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Hehemann, David G.

Publications and source records attributed to Hehemann, David G..

Synthesis, Characterization and Decomposition Studies of Tris(N,N-dibenzyldithiocarbamato) Indium(III): Chemical Spray Deposition of Polycrystalline CuInS2 on Copper Films

Tris(bis(phenylmethyl)carbamodithioato-S,S ), commonly referred to as tris(N,Ndibenzyldithiocarbamato) indium(III), In(S2CNBz2)3, was synthesized and characterized by single crystal X-ray crystallography. The compound crystallizes in the triclinic space group P1 bar with two molecules per unit cell. The material was further characterized using a novel analytical system employing the combined powers of thermogravimetric analysis, gas chromatography/mass spectrometry and Fourier-Transform infrared spectroscopy to investigate its potential use as a precursor for the chemical vapor deposition (CVD) of thin film materials for photovoltaic applications. Upon heating, the material thermally decomposes to release CS2 and benzyl moieties in to the gas phase, resulting in bulk In2S3. Preliminary spray CVD experiments indicate that In(S2CNBz2)3 decomposed on a Cu substrate reacts to produce stoichiometric CuInS2 films.

Hehemann, David G.

Novel Route to Transition Metal Isothiocyanate Complexes Using Metal Powders and Thiourea

A new synthetic route to isothiocyanate-containing materials is presented. Eight isothiocyanate- 4-methylpyridine (y-picoline) compounds were prepared by refluxing metal powders (Mn, Fe, Co, Ni, and Cu) with thiourea in y-picoline. With the exception of compound 5,prepared with Co, the isothiocyanate ligand was generated in situ by the isomerization of thiourea to NH4+SCN- at reflux temperatures. The complexes were characterized by x-ray crystallography. Compounds 1,2, and 8 are the first isothiocyanate- 4-methylpyridine anionic compounds ever prepared and structurally characterized. Compounds 1 and 2 are isostructural with four equatorially bound isothiocyanate ligands and two axially bound y-picoline molecules. Compound 8 is a five-coordinate copper(II) molecule with a distorted square-pyramidal geometry. Coordinated picoline and two isothiocyanates form the basal plane and the remaining isothiocyanate is bound at the apex. Structural data are presented for all compounds.

Harris, Jerry D.

Dye-Sensitized Solar Cells for Space Power

During the course of this grant, dye-sensitized solar cells were prepared and characterized. The solar cells were prepared using materials (dyes, electrolytes, transparent conductive oxide coated glass, nanocrystalline TiO2) entirely prepared in-house, as well as prepared using materials available commercially. Complete cells were characterized under simulated AM0 illumination. The best cell prepared at NASA had an AM0 efficiency of 1.22% for a 1.1 sq cm cell. Short circuit current (Isc), open circuit voltage (Voc) and fill factor (FF) for the cell were 6.95 mA, 618 mV and 42.8%, respectively. For comparison purposes, two commercially prepared dye-sensitized solar cells were obtained from Solaronix SA, Aubonne, Switzerland. The Solaronix cells were also characterized under simulated AM0 illumination. The best cell from Solaronix had an active area of 3.71 sq cm and measured an AM0 efficiency of 3.16%. with Isc, Voc and FF of 45.80 mA, 669.6 mV and 52.3%, respectively. Both cells from Solaronix were rapid thermal cycled between -80 C and 80 C. Thermal cycling led to a 4.6% loss of efficiency in one of the cells and led to nearly a complete failure in the second cell.

Harris, Jerry D.

New Solid Polymer Electrolytes for Improved Lithium Batteries

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

Hehemann, David G.

Inerting Aircraft Fuel Systems Using Exhaust Gases

Our purpose in this proposal was to determine the feasibility of using carbon dioxide, possibly obtained from aircraft exhaust gases as a substance to inert the fuel contained in fuel tanks aboard aircraft. To do this, we decided to look at the effects carbon dioxide has upon commercial Jet-A aircraft fuel. In particular, we looked at the solubility of CO2 in Jet-A fuel, the pumpability of CO2-saturated Jet-A fuel, the flashpoint of Jet-A fuel under various mixtures of air and CO2, the static outgassing of CO2-Saturated Jet-A fuel and the dynamic outgassing of Jet-A fuel during pumping of Jet-A fuel.

Hehemann, David G.

Chemical Fabrication Used to Produce Thin-Film Materials for High Power-to- Weight-Ratio Space Photovoltaic Arrays

The key to achieving high specific power (watts per kilogram) space solar arrays is the development of a high-efficiency, thin-film solar cell that can be fabricated directly on a flexible, lightweight, space-qualified durable substrate such as Kapton (DuPont) or other polyimide or suitable polymer film. Cell efficiencies approaching 20 percent at AM0 (air mass zero) are required. Current thin-film cell fabrication approaches are limited by either (1) the ultimate efficiency that can be achieved with the device material and structure or (2) the requirement for high-temperature deposition processes that are incompatible with all presently known flexible polyimide or other polymer substrate materials. Cell fabrication processes must be developed that will produce high-efficiency cells at temperatures below 400 degrees Celsius, and preferably below 300 degress Celsius to minimize the problems associated with the difference between the coefficients of thermal expansion of the substrate and thin-film solar cell and/or the decomposition of the substrate.

Hepp, Aloysius F.

One-step synthesis of dithiocarbamates from metal powders

Neutral metal dithiocarbamate complexes (M(NR2CS2)X) are well-known precursors to metal sulfides, a class of materials with numerous technological applications. We are involved in a research effort to prepare new precursors to metal sulfides using simple, reproducible synthetic procedures. We describe the results of our synthetic and characterization studies for M = Fe, Co, Ni, Cu. and In. For example, treatment of metallic indium with tetramethylthiuram disulfide (tmtd) in 4-methylpyridine (4-Mepy) at 25 deg C produces a new homoleptic indium (III) dithiocarbamate, In(N(CH3)2CS2)3(I), in yields of over 60 percent. The indium (III) dithiocarbamate was characterized by X-ray crystallography; (I) exists in the solid state as discrete distorted-octahedral molecules. Compound (I) crystallizes in the P1bar (No. 2) space group with lattice parameters: a = 9.282(1) A, b = 10.081(1) A, c = 12.502 A, alpha = 73.91(1) deg, beta = 70.21(1) deg, gamma = 85.8(1)deg, and Z = 2. X-ray diffraction and mass spectral data were used to characterize the products of the analogous reactions with Fe, Co, Ni, and Cu. We discuss both use of dithiocarbamates as precursors and our approach to their preparation.

Hepp, Aloysius F.

Synthesis and decomposition of a novel carboxylate precursor to indium oxide

Reaction of metallic indium with benzoyl peroxide in 4-1 methylpyridine (4-Mepy) at 25 C produces an eight-coordinate mononuclear indium(III) benzoate, In(eta(sup 2)-O2CC6H5)3(4-Mepy)2 4H2O (I), in yields of up to 60 percent. The indium(III) benzoate was fully characterized by elemental analysis, spectroscopy, and X-ray crystallography; (I) exists in the crystalline state as discrete eight-coordinate molecules; the coordination sphere around the central indium atom is best described as pseudo-square pyramidal. Thermogravimetric analysis of (I) and X-ray diffraction powder studies on the resulting pyrolysate demonstrate that this new benzoate is an inorganic precursor to indium oxide. Decomposition of (I) occurs first by loss of 4-methylpyridine ligands (100 deg-200 deg C), then loss of benzoates with formation of In2O3 at 450 C. We discuss both use of carboxylates as precursors and our approach to their preparation.

Hepp, Aloysius F.