Catenated phosphorus materials and their preparation

Chemistry of inorganic compounds – Phosphorus or compound thereof – Nitrogen containing

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423299, 423322, C01B 2508

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active

048225819

ABSTRACT:
High phosphorus polyphosphides, namely MP.sub.x, where M is an alkali metal (Li, Na, K, Rb, and Cs) or metals mimicking the bonding behavior of an alkali metal, and x=7 to 15 or very much greater than 15 (new forms of phosphorus) are useful semiconducutors in their crystalline, polycrystalline and amorphous forms (boules and films). MP.sub.15 appears to have the best properties and KP.sub.15 is the easier to synthesize. P may include other pnictides as well as other trivalent atomic species. Resistance lowering may be accomplished by doping with Ni, Fe, Cr, and other metals having occupied d or f outer electronic levels; or by incorporation of As and other pnictides. Top contacts forming junction devices doped with Ni and employing Ni as a back contact comprise Cu, Al, Mg, Ni, Au, Ag, and Ti. Photovoltaic, photoresistive, and photoluminescent devices are also disclosed. All semiconductor applications appear feasible.
These semiconductors belong to the class of polymer forming, trivalent atomic species forming homatomic, covalent bonds having a coordination number slightly less than 3. The predominant local order appears to be all parallel pentagonal tubes in all forms, including amorphous, except for the monoclinic and twisted fiber allotropes of phosphorus.
Large crystal monoclinic phosphorus (a birefringent material) in two habits, a twisted fiber phosphorus allotrope and a star shaped fibrous high phosphorus material are also disclosed.
Single and multiple source vapor transport, condensed phase, melt quench, flash evaporation, chemical vapor deposition, and molecular flow deposition may be employed in synthesizing these materials. Vapor transport may be employed to purify phosphorus.
The materials may be employed as protective coatings, optical coatings, fire retardants, fillers and reinforcing fillers for plastics and glasses, antireflection coatings for infrared optics, infrated transmitting windows, and optical rotators.

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