BP: synthesis and properties of boron phosphide

Cubic boron phosphide, BP, is notorious for its difficult synthesis, thus preventing it from being a widely used material in spite of having numerous favorable technological properties. In the current work, three different methods of synthesis are developed and compared: from the high temperature reaction of elements, Sn flux assisted synthesis, and a solid state metathesis reaction. Structural and optical properties of the products synthesized from the three methods were thoroughly characterized. Solid state metathesis is shown to be the cleanest and most efficient method in terms of reaction temperature and time. Synthesis by Sn flux resulted in a novel Sn-doped BP compound. Undoped BP samples exhibit an optical bandgap of ~2.2 eV while Sn-doped BP exhibits a significantly smaller bandgap of 1.74 eV. All synthesized samples show high stability in concentrated hydrochloric acid, saturated sodium hydroxide solutions, and fresh aqua regia.

[1]  P. Gielisse,et al.  Raman spectra of AℓN, cubic BN and BP , 1968 .

[2]  J. Gullman The crystal structure of SnP , 1990 .

[3]  P. Sims,et al.  Crystalline (Al1-xBx)PSi3 and (Al1-xBx)AsSi3 tetrahedral phases via reactions of Al(BH4)3 and M(SiH3)3 (M = P, As) , 2015 .

[4]  P. Gielisse,et al.  Synthesis of single crystal boron phosphide , 1973 .

[5]  R. J. Archer,et al.  Optical Absorption, Electroluminescence, and the Band Gap of BP , 1964 .

[6]  W. Keller,et al.  Das erste closo‐Diphosphahexaboran P2B4Cl4 , 1988 .

[7]  P. Popper,et al.  Boron Phosphide, a III–V Compound of Zinc-Blende Structure , 1957, Nature.

[8]  B. Deboer,et al.  Crystal and molecular structure of phosphorus trifluoride- tris(difluoroboryl)borane, B4F6-PF3 , 1969 .

[9]  Jinwang Li,et al.  A facile high-yield solvothermal route to tin phosphide Sn4P3 , 2006 .

[10]  Y. Takahashi,et al.  Thermal conductivity of a boron phosphide single‐crystal wafer up to high temperature , 1989 .

[11]  R. A. Ruehrwein,et al.  The Preparation and Properties of Boron Phosphides and Arsenides1 , 1960 .

[12]  O. Lebedev,et al.  Highly Disordered Crystal Structure and Thermoelectric Properties of Sn3P4 , 2008 .

[13]  K. Eichele,et al.  Homoleptic cadmium and mercury compounds of stanna-closo-dodecaborate. , 2008, Inorganic chemistry.

[14]  P. Vogl,et al.  Dependence on volume of the phonon frequencies and the ir effective charges of several III-V semiconductors , 1983 .

[15]  Y. Kumashiro,et al.  Schottky barrier diodes using thick, well‐characterized boron phosphide wafers , 1985 .

[16]  E. Kelder,et al.  Polycrystalline Boron Phosphide Semiconductor Electrodes , 1989 .

[17]  Liyi Shi,et al.  Low temperature synthesis of boron phosphide nanocrystals , 2005 .

[18]  B. Stone,et al.  Semiconducting Properties of Cubic Boron Phosphide , 1960 .

[19]  M. Schroeder,et al.  LiB12PC, the first boron-rich metal boride with phosphorus--synthesis, crystal structure, hardness, spectroscopic investigations. , 2011, Chemistry.

[20]  J. M. Jackson,et al.  The Crystal Growth of Boron Monophosphide from Metal Phosphide Solutions , 1973 .

[21]  Y. Kumashiro Refractory semiconductor of boron phosphide , 1990 .

[22]  Yuri Grin,et al.  WinCSD: software package for crystallographic calculations (Version 4) , 2014 .