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[CH3NH3]PbX3 crystal structure. [1]

Methylammonium lead halides (MALHs) are solid compounds with perovskite structure and a chemical formula of [CH3NH3+Pb2+(X−)3, where X = Cl, Br or I. They have potential applications in solar cells, [2] lasers, light-emitting diodes, photodetectors, radiation detectors, [3] [4] scintillator, [5] magneto-optical data storage [6] and hydrogen production. [7]


Properties and synthesis

The first MALHs to be synthesized were the methylammonium derivatives [CH3NH3]SnX3 and [CH3NH3]PbX3. Their potential in the area of energy conversion wasn't realized until decades later. [8] In the [CH3NH3]PbX3 cubic crystal structure the methylammonium cation ([CH3NH3+) is surrounded by PbX6 octahedra. The X ions are not fixed and can migrate through the crystal with an activation energy of 0.6 eV; the migration is vacancy assisted. [1] The methylammonium cations can rotate within their cages. At room temperature the ions have the CN axis aligned towards the face directions of the unit cells and the molecules randomly change to another of the six face directions on a 3 ps time scale. [9]

Growth of a [CH3NH3]PbI3 single crystal in gamma-butyrolactone at 110 °C. The yellow color originates from the lead(II) iodide precursor. [7]
Growth of a [CH3NH3]PbBr3 single crystal in dimethylformamide at 80 °C. [7]

The solubility of MALHs strongly decreases with increased temperature: from 0.8 g/mL at 20 °C to 0.3 g/mL at 80 °C for [CH3NH3]PbBr3 in dimethylformamide. This property is used in the growth of MALH single crystals and films from solution, using a mixture of [CH3NH3]X and PbX2 powders as the precursor. The growth rates are 3–20 mm3/hour for [CH3NH3]PbI3 and reach 38 mm3/hour for [CH3NH3]PbBr3 crystals. [7]

The resulting crystals are metastable and dissolve in the growth solution when cooled to room temperature. They have bandgaps of 2.18 eV for [CH3NH3]PbBr3 and 1.51 eV for [CH3NH3]PbI3, while their respective carrier mobilities are 24 and 67 cm2/(V·s). [7] Their thermal conductivity is exceptionally low, ~0.5 W/(K·m) at room temperature for [CH3NH3]PbI3. [10]


Thermal decomposition of [CH3NH3]PbI3 gives methyl iodide (CH3I) and ammonia (NH3). [11] [12]

[CH3NH3]PbI3 → PbI2 + CH3I + NH3

Applications

MALHs have potential applications in solar cells, lasers, [13] light-emitting diodes, photodetectors, radiation detectors, [4] scintillator [5] and hydrogen production. [7] The power conversion efficiency of MALH solar cells exceeds 19%. [14] [15]

Historic references

  • Weber, Dieter (1978). "CH3NH3SnBrxI3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH3NH3SnBrxI3-x (x = 0-3), a Sn(II)-System with Cubic Perovskite Structure". Zeitschrift für Naturforschung B. 33 (8): 862–865. doi: 10.1515/znb-1978-0809. ISSN  1865-7117.
  • Weber, Dieter (1978-12-01). "CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur / CH3NH3PbX3 , a Pb(II)-System with Cubic Perovskite Structure". Zeitschrift für Naturforschung B. 33 (12): 1443–1445. doi: 10.1515/znb-1978-1214. ISSN  1865-7117. S2CID  93597007.*Grätzel, Michael (2014). "The light and shade of perovskite solar cells". Nature Materials. 13 (9): 838–842. doi: 10.1038/nmat4065. ISSN  1476-1122. PMID  25141800.

See also

References

Wikimedia Commons has media related to Methylammonium lead halides.
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  2. ^ Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo; Miyasaka, Tsutomu (2009-05-06). "Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells". Journal of the American Chemical Society. 131 (17): 6050–6051. doi: 10.1021/ja809598r. ISSN  0002-7863. PMID  19366264.
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  5. ^ a b Birowosuto, M. D. (16 November 2016). "X-ray Scintillation in Lead Halide Perovskite Crystals". Sci. Rep. 6: 37254. arXiv: 1611.05862. Bibcode: 2016NatSR...637254B. doi: 10.1038/srep37254. PMC  5111063. PMID  27849019.
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