTFE film is mechanically deposited onto a smooth glass substrate at specific temperatures by a friction transfer technique. Atomic resolution images of these films show that the chain-like helical structures of the PTFE macromolecules are aligned parallel to each other with an intermolecular spacing of 5.72 A, and individual fluorine atoms are clearly observed along these twisted molecular chains with an interatomic spacing of 2.75 A. Furthermore, the first direct AFM measurements for the radius of the fluorine-helix, and of the carbon-helix in sub-angstrom scale are reported as 1.70 A and 0.54 A respectively.

Lee, Jonathan A.,

Optical Computing Research at NASA

Scientists at the Marshall Space Flight Center (NASA), Universities Space Research Association (USRA), the University of Alabama in Huntsville (UAH), and the Alliance for Nonlinear Optics (ANLO) are working to develop thin-film organic-based materials useful for making optical devices. These devices can use photons exclusively to transmit data, or use both photons and electrons to form electronic/optical hybrids called electrooptic devices.

Abdeldayem, H. A.

Photonic and Opto-Electronic Applications of Polydiacetylene Films Photodeposited from Solution and Polydiacetylene Copolymer Networks

Polydiacetylenes (PDAS) are attractive materials for both electronic and photonic applications because of their highly conjugated electronic structures. They have been investigated for applications as both one-dimensional (linear chain) conductors and nonlinear optical (NLO) materials. One of the chief limitations to the use of PDAs has been the inability to readily process them into useful forms such as films and fibers. In our laboratory we have developed a novel process for obtaining amorphous films of a PDA derived from 2-methyl4-nitroaniline using photodeposition with Ultraviolet (UV) light from monomer solutions onto transparent substrates. Photodeposition from solution provides a simple technique for obtaining PDA films in any desired pattern with good optical quality. This technique has been used to produce PDA films that show potential for optical applications such as holographic memory storage and optical limiting, as well as third-order NLO applications such as all-optical refractive index modulation, phase modulation and switching. Additionally, copolymerization of diacetylenes with other monomers such as methacrylates provides a means to obtain materials with good processibility. Such copolymers can be spin cast to form films, or drawn by either melt or solution extrusion into fibers. These films or fibers can then be irradiated with UV to photopolymerize the diacetylene units to form a highly stable cross-linked PDA-copolymer network. If such films are electrically poled while being irradiated, they can achieve the asymmetry necessary for second-order NLO applications such as electro-optic switching. On Earth, formation of PDAs by the above mentioned techniques suffers from defects and inhomogeneities caused by convective flows that can arise during processing. By studying the formation of these materials in the reduced-convection, diffusion-controlled environment of space we hope to better understand the factors that affect their processing, and thereby, their nature and properties. Ultimately it may even be feasible to conduct space processing of PDAs for technological applications.

Paley, Mark S.

Space Product Development of Commercial NLO Materials

Growth on selected substrates under various processing conditions have been useful for preparing highly oriented and otherwise promising films of organic compounds for optical thin films and waveguides. The significance of processing conditions to uniformity in thickness, degree of orientation, film quality, and optical properties for a specific processing technique is the general focus of work in this area. A study on the effect of processing conditions relevant to thin-film deposition by various techniques is particularly difficult because of the possibility that convection may play a major role in some cases. It is a goal of some researchers to produce good quality anisotropic films, therefore, an important, yet understudied, requirement should be to assess the role of gravity during certain processing methods. This may be particularly true for the vapor deposition of diacetylenes where subsequent polymerization in the crystal is topochemical and occurs readily only when neighboring monomer molecules are sufficiently close and suitably oriented. Likewise, this requirement is equally viable for the vapor deposition of certain materials such as Pcs in view of the results of microgravity experiments by 3M Corporation involving the preparation of thin films of copper Pc (CuPc). Microgravity-grown CuPc had several desirable features which indicate that the vapor growth of organic films in low-g may result in better quality films for optical and electrical applications. Indeed, other materials vapor deposited onto specific substrates in microgravity produce films potentially beneficial for electro-optic applications. A novel technique, recently discovered, for growing polydiacetylene thin films involves exposing a transparent substrate, in contact with diacetylene monomer solution, to ultraviolet (LTV) light. A polymer film deposits on the side of the substrate in contact with monomer in solution, and there are distinct gravitational effects, which influence film quality. Good quality thin films elude growth from solutions absent of uniform flow fields and homogeneous temperature distributions near the substrate surfaces. The flow fields and temperature distributions during the polymerization process by exposure to UV light details the nature of gravitational influences on this process.

Frazier, Donald O.

Microgravity Processing and Photonic Applications of Organic and Polymeric Materials

Some of the primary purposes of this work are to study important technologies, particularly involving thin films, relevant to organic and polymeric materials for improving applicability to optical circuitry and devices and to assess the contribution of convection on film quality in unit and microgravity environments. Among the most important materials processing techniques of interest in this work are solution-based and by physical vapor transport, both having proven gravitational and acceleration dependence. In particular, PolyDiAcetylenes (PDA's) and PhthaloCyanines (Pc's) are excellent NonLinear Optical (NLO) materials with the promise of significantly improved NLO properties through order and film quality enhancements possible through microgravity processing. Our approach is to focus research on integrated optical circuits and optoelectronic devices relevant to solution-based and vapor processes of interest in the Space Sciences Laboratory at the Marshall Space Flight Center (MSFC). Modification of organic materials is an important aspect of achieving more highly ordered structures in conjunction with microgravity processing. Parallel activities include characterization of materials for particular NLO properties and determination of appropriation device designs consistent with selected applications. One result of this work is the determination, theoretically, that buoyancy-driven convection occurs at low pressures in an ideal gas in a thermalgradient from source to sink. Subsequent experiment supports the theory. We have also determined theoretically that buoyancy-driven convection occurs during photodeposition of PDA, an MSFC-patented process for fabricating complex circuits, which is also supported by experiment. Finally, the discovery of intrinsic optical bistability in metal-free Pc films enables the possibility of the development of logic gate technology on the basis of these materials.

Frazier, Donald O.

Microgravity Processing and Photonic Applications of Organic and Polymeric Materials

In recent years, a great deal of interest has been directed toward the use of organic materials in the development of high-efficiency optoelectronic and photonic devices. There is a myriad of possibilities among organics which allow flexibility in the design of unique structures with a variety of functional groups. The use of nonlinear optical (NLO) organic materials such as thin-film waveguides allows full exploitation of their desirable qualities by permitting long interaction lengths and large susceptibilities allowing modest power input. There are several methods in use to prepare thin films, such as Langmuir-Blodgett (LB) and self-assembly techniques, vapor deposition, growth from sheared solution or melt, and melt growth between glass plates. Organics have many features that make them desirable for use in optical devices such as high second- and third-order nonlinearities, flexibility of molecular design, and damage resistance to optical radiation. However, their use in devices has been hindered by processing difficulties for crystals and thin films. In this chapter, we discuss photonic and optoelectronic applications of a few organic materials and the potential role of microgravity on processing these materials. It is of interest to note how materials with second- and third-order nonlinear optical behavior may be improved in a diffusion-limited environment and ways in which convection may be detrimental to these materials.

Frazier, Donald O.

Nonlinear Optical Properties of Organic and Polymeric Thin Film Materials of Potential for Microgravity Processing Studies

In this paper, we will take a closer look at the state of the art of polydiacetylene, and metal-free phthalocyanine films, in view of the microgravity impact on their optical properties, their nonlinear optical properties and their potential advantages for integrated optics. These materials have many attractive features with regard to their use in integrated optical circuits and optical switching. Thin films of these materials processed in microgravity environment show enhanced optical quality and better molecular alignment than those processed in unit gravity. Our studies of these materials indicate that microgravity can play a major role in integrated optics technology. Polydiacetylene films are produced by UV irradiation of monomer solution through an optical window. This novel technique of forming polydiacetylene thin films has been modified for constructing sophisticated micro-structure integrated optical patterns using a pre-programmed UV-Laser beam. Wave guiding through these thin films by the prism coupler technique has been demonstrated. The third order nonlinear parameters of these films have been evaluated. Metal-free phthalocyanine films of good optical quality are processed in our laboratories by vapor deposition technique. Initial studies on these films indicate that they have excellent chemical, laser, and environmental stability. They have large nonlinear optical parameters and show intrinsic optical bistability. This bistability is essential for optical logic gates and optical switching applications. Waveguiding and device making investigations of these materials are underway.

Abdeldayem, Hossin

Optical Computers and Space Technology

The rapidly increasing demand for greater speed and efficiency on the information superhighway requires significant improvements over conventional electronic logic circuits. Optical interconnections and optical integrated circuits are strong candidates to provide the way out of the extreme limitations imposed on the growth of speed and complexity of nowadays computations by the conventional electronic logic circuits. The new optical technology has increased the demand for high quality optical materials. NASA's recent involvement in processing optical materials in space has demonstrated that a new and unique class of high quality optical materials are processible in a microgravity environment. Microgravity processing can induce improved orders in these materials and could have a significant impact on the development of optical computers. We will discuss NASA's role in processing these materials and report on some of the associated nonlinear optical properties which are quite useful for optical computers technology.

Abdeldayem, Hossin A.

Preparation of polymeric diacetylene thin films for nonlinear optical applications

A method for producing polymeric diacetylene thin films having desirable nonlinear optical characteristics has been achieved by producing amorphous diacetylene polymeric films by simultaneous polymerization of diacetylene monomers in solution and deposition of polymerized diacetylenes on to the surface of a transparent substrate through which ultraviolet light has been transmitted. These amorphous polydiacetylene films produced by photo-deposition from solution possess very high optical quality and exhibit large third order nonlinear optical susceptibilities, such properties being suitable for nonlinear optical devices such as waveguides and integrated optics.

Frazier, Donald O.

Polydiacetylene thin films for nonlinear optical applications

One very promising class of organic compounds for nonlinear optical (NLO) applications are polydiacetylenes, which are novel in that they are highly conjugated polymers which can also be crystalline. Polydiacetylenes offer several advantages over other organic materials: because of their highly conjugated electronic structures, they are capable of possessing large optical nonlinearities with fast response times; because they are crystalline, they can be highly ordered, which is essential for optimizing their NLO properties; and, last, because they are polymeric, they can be formed as thin films, which are useful for device fabrication. We have actively been carrying out ground-based research on several compounds of interest.

Paley, Mark S.

Synthesizing Diacetylenes With Nonlinear Optical Properties

Diacetylene compounds being investigated to determine whether they have nonlinear optical properties making them useful for four-wave mixing, generation of third harmonics, phase conjugation, and like. Diacetylene monomers synthesized by sequences of chemical reactions. Monomers polymerized by ultraviolet light, forming potentially useful nonlinear optical materials.

Mcmanus, Samuel P.

Films Containing Optically Nonlinear Diacetylene Monomer

Solid films exhibiting nonlinear optical properties prepared as mixtures of poly(methyl methacrylate) with various amounts of diacetylene monomer called "compound 1" in article, "Synthesizing Diacetylenes With Nonlinear Optical Properties" (MFS-26186). Useful as phase-conjugate mirrors in laser-beam communications and as optical switches in optical computers. This particular diacetylene monomer exhibits strong third-order nonlinear optical properties, both in pure form and in solution.

Paley, Mark S.

The Crystal and Molecular Structure of an Asymmetric Diacetylene Monomer, 6-(2-methyl-4-nitroanilino)-2,4-hexadiyne-1-ol

The crystal and molecular structure of an asymmetric diacetylene monomer has been determined from x-ray diffraction data. The crystals, obtained from an acetone/pentane solution, are orthorhombic, Fdd2 with Z = 16 in a unit cell having dimensions of a = 42.815(6) A, b = 22.224(5) A, c = 4.996(l) A. The structure was solved by direct methods and refined by least- squares techniques to an R(sub F) of 6.4% for 988 reflections and 171 variables. The diacetylene chains are disposed in the unit cell in a complex manner in order to satisfy the hydrogen- bonding, crystal packing, and symmetry requirements of the system. The solid state polymerization mechanism is discussed with respect to the geometric disposition of the diacetylene chains. These chains are far apart and incorrectly oriented with respect to each other to permit polymerization in the crystal by means of 1,4-addition, consistent with the Baughman mechanistic model.

Vlasse, Marcus

Colorimetric Detection Of Substances In Liquids And Gases

Thin polymer films containing solvatochromic dyes used as sensing elements to detect substances dissolved in liquids and gases. Dyes do not react with liquids in which dissolved, but do respond to changes in chemical compositions by changing color. Concentration determined visually by comparison of color with predetermined standard chart, or spectrophotometrically.

Harris, J. Milton