Zinc phosphide

Last updated
Zinc phosphide [1]
Zn3P2structure.jpg
Names
Other names
trizinc diphosphide
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.013.859 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-867-3
PubChem CID
UNII
  • InChI=1S/2P.3Zn Yes check.svgY
    Key: NQDYSWQRWWTVJU-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/2P.3Zn/rP2Zn3/c3-1-5-2-4
    Key: NQDYSWQRWWTVJU-WGUIJFGEAN
  • [Zn]=P[Zn]P=[Zn]
Properties
Zn3P2
Molar mass 258.12 g/mol
Appearancedark gray
Odor characteristic [2]
Density 4.55 g/cm3
Melting point 1,160 °C (2,120 °F; 1,430 K)
reacts
Solubility insoluble in ethanol, soluble in benzene, reacts with acids
Band gap 1.4-1.6 eV (direct) [3]
Structure
Tetragonal, tP40
P42/nmc, No. 137
a = 8.0785 Å, c = 11.3966 Å [4]
8
Hazards
Occupational safety and health (OHS/OSH):
Ingestion hazards
Fatal, acutely toxic
Inhalation hazards
High
GHS labelling: [2]
GHS-pictogram-flamme.svg GHS-pictogram-skull.svg
Danger
H260, H300
P223, P231+P232, P264, P270, P280, P301+P310, P321, P330, P335+P334, P370+P378, P402+P404, P405, P501
NFPA 704 (fire diamond)
[2]
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
4
3
2
W
Lethal dose or concentration (LD, LC):
Oral
42.6 mg/kg (Rat)
12 mg/kg (Rat)
Dermal
1123 mg/kg (Rat)
2000 mg/kg (Rabbit) [2]
Safety data sheet (SDS)ThermoFisher Scientific, revised 02/2020 [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Zinc phosphide (Zn3 P2) is an inorganic chemical compound. It is a grey solid, although commercial samples are often dark or even black. It is used as a rodenticide. [5] Zn3P2 is a II-V semiconductor with a direct band gap of 1.5 eV [6] and may have applications in photovoltaic cells. [7] A second compound exists in the zinc-phosphorus system, zinc diphosphide (ZnP2).

Contents

Synthesis and reactions

Zinc phosphide can be prepared by the reaction of zinc with phosphorus; however, for critical applications, additional processing to remove arsenic compounds may be needed. [8]

6 Zn + P4 → 2 Zn3P2

Another method of preparation include reacting tri-n-octylphosphine with dimethylzinc. [9]

Zinc phosphide reacts with water to produce highly toxic phosphine (PH3) and zinc hydroxide (Zn(OH)2):

Zn3P2 + 6 H2O → 2 PH3 + 3 Zn(OH)2

Structure

Zn3P2 has a room-temperature tetragonal form that converts to a cubic form at around 845 °C. [10] In the room-temperature form there are discrete P atoms, zinc atoms are tetrahedrally coordinated and phosphorus six coordinate, with zinc atoms at 6 of the vertices of a distorted cube. [11]

The crystalline structure of zinc phosphide is very similar to that of cadmium arsenide (Cd3As2), zinc arsenide (Zn3As2) and cadmium phosphide (Cd3P2). These compounds of the Zn-Cd-P-As quaternary system exhibit full continuous solid-solution. [12]

Applications

Photovoltaics

Zinc phosphide is an ideal candidate for thin film photovoltaic applications, for it has strong optical absorption and an almost ideal band gap (1.5eV). In addition to this, both zinc and phosphorus are found abundantly in the Earth's crust, meaning that material extraction cost is low compared with that of other thin film photovoltaics. Both zinc and phosphorus are also nontoxic, which is not the case for other common commercial thin film photovoltaics, like cadmium telluride. [13]

Researchers at the University of Alberta were the first to successfully synthesize colloidal zinc phosphide. Before this, researchers were able to create efficient solar cells from bulk zinc phosphide, but their fabrication required temperatures greater than 850 °C or complicated vacuum deposition methods. By contrast, colloidal zinc phosphide nanoparticles, contained in a zinc phosphide “ink”, allows for inexpensive, easy large-scale production, by means of slot-die coating or spray coating. [14]

The testing and development of these zinc phosphide thin films is still in its early stages, but early results have been positive. Prototype heterojunction devices fabricated from zinc phosphide nanoparticle ink exhibited a rectification ratio of 600 and photosensitivity with an on/off ratio near 100. These are both acceptable suitability benchmarks for solar cells. Development still needs to be made on optimizing the nanoparticle ink formation and device architecture before commercialization is possible, but commercial spray-on zinc phosphide solar cells may be possible within ten years. [15]

Pest control

Rodenticide

Metal phosphides have been used as rodenticides. A mixture of food and zinc phosphide is left where the rodents can eat it. The acid in the digestive system of the rodent reacts with the phosphide to generate toxic phosphine gas. This method of vermin control has possible use in places where rodents are immune to other common poisons. Other pesticides similar to zinc phosphide are aluminium phosphide and calcium phosphide.

Zn3P2 + 6H+ → 3Zn++ + PH3 ↑ [16]

Zinc phosphide is typically added to rodent baits in amount of around 0.75-2%. Such baits have a strong, pungent garlic-like odor characteristic of phosphine liberated by hydrolysis. The odor attracts rodents, but has a repulsive effect on other animals; However, birds, notably wild turkeys, are not sensitive to the smell. The baits have to contain sufficient amount of zinc phosphide in sufficiently attractive food in order to kill rodents in a single serving; a sublethal dose may cause aversion towards zinc phosphide baits encountered by surviving rodents in the future.

Rodenticide-grade zinc phosphide usually comes as a black powder containing 75% of zinc phosphide and 25% of antimony potassium tartrate, an emetic to cause vomiting if the material is accidentally ingested by humans or domestic animals. However, it is still effective against rats, mice, guinea pigs and rabbits, none of which have a vomiting reflex. [17]

Pest control in New Zealand

The New Zealand Environmental Protection Authority has approved the import and manufacture of Microencapsulated Zinc Phosphide (MZP Paste) for the ground control of possums. The application was made by Pest Tech Limited, with support from Connovation Ltd, Lincoln University and the Animal Health Board. It will be used as an additional vertebrate poison in certain situations. Unlike 1080 poison, it cannot be used for aerial application. [18]

Safety

Zinc phosphide is highly toxic, especially when ingested or inhaled. The reason for its toxicity is the release of phosphorus compounds, usually phosphine, when it reacts with water and acids. Phosphine is very toxic and, with trace amounts of P2H4, pyrophoric. Phosphine is also denser than air and may remain close to the ground without sufficient ventilation.

Related Research Articles

<span class="mw-page-title-main">Phosphine</span> Chemical compound hydrogen phosphide

Phosphine (IUPAC name: phosphane) is a colorless, flammable, highly toxic compound with the chemical formula PH3, classed as a pnictogen hydride. Pure phosphine is odorless, but technical grade samples have a highly unpleasant odor like rotting fish, due to the presence of substituted phosphine and diphosphane (P2H4). With traces of P2H4 present, PH3 is spontaneously flammable in air (pyrophoric), burning with a luminous flame. Phosphine is a highly toxic respiratory poison, and is immediately dangerous to life or health at 50 ppm. Phosphine has a trigonal pyramidal structure.

<span class="mw-page-title-main">Rodenticide</span> Chemical used to kill rodents

Rodenticides are chemicals made and sold for the purpose of killing rodents. While commonly referred to as "rat poison", rodenticides are also used to kill mice, squirrels, woodchucks, chipmunks, porcupines, nutria, beavers, and voles. Despite the crucial roles that rodents play in nature, there are times when they need to be controlled.

Phosphorus trifluoride (formula PF3), is a colorless and odorless gas. It is highly toxic and reacts slowly with water. Its main use is as a ligand in metal complexes. As a ligand, it parallels carbon monoxide in metal carbonyls, and indeed its toxicity is due to its binding with the iron in blood hemoglobin in a similar way to carbon monoxide.

<span class="mw-page-title-main">Phosphide</span>

In chemistry, a phosphide is a compound containing the P3− ion or its equivalent. Many different phosphides are known, with widely differing structures. Most commonly encountered on the binary phosphides, i.e. those materials consisting only of phosphorus and a less electronegative element. Numerous are polyphosphides, which are solids consisting of anionic chains or clusters of phosphorus. Phosphides are known with the majority of less electronegative elements with the exception of Hg, Pb, Sb, Bi, Te, and Po. Finally, some phosphides are molecular.

<span class="mw-page-title-main">Cadmium selenide</span> Chemical compound

Cadmium selenide is an inorganic compound with the formula CdSe. It is a black to red-black solid that is classified as a II-VI semiconductor of the n-type. It is a pigment but applications are declining because of environmental concerns

<span class="mw-page-title-main">Calcium phosphide</span> Chemical compound

Calcium phosphide (CP) is the inorganic compound with the formula Ca3P2. It is one of several phosphides of calcium, being described as the salt-like material composed of Ca2+ and P3−. Other, more exotic calcium phosphides have the formula CaP / Ca2P2, CaP3, and Ca5P8.

<span class="mw-page-title-main">Metalorganic vapour-phase epitaxy</span> Method of producing thin films (polycrystalline and single crystal)

Metalorganic vapour-phase epitaxy (MOVPE), also known as organometallic vapour-phase epitaxy (OMVPE) or metalorganic chemical vapour deposition (MOCVD), is a chemical vapour deposition method used to produce single- or polycrystalline thin films. It is a process for growing crystalline layers to create complex semiconductor multilayer structures. In contrast to molecular-beam epitaxy (MBE), the growth of crystals is by chemical reaction and not physical deposition. This takes place not in vacuum, but from the gas phase at moderate pressures. As such, this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys, and it has become a major process in the manufacture of optoelectronics, such as Light-emitting diodes. It was invented in 1968 at North American Aviation Science Center by Harold M. Manasevit.

<span class="mw-page-title-main">Sodium phosphide</span> Chemical compound

Sodium phosphide is the inorganic compound with the formula Na3P. It is a black solid. It is often described as Na+ salt of the P3− anion. Na3P is a source of the highly reactive phosphide anion. It should not be confused with sodium phosphate, Na3PO4.

Organophosphorus chemistry is the scientific study of the synthesis and properties of organophosphorus compounds, which are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective insecticides, although some are extremely toxic to humans, including sarin and VX nerve agents.

<span class="mw-page-title-main">Aluminium phosphide</span> Chemical compound

Aluminium phosphide is a highly toxic inorganic compound with the chemical formula AlP, used as a wide band gap semiconductor and a fumigant. This colorless solid is generally sold as a grey-green-yellow powder due to the presence of impurities arising from hydrolysis and oxidation.

Indium(III) sulfide (Indium sesquisulfide, Indium sulfide (2:3), Indium (3+) sulfide) is the inorganic compound with the formula In2S3.

Organophosphines are organophosphorus compounds with the formula PRnH3−n, where R is an organic substituent. These compounds can be classified according to the value of n: primary phosphines (n = 1), secondary phosphines (n = 2), tertiary phosphines (n = 3). All adopt pyramidal structures. Organophosphines are generally colorless, lipophilic liquids or solids. The parent of the organophosphines is phosphine (PH3).

<span class="mw-page-title-main">Diphenadione</span> Chemical compound

Diphenadione is a vitamin K antagonist that has anticoagulant effects and is used as a rodenticide against rats, mice, voles, ground squirrels and other rodents. The chemical compound is an anti-coagulant with active half-life longer than warfarin and other synthetic 1,3-indandione anticoagulants.

Zinc arsenide (Zn3As2) is a binary compound of zinc with arsenic which forms gray tetragonal crystals. It is an inorganic semiconductor with a band gap of 1.0 eV.

Quantum dots (QDs) are semiconductor nanoparticles with a size less than 10 nm. They exhibited size-dependent properties especially in the optical absorption and the photoluminescence (PL). Typically, the fluorescence emission peak of the QDs can be tuned by changing their diameters. So far, QDs were consisted of different group elements such as CdTe, CdSe, CdS in the II-VI category, InP or InAs in the III-V category, CuInS2 or AgInS2 in the I–III–VI2 category, and PbSe/PbS in the IV-VI category. These QDs are promising candidates as fluorescent labels in various biological applications such as bioimaging, biosensing and drug delivery.

Zinc diphosphide (ZnP2) is an inorganic chemical compound. It is a red semiconductor solid with a band gap of 2.1 eV. It is one of the two compounds in the zinc-phosphorus system, the other being zinc phosphide (Zn3P2).

Zinc cadmium phosphide arsenide (Zn-Cd-P-As) is a quaternary system of group II (IUPAC group 12) and group V (IUPAC group 15) elements. Many of the inorganic compounds in the system are II-V semiconductor materials. The quaternary system of II3V2 compounds, (Zn1−xCdx)3(P1−yAsy)2, has been shown to allow solid solution continuously over the whole compositional range. This material system and its subsets have applications in electronics, optoelectronics, including photovoltaics, and thermoelectrics.

Cadmium phosphide (Cd3P2) is an inorganic chemical compound. It is a grey or white bluish solid semiconductor material with a bandgap of 0.5 eV. It has applications as a pesticide, material for laser diodes and for high-power-high-frequency electronics.

Lithium phosphide is an inorganic compound of lithium and phosphorus with the chemical formula Li
3P.

<span class="mw-page-title-main">Lanthanum phosphide</span> Chemical compound

Lanthanum phosphide is an inorganic compound of lanthanum and phosphorus with the chemical formula LaP.

References

  1. ↑ Lide, David R. (1998). Handbook of Chemistry and Physics (87 ed.). Boca Raton, FL: CRC Press. pp. 4–100. ISBN   0-8493-0594-2.
  2. 1 2 3 4 5 "ThermoFisher Scientific safety data sheet". fishersci.com. Thermo Fisher Scientific. 2020-02-21. Retrieved 2020-11-02.
  3. ↑ Teng, F.; Hu, K.; Ouyang, W.; Fang, X. (2018). "Photoelectric Detectors Based on Inorganic p-Type Semiconductor Materials". Advanced Materials. 30 (35): 1706262. Bibcode:2018AdM....3006262T. doi:10.1002/adma.201706262. PMID   29888448. S2CID   47016453.
  4. ↑ Zanin, I. E.; Aleinikova, K. B.; Afanasiev, M. M.; Antipin, M. Yu. (2004). "Structure of Zn3P2". Journal of Structural Chemistry. 45 (5): 844–848. doi:10.1007/s10947-005-0067-9. S2CID   101460207.
  5. ↑ Bettermann, G.; Krause, W.; Riess, G.; Hofmann, T. (2002). "Phosphorus Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a19_527. ISBN   3527306730.
  6. ↑ Kimball, Gregory M.; Müller, Astrid M.; Lewis, Nathan S.; Atwater, Harry A. (2009). "Photoluminescence-based measurements of the energy gap and diffusion length of Zn[sub 3]P[sub 2]" (PDF). Applied Physics Letters. 95 (11): 112103. Bibcode:2009ApPhL..95k2103K. doi:10.1063/1.3225151. ISSN   0003-6951.
  7. ↑ Specialist Periodical Reports, Photochemistry, 1981, Royal Society of Chemistry, ISBN   9780851860954
  8. ↑ F. Wagenknecht and R. Juza "Zinc Phosphides" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1080-1.
  9. ↑ Luber, Erik J.; Mobarok, Md Hosnay; Buriak, Jillian M. (2013). "Solution-Processed Zinc Phosphide (α-Zn3P2) Colloidal Semiconducting Nanocrystals for Thin Film Photovoltaic Applications". ACS Nano. 7 (9): 8136–8146. doi:10.1021/nn4034234. ISSN   1936-0851. PMID   23952612.
  10. ↑ Evgeniĭ I︠U︡rʹevich Tonkov, 1992, High Pressure Phase Transformations: A Handbook, Vol 2, Gordon and Breach Science Publishers, ISBN   9782881247590
  11. ↑ Wells A.F. (1984) Structural Inorganic Chemistry 5th edition Oxford Science Publications ISBN   0-19-855370-6
  12. ↑ Trukhan, V. M.; Izotov, A. D.; Shoukavaya, T. V. (2014). "Compounds and solid solutions of the Zn-Cd-P-As system in semiconductor electronics". Inorganic Materials. 50 (9): 868–873. doi:10.1134/S0020168514090143. S2CID   94409384.
  13. ↑ Luber, Erik J. (2013). "Solution-Processed Zinc Phosphide (α-Zn 3 P 2 ) Colloidal Semiconducting Nanocrystals for Thin Film Photovoltaic Applications". ACS Nano. 7 (9): 8136–8146. doi:10.1021/nn4034234. PMID   23952612.
  14. ↑ "Colloidal zinc phosphide for photovoltaics - nanotechweb.org". Archived from the original on 2013-09-16.
  15. ↑ "Home".
  16. ↑ "Zinc Phosphide Technical Fact Sheet". npic.orst.edu.
  17. ↑ "Why rats can't vomit". Ratbehavior.org. Retrieved 2013-08-17.
  18. ↑ Environment Risk Management Authority New Zealand. "Zinc phosphide pest poison approved with controls" . Retrieved 2011-08-14.
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