- Ga(N,P) Growth on Si and Decomposition Studies of the N-P Precursor Di- tert-butylaminophosphane (DTBAP)
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III/V semiconductors containing small amounts of nitrogen (dilute nitrides) are promising for applications such as lasers and solar cells. Metal-organic vapor-phase epitaxy (MOVPE) is a widely used technique for growing III/V semiconductors on an industrial scale, and the growth of dilute nitrides with this method is promising for later successful market entry. The main issues of dilute nitrides are carbon incorporation and low nitrogen incorporation efficiency of the conventional N precursors. Due to the high N incorporation efficiency and the low decomposition temperature of the As and N precursor di-tert-butylaminoarsane (DTBAA), a similar P- and N-containing precursor, di-tert-butylaminophosphane (DTBAP), was synthesized and purified on a laboratory scale. Growth studies using this precursor were carried out in this work realizing Ga(N,P)/GaP multi quantum wells on Si and GaP substrates. The structures show evidence of N incorporation, and good layer structures were confirmed by high-resolution X-ray diffraction. Following the influence of different growth parameters on the N incorporation, the growth rate and surface morphology were characterized to set a foundation for possible growth applications in the future. DTBAP shows many advantages over the conventional N source 1,1-dimethylhydrazine (UDMHy) such as a much lower decomposition temperature of 310 °C and the realization of Ga(N,P) layers grown at temperatures as low as 475 °C with a high N incorporation of over 10percent. Furthermore, the gas-phase decomposition of DTBAP has been studied with a real-time fast Fourier transform quadrupole ion trap mass spectrometer attached inline to the MOVPE reactor. The decomposition of DTBAP behaves very similarly to the As analogue DTBAA. On the one hand, the tert-butyl groups attached to DTBAP decompose radically, leading to the formation of isobutane, and decompose, on the other hand, by β-H elimination, leading to the formation of isobutene. Furthermore, the decomposition products indicate a direct cleavage of the P-N bond of the molecule, resulting in the formation of aminyl radicals (NH2?). The formation of NH2? explains the high N incorporation efficiency of DTBAP at low temperatures as well as its limitations due to loss of NH3 at higher temperatures.
- Glowatzki, Johannes,H?nisch, Carsten Von,Hepp, Thilo,K?ster, Marcel,Ma?meyer, Oliver,Odofin, Ebunoluwa,Stolz, Wolfgang,Volz, Kerstin
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- Novel sterically hindered ferrocenyl-phosphonium salt
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New sterically hindered ferrocenyl containing phosphonium salt was synthesized in two steps starting from ferrocene. To avoid halogen contamination di-tert-butylferrocenylphosphine was quaternized with methyl bis(trifluoromethanesulfonyl)imide directly. Obtained phosphonium salt was characterized with several physical methods.
- Kadyrgulova, Liliya,Ermolaev, Vadim,Gilmanova, Leysan,Miluykov, Vasiliy
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- Synthesis of ternary group 13/15 chain compounds
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Herein we present the synthesis and characterisation of the seven-membered group 13/15 chain compound HB{N(H)PtBu2BH3}2 (3) obtained from the reaction of tBu2PNH2 (1) with Me2S·BH3. Furthermore, we describe the synthesis of the aluminium and gallium compounds tBu2PN(H)AltBu2N(H)P(H)tBu2 (4) and tBu2(H)PN(H)GatBu3 (5) derived from the reaction of tBu2PNH2 (1) with MtBu3 (M = Al, Ga).
- K?ster, Marcel,Kreher, Annikka,Von H?nisch, Carsten
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- Ferrocene-containing sterically hindered phosphonium salts
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The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations b
- Ermolaev, Vadim,Gerasimova, Tatiana,Kadyrgulova, Liliya,Shekurov, Ruslan,Dolengovski, Egor,Kononov, Aleksandr,Miluykov, Vasily,Sinyashin, Oleg,Katsyuba, Sergei,Budnikova, Yulia,Khrizanforov, Mikhail
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- Reactivity of Phosphanylphosphinidene Complex of Tungsten(VI) toward Phosphines: A New Method of Synthesis of catena-Polyphosphorus Ligands
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The reactivity of an anionic phosphanylphosphinidene complex of tungsten(VI), [(2,6-i-Pr2C6H3N)2(Cl)W(η2-t-Bu2P=P)]Li·3DME toward PMe3, halogenophosphines, and iodine was investigated. Reaction of the starting complex with Me3P led to formation of a new neutral phosphanylphosphinidene complex, [(2,6-i-Pr2C6H3N)2(Me3P)W(η2-t-Bu2P=P)]. Reactions with halogenophosphines yielded new catena-phosphorus complexes. From reaction with Ph2PCl and Ph2PBr, a complex with an anionic triphosphorus ligand t-Bu2P-P(-)-PPh2 was isolated. The main product of reaction with PhPCl2 was a tungsten(VI) complex with a pentaphosphorus ligand, t-Bu2P-P(-)-P(Ph)-P(-)-P-t-Bu2. Iodine reacted with the starting complex as an electrophile under splitting of the P-P bond in the t-Bu2P=P unit to yield [(1,2-η-t-Bu2P-P-P-t-Bu2)W(2,6-i-Pr2C6H3N)2Cl], t-Bu2PI, and phosphorus polymers. The molecular structures of the isolated products in the solid state and in solution were established by single crystal X-ray diffraction and NMR spectroscopy. (Chemical Equation Presented).
- Grubba, Rafa?,Ordyszewska, Anna,Kaniewska, Kinga,Ponikiewski, ?ukasz,Chojnacki, Jaros?aw,Gudat, Dietrich,Pikies, Jerzy
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p. 8380 - 8387
(2015/09/21)
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- METHOD FOR PREPARING HALOGENATED ORGANOPHOSPHINES
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The present application relates to a process for preparing a halogenated organophosphine, comprising reacting a primary or secondary organophosphine with a halogenating agent selected from (A) a compound of formula (I) : (HaI)3C-C(O)-X (I) wherein X is selected from alkyl, aryl, aralkyl, alkaryl, cycloalkyl, NR1R2, C(HaI)3, OR3, -0-C(O)-R3', or -Y-Z-Y-C(O)- C(HaI)3; R1 and R2 are each independently selected from hydrogen, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl; R3 is selected from H, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, or triorganosilyl; R3' is selected from C(HaI)3, alkyl, aryl, aralkyl, alkaryl, cycloalkyl; Y is independently selected from 0 or NH; Z is independently selected from alkylene, arylene, aralkylene, alkarylene, or cycloakylene; and Hal is selected from Cl or Br; or (B) a derivative of a polyol, polyamine or polyaminoalcohol comprising two or more hydroxyl and/or amino groups, in which a hydrogen atom in each of the hydroxyl and/or amino groups is replaced with a group -C(O)-C(HaI)3, wherein Hal is selected from Cl or Br.
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Page/Page column 17
(2009/12/28)
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- Sterically crowded diphosphinomethane ligands: Molecular structures, UV-photoelectron spectroscopy and a convenient general synthesis of tBu2PCH2PtBu2 and related species
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A series of highly crowded symmetric and unsymmetric diphosphinomethanes R2PCH2PR′2, important ligands in transition metal chemistry and catalysis, namely tBu2PCH2ptBu2 (dtbpm, 11), Cy2PCH2PCy2 (dcpm, 2), tBu2PCH2PCy2 (ctbpm, 3), tBu2PCH2PiPr2 (iptbpm, 4) and tBu2PCH2PPh2 (ptbpm, 5), has been prepared in high yields, using a general and convenient route, which is described in detail for 1. Other than 4, which is a colourless liquid, these compounds are crystalline solids at room temperature. Their molecular structures have been determined by single crystal X-ray diffraction, along with that of the higher homologue of 1, tBu2CH2CH2tBu 2 (dtbpe, 6). The solid-state structures of the dioxide of 1, tBu2P(O)CH2P(O)tBu2 (7), and of two phosphonium cations derived from 1, protonated [tBu2P(H)CH2PtBu2] + (8+) and the chlorophosphonium ion [tBu2P(Cl)CH2PtBu2] + (9+), are also described and show a distinct structural influence of the tetracoordinate P centres. The gas phase UV-photoelectron spectra of the diphosphines 1-6 have been measured. Their first two ionisation potentials are found to be nearly degenerate and all are in the low energy range from 7.5 to 7.8 eV. Comparison with related mono- and bidentate phosphines demonstrates that 1-6 are excellent σ-donors towards metals, in accord with their known coordination chemistry. Molecular geometries and electronic structures of the diphosphine systems have been studied by quantum chemical calculations and are compared to experiment. Unlike standard semiempirical methods (AM1, PM3, MNDO), which give rather poor minimum structures and seem inadequate for such sterically crowded systems, ab initio calculations (RHF/6-31G**) predict molecular geometries with reasonable accuracy and reflect the observed trends in experimental ionisation potentials.
- Eisentraeger, Frank,Goethlich, Alexander,Gruber, Irene,Heiss, Helmut,Kiener, Christoph A.,Krueger, Carl,Notheis, J. Ulrich,Rominger, Frank,Scherhag, Gunter,Schultz, Madeleine,Straub, Bernd F.,Volland, Martin A. O.,Hofmann, Peter
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p. 540 - 550
(2007/10/03)
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- REACTION OF SECONDARY PHOSPHINES WITH CARBON TETRACHLORIDE. SYNTHESIS OF ALKYLACYLCHLOROPHOSPHINES
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We present a method for the synthesis of hitherto unknown chlorides of alyklacylphosphinic acids by reaction of alkylacylphosphines with carbon tetrachloride in the presence of triethylamine.We have discovered a reaction of chlorides of alkylacylphosphinic acids in which intermolecular migration of an acyl group takes place.
- Veits, Yu. A.,Neganova, E. G.,Filippov, M. V.,Borisenko, A. A.,Foss, V. L.
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p. 114 - 118
(2007/10/02)
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- Unsymmetrically Substituted Phosphino Sulfur Diimides - NMR Studies on the Configuration in Solution
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The phosphino-substituted sulfur diimides S(N-Pt-Bu2)2 (1), t-Bu2P(NSN)PRR' (R = R' = phenyl (2a), cyclohexyl (2b), isopropyl (2c), ethyl (2d); R = phenyl, R' = tert-butyl (2e)) and t-Bu2P(NSN)t-Bu (3) were studied in solution by 1H, 13C and 31P NMR spectroscopy.The coupling constants 4J(31P31P) of the compounds containing different phosphino groups, 2a-e, depend both on the nature of the solvent and the temperature.The NMR results are interpreted in accord with a rapid Z/EE/Z interconversion at room temperature and the predominance of a single configurational isomer at low temperatures.There is no indication for the presence of the "symmetrical" configurations, Z/Z or E/E respectively, in solution in appreciable amounts. 15N NMR data are also reported for a series of sulfur diimides. - Keywords: Phosphino-Substituted Sulfur Diimides, 15N NMR Spectra, 31P NMR Spectra, Configurational Isomerism of Sulfur Diimides
- Herberhold, Max,Frank, Stefan M.,Wrackmeyer, Bernd
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p. 985 - 992
(2007/10/02)
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- DARSTELLUNG UND NMR-SPEKTROSKOPISCHE CHARAKTERISIERUNG EINIGER DI-n-ALKYL- UND n-ALKYLARYL-CHLOROPHOSPHANE
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A series of di-n-alkyl and n-alkylaryl chlorophosphines has been prepared by the reaction of tetraorganodiphosphines with chlorodiphenyl or dichlorophenyl phosphine and characterized by 31P and 13C NMR spectra.
- Wolfsberger, W
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p. 167 - 174
(2007/10/02)
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- Low Coordinated Phosphorus Compounds, 30 - 1-Chloro-2-phenyl-2-(trimethylsilyl)-1-phosphaethene as a Structural Part for New Phosphaalkenes
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New phosphorus-substituted phosphaalkenes are synthesized via a reaction of 1-chloro-2-phenyl-2-(trimethylsilyl)-1-phosphaethene (1) with alcohols, amines, amides, phosphanes, and organometallic reagents.Their structures are well documented by NMR data and in the case of compounds 3a, 5a, and 13 also by an X-ray analysis.Properties and some reactions of the new compounds are given.
- Appel, Rolf,Kuendgen, Ursula,Knoch, Falk
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p. 1352 - 1370
(2007/10/02)
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