Cadmium arsenide

Cadmium arsenide
Names
Other names
Tricadmium diarsenide
Identifiers
12006-15-4
ChemSpider 10678197
EC number 234-484-1
Jmol-3D images Image
Properties
Cd
3As
Molar mass 487.08 g/mol
Appearance solid, dark grey
Density 3.031
Melting point 716 °C (1,321 °F; 989 K)
decomposes in water
Hazards
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oil Health code 4: Very short exposure could cause death or major residual injury. E.g., VX gas Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazard W: Reacts with water in an unusual or dangerous manner. E.g., cesium, sodiumNFPA 704 four-colored diamond
1
4
0
no data
US health exposure limits (NIOSH):
5 micrograms (Cd)/m3
Except where noted otherwise, data is given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

Cadmium arsenide (Cd3As2) is an inorganic, crystalline semiconductor with a tetragonal structure in the II-V family. Cadmium arsenide shows the Nernst effect.

Properties

Thermal

Cd
3As
2(s) is proven to dissociate thermally between 220° to 280° according to the reaction

Cd
3As
2(s) → 3Cd
(g) + 0.5 As
4(g)[1]

An energy barrier was found for the nonstoichiometric vaporization of arsenic due to the irregularity of the partial pressures with temperature. The range of the energy gap is from 0.5 to 0.6 eV. Cd
3As melts at 716 °C and changes phase at 615 °C/[2]

Phase Transition

Pure cadmium arsenide undergoes several phase transitions at high temperatures, making phases labeled α (stable phase), α’, α” (metastable phase), β.[3] At 593° the polymorphic transition α → β happens.

α-Cd
3As <-> α’-Cd
3As happens at ~500K.

α’-Cd
3As <-> α’’-Cd
3As happens at ~742 and is a regular first order phase transition with marked hysteresis loop.

α”-Cd
3As <-> β-Cd
3As happens at 868 K.

Singly crystal x-ray diffraction was used to determine the lattice parameters of Cd
3As between 23 and 700 °C. Transition α → α′ happens slowly and there is most likely an intermediate phase. The transition α′ → α″ occurs much faster than α → α′ and has very small thermal hysteresis. This transition results in a change in the fourfould axis of the tetragonal cell, causing Crystal twinning. The width of the loop is independent of the rate of heating although it becomes narrower after several temperature cycles.[4]

Electronic

The compound cadmium arsenide has a lower vapor pressure (0.8 atm) than both cadmium and arsenic separately. Cadmium arsenide does not decompose when it is vaporized and re-condensed. Carrier Concentration in Cd
3As are usually between 1 and 4 x 1018 electrons/cm3. Despite having high carrier concentrations, the electron mobilities are also very high (up to 10,000 cm2/Vs at room temperature).[5]

In 2014 Cd
3As
2 was shown to be a “semi-metal” material analogous to graphene that exists in a 3D form that should be much easier to shape into electronic devices.[6][7] Three-dimensional (3D) topological Dirac semimetals (TDSs) are bulk analogues of graphene that also exhibit non-trivial topology in its electronic structure that shares similarities with topological insulators. Moreover, a TDS can potentially be driven into other exotic phases (such as Weyl semimetals, axion insulators and topological superconductors), Angle-resolved photoemission spectroscopy revealed a pair of 3D Dirac fermions in Cd
3As
2. Compared with other 3D TDSs, for example, β-cristobalite BiO
2 and Na3Bi, Cd
3As
2 is stable and has much higher Fermi velocities. In situ doping was used to tune its Fermi energy.[7][8]

Conducting

Cadmium Arsenide is a II-V semiconductor showing degenerate N-type semiconductor intrinsic conductivity with a large mobility, low effective mass and highly non parabolic conduction band, or a Narrow-gap semiconductor. It displays an inverted band structure, and the optical energy gap, eg, is less than 0. When deposited by thermal evaporation (deposition), cadmium arsenide displayed the Schottky (Thermionic emission) and Poole–Frenkel effect at high electric fields.[9]

Preparation

Cadmium arsenide can be prepared as amorphous semiconductive glass. According to Hiscocks and Elliot,[2] the preparation of cadmium arsenide was made from cadmium metal, which had a purity of 6 N from Kock-Light Laboratories Limited. Hoboken supplied β-arsenic with a purity of 99.999%. Stoichiometric proportions of the elements cadmium and arsenic were heated together. Separation was difficult and lengthy due to the ingots sticking to the silica and breaking. Liquid encapsulated Stockbarger growth was created. Crystals are pulled from volatile melts in liquid encapsulation. The melt is covered by a layer of inert liquid, usually B2O3, and an inert gas pressure greater than the equilibrium vapor pressure is applied. This eliminates the evaporation from the melt which allows seeding and pulling to occur through the B2O3 layer.

Crystal Structure

The unit cell of Cd
3As
2 is tetragonal. The arsenic ions are cubic close packed and the cadmium ions are tetrahedrally coordinated. The vacant tetrahedral sites provoked research by von Stackelberg and Paulus (1935), who determined the primary structure. Each arsenic ion was surrounded by cadmium ions at six of the eight corners of a distorted cube and the two vacant sites were at the diagonals.[10]

Nernst Effect

Cadmium arsenide is used in infrared detectors using the Nernst effect, and in thin-film dynamic pressure sensors. It can be also used to make magnetoresistors, and in photodetectors.[11]

Cadmium arsenide can be used as a dopant for HgCdTe.

References

  1. ↑ Westmore, J. B.; Mann, K. H.; Tickner, A. W. (1964). "Mass Spectrometric Study of the Nonstoichiometric Vaporization of Cadmium Arsenide1". The Journal of Physical Chemistry 68 (3): 606. doi:10.1021/j100785a028.
  2. ↑ 2.0 2.1 Hiscocks, S. E. R.; Elliott, C. T. (1969). "On the preparation, growth and properties of Cd3As2". Journal of Materials Science 4 (9): 784. doi:10.1007/BF00551073.
  3. ↑ Pietraszko, A.; Łukaszewicz, K. (1969). "A refinement of the crystal structure of α-Cd3As2". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 25 (5): 988. doi:10.1107/S0567740869003323.
  4. ↑ Pietraszko, A.; Łukaszewicz, K. (1973). "Thermal expansion and phase transitions of Cd3As2 and Zn3As2". Physica Status Solidi (a) 18 (2): 723. doi:10.1002/pssa.2210180234.
  5. ↑ Dowgiałło-Plenkiewicz, B.; Plenkiewicz, P. (1979). "Inverted band structure of Cd3As2". Physica Status Solidi (b) 94: K57. doi:10.1002/pssb.2220940153.
  6. ↑ Neupane, M.; Xu, S. Y.; Sankar, R.; Alidoust, N.; Bian, G.; Liu, C.; Belopolski, I.; Chang, T. R.; Jeng, H. T.; Lin, H.; Bansil, A.; Chou, F.; Hasan, M. Z. (2014). "Observation of a three-dimensional topological Dirac semimetal phase in high-mobility Cd3As2". Nature Communications 5. doi:10.1038/ncomms4786.
  7. ↑ 7.0 7.1 Liu, Z. K.; Jiang, J.; Zhou, B.; Wang, Z. J.; Zhang, Y.; Weng, H. M.; Prabhakaran, D.; Mo, S. K.; Peng, H.; Dudin, P.; Kim, T.; Hoesch, M.; Fang, Z.; Dai, X.; Shen, Z. X.; Feng, D. L.; Hussain, Z.; Chen, Y. L. (2014). "A stable three-dimensional topological Dirac semimetal Cd3As2". Nature Materials. doi:10.1038/nmat3990.
  8. ↑
  9. ↑ Din, M.; Gould, R. D. (2006). "Van der Pauw resistivity measurements on evaporated thin films of cadmium arsenide, Cd3As2". Applied Surface Science 252 (15): 5508. doi:10.1016/j.apsusc.2005.12.151.
  10. ↑ Ali, M. N.; Gibson, Q.; Jeon, S.; Zhou, B. B.; Yazdani, A.; Cava, R. J. (2014). "The Crystal and Electronic Structures of Cd3As2, the Three-Dimensional Electronic Analogue of Graphene". Inorganic Chemistry 53 (8): 4062. doi:10.1021/ic403163d. PMID 24679042.
  11. ↑ . doi:10.1109/SMELEC.1998.781173. Missing or empty |title= (help)

External links