Platinum diselenide

Platinum diselenide is a transition metal dichalcogenide (TMDC) consisting of the metal platinum and the non-metal selenium with the formula PtSe2. Being a layered substance, PtSe2 can be split into thin layers down to three atoms thick called monolayers. PtSe2 is a semimetal or semiconductor depending on thickness.

Platinum diselenide
Names
Other names
Platinum(IV) selenide
Sudovikovite
Identifiers
3D model (JSmol)
Properties
PtSe2
Molar mass 353.026 g·mol−1
Appearance opaque metallic yellowish white
Density 9.54
Melting point decomposes
insoluble
Band gap 0 (bulk) 1.3 eV monolayer
Structure
space group P3m1 164 hexagonal
a = 3.728[1], c = 5.031
octahedral
Related compounds
Other anions
 platinum disulfide platinum ditelluride PtSeTe PtSSe
Other cations
 palladium diselenide NiSeTe
Related platinum selenides
 Luberoite Pt5Se4
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N (what is YN ?)
Infobox references

Formation

Minozzi was the first to report synthesising platinum diselenide from the elements in 1909.[2]

Platinum diselenide can be formed by heating thin foils of platinum in selenium vapour at 400 °C.[3][4]

A platinum 111 surface exposed to selenium vapour at 270 °C forms a monolayer of PtSe2.[5]

In addition to these selenization methods, PtSe2 can be made by precipitation in water solution of Pt(IV) treated with hydrogen selenide, or by heating platinum tetrachloride with elemental selenium.[2]

Natural occurrence

Platinum diselenide occurs naturally as the mineral Sudovikovite. It was named after Russian petrologist, N.G. Sudovikov who lived from 1903 to 1966. The mineral's hardness is 2 to 21/2. Sudovikovite was found in the Srednyaya Padma mine, Velikaya Guba uranium-vanadium deposit, Zaonezhie peninsula, Karelia Republic, Russia.[6]

Properties

Platinum diselenide forms crystals in the cadmium iodide structure. This means that the substance forms layers. Each of the monolayers has a central bed of platinum atoms, with a sheet of selenium atoms above and below. This structure is also called "1T" and has an trigonal structure. The layers are only weakly bonded together, and it is possible to exfoliate layers to bilayers or monolayers.[7]

In bulk the material is semi-metallic, but when reduced to few layers it becomes a semiconductor.[7][8] The conductivity of the bulk material is 620,000 S/m.[9]

The XPS spectrum shows a peak at 72.3 eV from Pt 4f core, and also has peaks from Pt 5p3/2[7] and Se 3d3/2 and 3d5/2 at 55.19and 54.39 eV.[5]

Phonon vibrations are designated by the infrared active A2u (Se vibrating out of plane opposite to Pt), Eu (in layer vibration, Se opposite to Pt), and Raman active A1g (Se top and bottom atoms moving out of plane in opposite directions 205 cm−1), and Eg (In plane, top and botom Se atoms moving opposite 175 cm−1). In the Raman spectrum, the A1g is lessened when stimulated emissions polarised perpendicular to the incoming rays are measured. The Eg mode is red-shifted when more layers are stacked. (166 cm−1 for bilayer and 155 cm−1 for bulk material) The A1g emission only has a slight change when thickness varies.[7]

The band gap is calculated as 1.2 eV for monolayers, and 0.21 eV for bilayers. For a trylayer or thicker the substance loses a bandgap and becomes semimetallic.[5]

PtSe2 can change its conductance in the presence of particular gases, such as nitrogen dioxide. Within a few seconds, NO2 absorbs on the surface of the PtSe2 material and lowers the resistance. When the gas is absent, high resistance returns again in about a minute.[3]

The Seebeck coefficient of PtSe2 is 40 μV/K.[10]

Although pristine platinum diselenide is nonmagnetic, the presence of platinum vacancies and strain were predicted to induce magnetism.[11] Later magneto-transport studies [12] have indeed shown that defective PtSe2 exhibits magnetic properties. Due to RKKY interaction between magnetic Pt-vacancies, this results in layer-dependent ferromagnetic or anti-ferromagnetic behavior.

Monolayers of platinum diselenide show helical spin texture, which is not expected for centrosymmetric materials such as this. This property could be due to a local dipole induced Rashba effect. It means that PtSe2 is a potential spintronics material.[13]

Reactions

Water can physisorb to the surface of platinum diselenide with an energy of −0.19 eV, and similarly for oxygen with energy −0.13 eV. Water and oxygen do not react at toom temperature, because significant energy would be required to break apart the molecules.[9]

Comparison

Palladium diselenide has a different modified pyrite structure. Palladium ditelluride has a similar structure to platinum diselenide.[14] Platinum disulfide is a semiconductor, and platinum ditelluride is metallic in nature.

More complex substances with platinum and selenium also exist, including the quaternary chalcogenides Rb2Pt3USe6 and Cs2Pt3USe6[15]

Jacutingaite is a ternary platinum selenide HgPtSe3.[16]

Use

Platinum diselenide is proposed for use as a mid-infra red detector superior to black phosphorus in durability in air. Also it can work as a catalyst, and can be built into field effect transistors.[9]

Combined with graphene it can be a photocatalyst, converting water and oxygen to reactive hydroxyl radical and superoxide. This reaction works when photons produce holes and electrons. The holes can neutralise hydroxide to make hydroxyl, and the electrons attach to oxygen to make superoxide. These reactive species can mineralise organic matter.

References
  1. Guo, G Y; Liang, W Y (10 March 1986). "The electronic structures of platinum dichalcogenides: PtS2 , PtSe2 and PtTe2". Journal of Physics C: Solid State Physics. 19 (7): 995–1008. Bibcode:1986JPhC...19..995G. doi:10.1088/0022-3719/19/7/011.
  2. Grønvold, Fredrik; Haakon, Haraldsen; Kjekshus, Arne (1960). "On the sulfides, selenides and tellurides of platinum" (PDF). Acta Chemica Scandinavica. 14 (9): 1879–1893. doi:10.3891/acta.chem.scand.14-1879.
  3. "Ultra-fast, ultra-sensitive PtSe2 gas sensors". PhysOrg. 13 January 2017. Retrieved 17 March 2017.
  4. Yim, Chanyoung; Lee, Kangho; McEvoy, Niall; O’Brien, Maria; Riazimehr, Sarah; Berner, Nina C.; Cullen, Conor P.; Kotakoski, Jani; Meyer, Jannik C.; Lemme, Max C.; Duesberg, Georg S. (25 October 2016). "High-Performance Hybrid Electronic Devices from Layered PtSe2 Films Grown at Low Temperature". ACS Nano. 10 (10): 9550–9558. arXiv:1606.08673. doi:10.1021/acsnano.6b04898. PMID 27661979. S2CID 22259155.
  5. Wang, Yeliang; Li, Linfei; Yao, Wei; Song, Shiru; Sun, J. T.; Pan, Jinbo; Ren, Xiao; Li, Chen; Okunishi, Eiji; Wang, Yu-Qi; Wang, Eryin; Shao, Yan; Zhang, Y. Y.; Yang, Hai-tao; Schwier, Eike F.; Iwasawa, Hideaki; Shimada, Kenya; Taniguchi, Masaki; Cheng, Zhaohua; Zhou, Shuyun; Du, Shixuan; Pennycook, Stephen J.; Pantelides, Sokrates T.; Gao, Hong-Jun (10 June 2015). "Monolayer PtSe2, a New Semiconducting Transition-Metal-Dichalcogenide, Epitaxially Grown by Direct Selenization of Pt". Nano Letters. 15 (6): 4013–4018. Bibcode:2015NanoL..15.4013W. doi:10.1021/acs.nanolett.5b00964. OSTI 1185929. PMID 25996311.
  6. "Sudovikovite: Sudovikovite mineral information and data". www.mindat.org. Retrieved 19 March 2017.
  7. O’Brien, Maria; McEvoy, Niall; Motta, Carlo; Zheng, Jian-Yao; Berner, Nina C; Kotakoski, Jani; Elibol, Kenan; Pennycook, Timothy J; Meyer, Jannik C; Yim, Chanyoung; Abid, Mohamed; Hallam, Toby; Donegan, John F; Sanvito, Stefano; Duesberg, Georg S (13 April 2016). "Raman characterization of platinum diselenide thin films". 2D Materials. 3 (2): 021004. arXiv:1512.09317. Bibcode:2016TDM.....3b1004O. doi:10.1088/2053-1583/3/2/021004. S2CID 119271642.
  8. Ciarrocchi, Alberto; Avsar, Ahmet; Ovchinnikov, Dmitry; Kis, Andras (2018-03-02). "Thickness-modulated metal-to-semiconductor transformation in a transition metal dichalcogenide". Nature Communications. 9 (1): 919. doi:10.1038/s41467-018-03436-0. ISSN 2041-1723. PMC 5834615. PMID 29500434.
  9. Zhao, Yuda; Qiao, Jingsi; Yu, Zhihao; Yu, Peng; Xu, Kang; Lau, Shu Ping; Zhou, Wu; Liu, Zheng; Wang, Xinran; Ji, Wei; Chai, Yang (February 2017). "High-Electron-Mobility and Air-Stable 2D Layered PtSe2 FETs". Advanced Materials. 29 (5): 1604230. doi:10.1002/adma.201604230. hdl:10397/65694. PMID 27886410.
  10. Hulliger, F. (March 1965). "Electrical properties of some nickel-group chalcogenides". Journal of Physics and Chemistry of Solids. 26 (3): 639–645. Bibcode:1965JPCS...26..639H. doi:10.1016/0022-3697(65)90140-X.
  11. Zulfiqar, Muhammad; Zhao, Yinchang; Li, Geng; Nazir, Safdar; Ni, Jun (3 November 2016). "Tunable Conductivity and Half Metallic Ferromagnetism in Monolayer Platinum Diselenide: A First-Principles Study". The Journal of Physical Chemistry C. 120 (43): 25030–25036. doi:10.1021/acs.jpcc.6b06999.
  12. Avsar, Ahmet; Ciarrocchi, Alberto; Pizzochero, Michele; Unuchek, Dmitrii; Yazyev, Oleg V.; Kis, Andras (July 2019). "Defect induced, layer-modulated magnetism in ultrathin metallic PtSe2". Nature Nanotechnology. 14 (7): 674–678. doi:10.1038/s41565-019-0467-1. ISSN 1748-3387. PMC 6774792. PMID 31209281.
  13. Yao, Wei; Wang, Eryin; Huang, Huaqing; Deng, Ke; Yan, Mingzhe; Zhang, Kenan; Miyamoto, Koji; Okuda, Taichi; Li, Linfei; Wang, Yeliang; Gao, Hongjun; Liu, Chaoxing; Duan, Wenhui; Zhou, Shuyun (31 January 2017). "Direct observation of spin-layer locking by local Rashba effect in monolayer semiconducting PtSe2 film". Nature Communications. 8: 14216. Bibcode:2017NatCo...814216Y. doi:10.1038/ncomms14216. PMC 5290424. PMID 28139646.
  14. Dey, Sandip; Jain, Vimal K. (2004). "Platinum group metal chalcogenides" (PDF). Platinum Metals Review. 48 (1): 16–29.
  15. Oh, George N.; Choi, Eun Sang; Ibers, James A. (2 April 2012). "Syntheses and Characterization of Nine Quaternary Uranium Chalcogenides Among the Compounds A2 M3 UQ6(A = K, Rb, Cs; M = Pd, Pt; Q = S, Se)". Inorganic Chemistry. 51 (7): 4224–4230. doi:10.1021/ic2027048. PMID 22424143. S2CID 29859041.
  16. Drabek, M.; Vymazalova, A.; Cabral, A. R. (10 July 2012). "THE SYSTEM Hg-Pt-Se AT 400 C: PHASE RELATIONS INVOLVING JACUTINGAITE". The Canadian Mineralogist. 50 (2): 441–446. doi:10.3749/canmin.50.2.441.
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