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A New Acceptor (N-type) Polyphenylenevinylene Building Block: SF-PPV-I

A new sulfone derivatized acceptor (n-type) polyphenylenevinylene "SF-PPV" with nano meter sizes and functional terminals has been synthesized and characterized. The SF-PPV-I that contains hydrocarbon alkyl-sulfone moieties has a strong photoluminescence in both solution and in solid thin film states. In dichloromethane, the 5-10 nm sized SF-PPV has a maximum emission at about 530 nm with excitation maximum at about 490 nm. UV-VIS shows a absorption peak onsite at about 500 nm. Optical spectroscopy and electrochemical studies revealed that the SF-PPV-I has an LUMO level at about -3.6 eV (relative to vacuum), and an HOMO level at about -6.1 eV. The average size (length) of SF-PPV-I can be controlled on the nano meter scale via synthetic means. The SF-PPV has the potential in developing polymer based supramolecular opto-electronic semiconductor devices.

Wang, Yiqing↗

Synthesis and Characterization of SF-PPV-I

Conjugated electro-active polymers find their potential applications in developing variety inexpensive and flexible shaped electronic and photonic devices, such as photovoltaic or photo/electro light emitting devices. In many of these opto-electronic polymeric materials, certain electron rich donors and electron deficient acceptors are needed in order to fine-tune the electronic or photonic properties of the desired materials and structures. While many donor type of conjugated polymers have been widely studied and developed in the past decades, there are relatively fewer acceptor type of conjugated polymers have been developed. Key acceptor type conjugated polymers developed so far include C60 and CN-PPV, and each has its limitations. Due to the complexity and diversity of variety future electronic materials and structural needs, alternative and synthetically amenable acceptor conjugated polymers need to be developed. In this paper, we present the synthesis and characterization of a new acceptor conjugated polymer, a sulfone derivatized polyphenylenevinylene "SF-PPV".

Wang, Y.↗

Novel High Efficient Organic Photovoltaic Materials: Appendix for Summary of Research

There are many different kinds of conjugated polymers that may be useful in photovoltaic devices. So far, the most popular and successful conjugated polymers used in photovoltaic devices include poly(1,4-)phenylenevinylenes (PPV), C60 and their derivatives. The discovery of electro-luminescence in PPV has stimulated a great deal of interest in developing "plastic" solid-state semiconductor devices. The overall synthetic methodology for the preparation of PPV can be divided into three main categories: (1) side chain derivatization, (2) precursor approach, and (3) in-situ polymerization. In this project, the first method was adopted. As discussed in project proposal and literatures, the overall efficiency of photovoltaic devices containing conjugated polymers is determined by the materials ability to generate excitons from incoming radiation, and then to separate the charges at donor/acceptor interfaces, and then to transport charges to respective electrodes. Given that effective exciton diffusion range are typical less then 30 nm, unique morphological structures are needed. This need led to several research groups to the idea that interpenetrating or bi-continuous networks of donor (electron donating) and acceptor (electron withdrawing) polymers should give better results. One approach involved the use of functionalized PPV. The attachment of electron withdrawing cyano groups to a PPV forms the CN-PPV, making it a strong electron acceptor. Underivatized PPV is a generally considered a hole-transporting material. Using blends of MEH-PPV, a soluble donor PPV derivative, as a hole transporter and CN-PPV as an electron transporter, a quantum efficiencies of up to 6% was achieved.

Sun, Sam↗

Recent observations of HF and HCl in the upper stratosphere

Concentrations of gas phase hydrofluoric acid and hydrochloric acid have been determined in the upper stratosphere from near-infrared solar spectra recorded in the course of balloon flights from Palestine, Texas, in October 1978 and in September 1979. The average mixing ratios for HF deduced respectively from these flights are (4.8 plus or minus .3) x 10 to the -10th ppv above 30.3km and (6.2 plus or minus .5) x 10 to the -10th ppv above 36.8km. This observed difference is ascribed to an increase in the HF concentration out to at least 37km. The HCl mixing ratios deduced from the 1978 flight yield (4.5 plus or minus .6) x 10 to the -10th ppv at 21.7km, (7.5 plus or minus .7) x 10 to the -10th ppv at 27.5 km and (2.1 plus or minus .4) x 10 to the -9th ppv above 30.5km. Observations in 1979 imply an average HCl mixing ratio above 36.8km of (2.4 plus or minus .4) x 10 to the -9th ppv. Our data do not indicate a measurable temporal trend of the HCl concentration above 30km.

Zander, R.↗

Concentration of carbon monoxide in the upper stratosphere

The concentration of telluric carbon monoxide has been determined in the upper stratosphere from infrared solar spectra recorded by balloon in October 1978 and September 1979, over Texas. The average mixing ratios were found to be (2.1 plus or minus 3) x 10 to the -8th ppv and (3.7 plus or minus 0.4) x 10 the the -8th ppv above the float altitudes of 30.6 and 36.8 km, respectively. The concentration profile deduced from all the measurements indicates that the CO mixing ratio increases in the upper stratosphere, from (1 plus or minus 0.3) x 10 to the -8th ppv at 30.6 km, to about 4 x 10 to the -8th ppv above 41 km.

Zander, R.↗

Synthesis and Characterization of a Novel -D-B-A-B- Block Copolymer System for Light Harvesting Applications

Supra-molecular or nano-structured electro-active polymers are potentially useful for developing variety inexpensive and flexible shaped opto-electronic devices. In the case of organic photovoltaic materials or devices, for instance, photo induced electrons and holes need to be separated and transported in organic acceptor (A) and donor (D) phases respectively. In this paper, preliminary results of synthesis and characterizations of a coupled block copolymers containing a conjugated donor block RO-PPV and a conjugated acceptor block SF-PPV and some of their electronic/optical properties are presented. While the donor block film has a strong PL emission at around 570 nm, and acceptor block film has a strong PL emission at around 590 nm, the PL emissions of final -B-D-B-A- block copolymer films were quenched over 99%. Experimental results demonstrated an effective photo induced electron transfer and charge separation due to the interfaces of donor and acceptor blocks. The system is very promising for variety light harvesting applications, including "plastic" photovoltaic devices.

Sun, Sam-Shajing↗

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Sun, Sam-Shajing↗

Novel High Efficient Organic Photovoltaic Materials

Solar energy is a renewable, nonpolluting, and most abundant energy source for human exploration of a remote site or outer space. In order to generate appreciable electrical power in space or on the earth, it is necessary to collect sunlight from large areas and with high efficiency due to the low density of sunlight. Future organic or polymer (plastic) solar cells appear very attractive due to their unique features such as light weight, flexible shape, tunability of energy band-gaps via versatile molecular or supramolecular design, synthesis, processing and device fabrication schemes, and much lower cost on large scale industrial production. It has been predicted that supramolecular and nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration due to improved electronic ultrastructure and morphology in comparison to polymer composite system. This presentation will describe our recent progress in the design, synthesis and characterization of a novel block copolymer system containing donor and acceptor blocks covalently attached. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (RO-PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (SF-PPV). The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block has a strong PL emission at around 560 nm, and acceptor block has a strong PL emission at around 520 nm, the PL emissions of final block copolymers are severely quenched. This verifies the expected electron transfer and charge separation due to interfaces of donor and acceptor nano phase separated blocks. The system therefore has potential for variety light harvesting applications, including high efficient photovoltaic applications.

Sun, Sam↗

ATMOS/ATLAS 1 measurements of sulfur hexafluoride (SF6) in the lower stratosphere and upper troposphere

Vertical profiles of sulfur hexafluoride (SF6) in the lower stratosphere and upper troposphere have been retrieved from 0.01/cm resolution infrared solar occultation spectra recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS (Atmospheric Laboratory for Applications and Science) 1 shuttle mission of March 24 to April 2, 1992. Based on measurements of the unresolved absorption by the SF6 mu(sub 3) band Q branch at 947.9/cm, average SF6 volume mixing ratios and 1-sigma uncertainties of 3.20 +/- 0.54 parts per trillion by volume (pptv; 10(exp -12) ppv) at 200 mbar (approximately 11.8 km) declining to 2.86 +/- 0.29 pptv at 100 mbar (approximately 16.2 km) and 1.95 +/- 0.50 pptv at 30 mbar (approximately 23.9 km) have been retrieved. The profiles show no obvious dependence with latitude over the range of the measurements (eight occultations spanning 28 deg S to 54 deg S). Assuming an exponential growth model and applying a correction for the interhemispheric concentration difference, an average SF6 rate of increase of 8.7 +/- 2.2% per year, 2 sigma, between 12 and 18 km has been derived by fitting the present measurements, ATMOS measurements from the April-May 1985 Spacelab 3 mission, and balloon-borne IR measurements obtained in March 1981 and June 1988.

Rinsland, C. P.↗