Stauffer Chemical Company

American Cyanamid Company

Cytec Technology Corporation

Mark A Kuck

John A Baumann

Christian G Michel

Rozalie Schachter

Paul M Raccah

Gary Kaui Miller

Donald H Valentine, Jr

C Joseph Calbick

Miguel Coll-Palagos

Lester P Van Brocklin

George E Hansen

Henry S Marek

Susan W Gersten

Alkyl arsines are made by a reaction of gaseous arsine and the corresponding gaseous olefin in contact with at least one Bronsted acid catalyst. Products produced thereby are mono- and di-substituted arsines, e.g. alkyl and di-alkyl arsines, which contain substantially no metallic or oxygenating impurities.

Process for making alkyl arsine compounds

Alkylphosphines are made by a reaction of gaseous phosphine and the corresponding gaseous olefin in contact with at least one non-oxidizing acid catalyst. Products produced thereby are alkylphosphines which contain substantially no metallic or oxygenating impurities. The process is a continuous process and employs a mineral acid catalyst either in solid form or as a liquid supported on a solid, inert material.

Process of making alkyl phosphine compounds by reacting an olefin and a

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 semiconductors 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.

Films of catenated phosphorus materials, their preparation and use, and

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.

Catenated phosphorus materials and their preparation

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 semiconductors 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, infrared transmitting windows, and optical rotators.

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 where x=7 to 15 or very much greater than 15 (new forms of phosphorus) are useful semiconductors 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. Rectifying Schottky junction devices doped with Ni and employing Ni as a back contact comprise Cu, Al, Mg, Ni, Au, Ag, and Ti as junction forming top contacts. Photovoltaic, photoresistive, and photoluminescent devices are also disclosed. All semiconductor applications appear feasible. 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.

Doping of catenated phosphorus materials

MP.sub.15, where M is an alkali metal is used in a generator of P.sub.4 gas. KP.sub.15 is preferred. The generator is heated to produce the P.sub.4 gas. The generator may be used in various deposition processes such as chemical vapor deposition, vacuum evaporation, and molecular beam deposition. It is particularly useful in high vacuum processes below 10.sup.-3 Torr, particularly below 10.sup.-4 Torr such as vacuum evaporation and molecular beam deposition, for example vapor phase epitaxy and molecular beam epitaxy.

P.sub.4 gas generator using the alkali metal polyphosphide MP.sub.15

Monoclinic phosphorus is produced in a single source vapor transport apparatus comprising a sealed evacuated ampoule containing a mixture or compound of phosphorus and an alkali metal with the phosphorus to alkali metal ratio being 11 or greater. The charge is heated to 550.degree.-560.degree. C. and the monoclinic phosphorus crystals are formed on the cooler surface at the top of the ampoule over the temperature range of 500.degree.-560.degree. C. The preferred heating temperature is in the neighborhood of 555.degree. C. and the preferred deposition temperature is in the neighborhood of 539.degree. C. Alkali metals that may be employed include sodium, potassium, rubidium and cesium. The monoclinic phosphorus crystals form in two habits. Those formed in the presence of sodium and cesium are in the form of flat square platelets up to 4 mm on a side and 2 mm thick. These platelets may be easily cleaved into thinner platelets, like mica. The other habit formed in the presence of potassium and rubidium is in the form of a truncated pyramid up to 4 mm.times.3 mm.times.2 mm high. This habit is hard to cleave. The crystals are semiconductors with a band gap, indicated by photoluminescence, of about 2.1 eV at room temperature. Powder X-ray diffraction, and differential thermal analysis are consistent with that reported for Hittorf's phosphorus prepared according to the prior art. The crystals are a deep red on transmission and birefringent, rotating the plane of polarization in a polarizing microscope. They contain from 50 to 2000 parts per million of alkali metal and therefore may be utilized as a form of very pure phosphorus as well as for their semiconducting and birefringent qualities and as phosphors.

Monoclinic phosphorus formed from vapor in the presence of an alkali

Liquid white phosphorus is distilled from red phosphorus in vacuo at 480.degree.-490.degree. C. The vapor is transferred in a conduit maintained at 250.degree. C. and condensed into liquid white phosphorus at room temperature. The liquid white phosphorus is then filtered to eliminate any condensed red phosphorus. The clear, colorless phosphorus produced may be utilized as a source of P.sub.4 species for chemical vapor deposition, sputtering, vacuum deposition, and molecular beam deposition of phosphorus, polyphosphide, and other phosphorus compound films for semiconductor and other applications including insulation and passivation.

Method of preparing high purity white phosphorus

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 where x=7 to 15 or very much greater than 15 (new forms of phosphorus) are useful semiconductors 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. Rectifying Schottky junction devices doped with Ni and employing Ni as a back contact comprise Cu, Al, Mg, Ni, Au, Ag, and Ti as junction forming top contacts. Photovoltaic, photoresistive, and photoluminescent devices are also disclosed. All semiconductor applications appear feasible. 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, infrared transmitting windows, and optical rotators.

Catenated phosphorus materials, their preparation and use, and

A process for the preparation of organophosphorus derivatives of organic hydroxyl or sulfhydryl compounds which includes the step of electrolyzing said organic hydroxyl or sulfhydryl compounds in an electrochemical cell having an anode comprising ferrophosphorus.

Electrochemical synthesis of organophosphorus compounds

A process for the preparation of organophosphorus derivatives of organic hydroxyl or sulfhydryl compounds which includes the step of electrolyzing said organic hydroxyl or sulfhydryl compounds in an electrochemical cell having an anode comprising elemental phosphorus.

Electrochemical synthesis of organophosphorus compounds from the element

The invention is a process for purifying elemental yellow phosphorus by contacting the yellow phosphorus with an aliphatic alcohol-tetraalkyl ammonium halide solution which effectively removes impurities and produces a colorless product.

Decolorization of elemental yellow phosphorus

Metal alkoxides, such as antimony glyoxide, are produced in the anolyte of a compartmented electrochemical cell, characterized by the seperation of the anolyte from the catholyte by an anion-exchange membrane. The anode comprises the sacrifical metal; the cathode is an indifferent material. Monohydric metal alkoxides also can be produced.

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Upper Montclair, NJ, United States of America

Mark A Kuck