Photochemistry of Conjugated Polymer/Lanthanide Blends (Srdanov)
National Science Foundation CHE0098240 7/1/2001-6/30/2004
Srdanov, Bazan
The primary goal of this proposal is to design blends of lanthanide complexes in conjugated polymers (L/P) for use in emerging optoelectronic technologies. A rational design of these blends for use in either display or communication applications will require an improved understanding of the photodynamics and electronic coupling between organic semiconductors, the ligand on the complex and the lanthanide metal center. To achieve these goals the proposal brings together an interdisciplinary research team with backgrounds in spectroscopy and organic synthesis. Such energy transfer could not take place in other L/P blends as well. We believe polymer-based LEDs containing Tb3+, Eu3+, Nd3+, and Er3+ would offer a number of applications. Monochromatic green and red emission from blends containing Tb3+ and Eu3+, respectively, may be used for developing inexpensive flat-panel full-color display technology. Our ultimate goal is to custom-make specific L/P blends for a desired application.

Bio-composite Materials for the Rapid, Reagent-less Detection of TNT in Sea Water
Office of Naval Research DURINT N00014--1-1-0239 1/1/2001-11/30/2003
Plaxco, David Baker, U of W, Bazan, Strouse, Heeger, Plaxco
The ideal technology for the detection of 2,4,6 trinotroluene (TNT) and TNT analogs in sea water would be sensitive, specific, real-time (<1s), continuous, reagent-less and compatible with the detection of aqueous analytes. We propose a water-compatible biosensor that couples high affinity protein-TNT binding with the robust physical properties of exogenous optical and electronic reporter groups via a novel signal transduction mechanism to produce sensitive, reagent-less real-time TNT detection.

Nanoscience Basis for Miniaturized, Intelligent Sensors (MIS)
Integrated Electro-optical, Nano-scale Biosensors
Office of Naval Research MIS2001P-43 8/1/2001-7/31/2003
Plaxco, Bazan, Heeger, Strouse, Morse
Proposed here is the development of a miniaturizable, opto-electronic bio-sensor approach that will pave the way for reusable, sub-micrometer scale, sense-and-respond devices characterized by unprecedented specificity, response times and signal to noise. The proposed study utilizes novel bio-optical composite materials that couple the speed, specificity and affinity of ligand-induced protein folding with the robust signaling properties of molecular- and nanomaterial-based optical reporters. These composites will be integrated with polymer LED and solid-state or polymer-based CCD/photodiode interrogation/detection systems -via novel, nanometer-scale, bio/abiotic interface chemistry- to construct a robust, highly scalable, highly generalizable opto-electronic sensor array.

Conjugated Polymer Composites for Use in Optoelectronic Devices
Office of Naval Research N00014-98-1-0759 1/1/2001-9/30/2003
Bazan
There are two main goals in this proposal. The first is to create composites containing conjugated polymers and lanthanide complexes for use in electroluminescent light emitting diodes and other optoelectronic devices such as photodetectors. These composites are formulated to emit monochromatic light in the visible and infrared ranges of the spectrum. They also hold the potential of overcoming the efficiency limitations of organic materials determined by spin recombination statistics. The second goal is to design perfectly defined organic materials of intermediate molecular dimensions with topological features that inhibit crystallization. These materials offer processing advantages over polymeric and small molecule counterparts. The efforts from our research group are of interest to US high-technology firms developing display technology based on organic materials and to academic scientists who require optimized materials in the study of structure/property relationships for the organic solid state.

Organic Materials of Intermediate Dimensions for Optoelectronic Technologies
National Science Foundation DMR-0097611 3/1/2001-2/28/2004
Bazan
This proposal descibes a research program with the goals of understanding how molecular topology can be used to control the organization of molecules in the solid state.

Luminescent Polyelectrolytes for use in Biosensors
National Science Foundation DMR-0099843 5/1/2001-4/30/2004
Heeger, Moses
We propose a research project directed toward determining the chain conformation of luminescent polyelectrolytes and the magnitude of the Coulomb binding energy of the polymer: quencher complexes. The luminescent polyelectrolytes to be studied include water soluble PPV derivatives and novel polyl-lysine polymers (polypeptide chains with cyanine dyes in J-aggregate configuration attached as side-chains). A series of quenchers with different charges have been developed and are available for these studies. Quenching of PL will be studied by changing the ion concentration in buffered aqueous solutions, by changing the concentration of acceptors, and by varying the temperature. The chain conformation of the luminescent polyelectrolytes will be determined (with and without quencher, surfactant etc), as a function of the Debye screening length (ion concentration) and as a function of molecular weight using light scattering and neutron scattering.

Photoexcitation Mechanisms and Transport Properties of Polarons and Solitons in Conjugated Polymers
National Science Foundation DMR00968202 11/1/2001-10/10/2004
Moses, Heeger
We propose to take advantage of a novel experimental approach recently developed in our labs and use an enhanced laser system to investigate some of the most fundamental questions in the field of conjugated polymers: questions such as: Are solitons primary excitations? What is the nature of soliton-soliton interaction? How does this interaction affect the soliton bi-molecular recombination dynamics, in particular as the soliton density is increased? Can one cross the insulator-metal transition at high soliton excitation densities? Is carrier generation possible in strictly one-dimensional systems (e.g. on a single polymer chain)? Or rather, is interchain coupling inherently required for carriers to escape geminate recombination? How are the carrier quantum efficiency, carrier recombination dynamics, and carrier transport affected by modifying the interchain coupling? What is the role of neutral excitons in the carrier photoexcitation process?
We propose to investigate these fundamental issues by measurements of fast transient IRAV absorption and fast transient photoconductivity in polyacetylene, PPV, and the various derivatives of PPV in solid form solutions.

MURI 2001 Topic 26: Subcontract on Polymeric Smart Skin Materials: Concepts, Materials, and Devices
U of W: MURI to AFOSR 413109 (AF MURI) 5/1/2001-11/30/2002
Heeger
This proposal is a subcontract to an AF proposal through University of Washington. Heeger will utilize molecules and polymers developed by Dalton and Harper groups to make self-contained electrochromic and/or light-emitting electrochemical cell devices for use as smart skins.

Unbiased, in-situ Life Detection Technology Based on Terahertz Circular Dichroism Spectroscopy
NASA NAG5-12150 5/15/2002-5/14/2003
Plaxco, Allen, S.J.
Terahertz circular dichroism (TCD) may provide a universal and unequivocal signature of living systems, regardless of their genesis. Here we propose a TCD-based search-for-life strategy that is founded on the argument that, irrespective of the specifics of their metabolism, all forms of chemical life will be based on folded polymers of > 500 atoms absorbing strongly at terahertz frequencies and exhibiting circular dichroism. This circular dichroism unambiguously distinguishes biological from abiological materials.
The primary thrust of the proposed research is to measure, document and understand the heretofore unexplored TCD spectra of a wide variety of terrestrial biopolymers. In order to perform these measurements we will build a novel TCD spectrometer based on UCSB's existing free electron laser. Using this TCD spectrometer, the TCD spectra of terrestrial biopolymers and abiological materials will be determined, allowing us to assess the potential of TCD as an astrobiological tool. The successful completion of the proposed research will also provide a novel characterization method for the functionally and clinically relevant global and sub-global dynamics of terrestrial biopolymers.

Biological Sensing with Terahertz Circular Dichroism Spectroscopy
Army DAAD19-02-1-0080 6/1/2002-5/31/2003
Plaxco, Allen
The terahertz (THz) absorption spectrum of biological molecules can provide a key to the effective, species-specific detection, identification and interrogation of biological warfare agents. However, while fingerprinting chemical species in the gas phase by THz spectroscopy is well established, the corresponding science of THz identification of condensed-phase biomolecules in the presence of strongly absorbing abiological materials (such as water) is poorly developed. The objective of the proposed research project is to establish a means for the ready and unambiguous detection of potential biological warfare (BW) agents in the presence of a strongly absorbing background via THz circular dichroism spectroscopy (TCDS).

NSF-Science & Technology Center on Materials and Devices for Information Technology Research
University of Washington 8/1/2002-7/31/2003
Heeger
Research Goals of the STC:
· Developing new photonic materials and components that can be coupled to 3-D microscale integrated optics for application to next-generation fiber optic and satellite telecommunications;
· To greatly improve bandwidth while diminishing optical loss and voltage requirements for data, voice and video information processing and transmission;
Research focus at UCSB:
The focus of this effort is to develop light-emitting devices, amplifiers, and lasers based on organic nanostructured materials that operate in the near infrared and at telecommunication wavelengths.

Catalysts for Selective Olefin Oligomerization and Polymerization
Department of Energy DE-FG03-98ER14910 12/1/2001-11/30/2002
Bazan
We have identified two important challenges in the area of organometallic chemistry and homogeneous catalysis. The first concerns the design of catalyst mixtures so that the individual catalysts (two or more) cooperate within the same medium to generate a single product, a strategy referred to as tandem catalysis. The second is the creation of catalysts, or catalyst schemes, that allow one to obtain non-statistical oligomerization processes. More specific targeting of product structure circumvents tedious separation techniques and the generation of less valuable and less useful byproducts. The recent rise in the cost of gasoline and natural gas, coupled to the energy crisis in California underscore the importance of finding more efficient industrial processes and better management of petrochemical resources.

"Plastic" Optoelectronics: Injection Lasers Fabricated from Soluble Semiconducting Polymers
Air Force Office of Scientific Research F49620-02-1-0127 3/1/2002-12/31/2005
Heeger, Moses, Bazan
High performance optoelectronic devices fabricated from semiconducting polymers have been demonstrated, including light emitting diodes (LEDs) and displays comprising polymer LEDs, light-emitting electrochemical cells, photovoltaic cells, photodiodes and optocouplers. Not only are the active elements of these optoeletronic devices fabricated from polymers, each of these different devices have been demonstrated on plastic substrates. This progress demonstrates that we are witnessing the beginning of a Revolution in "Plastic" Optoelectronics.
Notably absent from the list of electronic and optical devices that have been made from conjugated polymers, however, is one of the most important devices for modern technology - the diode injection laser. This proposal outlines a research program directed toward Injection Lasers Fabricated from Soluble Semiconducting Polymers.

Photochemistry of Conjugated Polymer/Lanthanide Blends (Bazan)
National Science Foundation CHE0098240 7/1/2001-6/30/2004
Bazan, Srdanov, V.
The primary goal of this proposal is to design blends of lanthanide complexes in conjugated polymers (L/P) for use in emerging optoelectronic technologies. A rational design of these blends for use in either display or communication applications will require an improved understanding of the photodynamics and electronic coupling between organic semiconductors, the ligand on the complex and the lanthanide metal center. To achieve these goals the proposal brings together an interdisciplinary research team with backgrounds in spectroscopy and organic synthesis.such energy transfer could not take place in other L/P blends as well. We believe polymer-based LEDs containing Tb3+, Eu3+, Nd3+, and Er3+ would offer a number of applications. Monochromatic green and red emission from blends containing Tb3+ and Eu3+, respectively, may be used for developing inexpensive flat-panel full-color display technology. Our ultimate goal is to custom-make specific L/P blends for a desired application.

Induced Collective Phenomena in Semiconductors: A Multicampus Research Project
UCSD UC-CLC SB020086 10/1/2001-9/30/2003
Heeger
At UCSB, we will carry out systematic investigations of injection-induced phenomena in conjugated polymers and oligomers using two approaches:
1. Photo-injection
2. Field effect injection
Semiconducting polymers will be prepared at UCSB and, in collaboration with colleagues at Los Alamos National Laboratory (LANL), field-effect structures will be developed and used as a means of probing the basic transport physics (including the metal-insulator transition and superconductivity). The generation of pin-hole free films of high dielectric oxides (such as aluminum oxide) will be an initial focus of the work at UCSB. Special effort will be dedicated to the detailed characterization of the morphology and chemical roughness of interfaces.
IR spectroscopy, steady state and photo-induced with 100 fs temporal resolution will be the primary focus of the research at UCSB. These ultrafast measurements open a new regime for study of the charge dynamics in semiconducting polymers.

Fabrication of PPV Linkers for Quantum Dot Assembly into Molecular-Like Structures
Los Alamos National Lab 42785-SOL-02 2K 1/1/2002-12/31/2002
Bazan
This Request for Proposal is for development of procedures for synthesis of thiol and phosophine terminated linkers based on poly(phenylvinylene) oligomers. Also the fabrication of linkers with 3, 4 and 5 repeating units for Los Alamos. We will also do consulting work on using these linkers for binding semiconductor quantum dots into molecular-like assemblies.

Research Experience for Teachers: Astrobiology and Space Science
NASA NAG5-12150 5/15/2002-5/14/2003
Plaxco, Allen
A NASA component focused on Astrobiology and Space Science will be added to the existing and very active UCSB MRL Research Experience for Teachers program. The NASA component will feature a summer internship for a local science teacher who will conduct primary research related to the parent project, "Life detection technology based on terahertz circular dichroism spectroscopy". This is followed by the development of a teaching unit that includes an investigative module for use in the home secondary school.

Organic Materials of Intermediate Molecular Dimensions for Light Emitting Diodes
UC-SMART 01-10110 8/27/2002-8/26/2003
Bazan
This proposal concerns the use of organic semiconductors in the manufacture of thin-film displays. The main focus is the development of novel organic molecular structures that are electroluminescent and thus can be incorporated within light emitting diode (LED) structures. These devices have the technological potential to revolutionize the means by which information is displayed and have commercially competitive features, such as ease of processability, resistance to shock, strong emission and even the possibility of being a component of an all-plastic electronic device.

Organic Materials of Intermediate Molecular Dimensions for Light Emitting Diodes
Dupont Displays Inc. SB030014 8/27/2002-8/26/2003
Bazan
This proposal concerns the use of organic semiconductors in the manufacture of thin-film displays. The main focus is the development of novel organic molecular structures that are electroluminescent and thus can be incorporated within light emitting diode (LED) structures. These devices have the technological potential to revolutionize the means by which information is displayed and have commercially competitive features, such as ease of processability, resistance to shock, strong emission and even the possibility of being a component of an all-plastic electronic device.