Physics:Corundum (structure)

From HandWiki

Corundum is the name for a structure prototype in inorganic solids, derived from the namesake polymorph of aluminum oxide (α-Al2O3).[1] Other compounds, especially among the inorganic solids, exist in corundum structure, either in ambient or other conditions. Corundum structures are associated with metal-insulator transition,[2] ferroelectricity,[3] polar magnetism,[4][5] and magnetoelectric effects.


The corundum structure has the space group R3c. It typically exists in binary compounds of the type A2B3, where A is metallic and B is nonmetallic, including sesquioxides (A2O3),[6] sesquisulfides (A2S3),[7] etc. When A is nonmetallic and B is metallic, the structure becomes the antiphase of corundum, called the anticorundum structure type,[8] with examples including β-Ca3N2[9] and borates. Ternary and multinary compounds can also exists in the corundum structure. The corundum-like structure with the composition A2BB'O6 is called double corundum.[4] A list of examples are tabulated below.

Crystal structure of corrundum. The unit cell contains 16 formulas R2W3 (R=red, W=white). Each red atom is surrounded by six white atoms, and each white by four red.
Materials that exist in the corundum structure
Chemical formula Alternative name Material type Reference
Al2O3 α-Al2O3 or corundum Oxide [1]
V2O3 Oxide [2][10]
Cr2O3 α-Cr2O3 Oxide [10]
Fe2O3 α-Fe2O3 or hematite Oxide [10]
Ga2O3 α-Ga2O3 Oxide [11]
In2O3 rh-In2O3 Oxide [12][13]
Ti2O3 α-Ti2O3 Oxide [14]
Mn2O3 ε-Mn2O3 Oxide [15]
Rh2O3 Oxide [16]
Ir2O3 α-Ir2O3 Oxide [17]
Tl2O3 Oxide [18]
Ca3N2 β-Ca3N2 Nitride [9]
In2S3 ε-In2S3 Sulfide [19]
Tm2S3 E-Tm2S3 or ε-Tm2S3 Sulfide [20]
Yb2S3 E-Yb2S3 or ε-Yb2S3 Sulfide [21]
Lu2S3 E-Lu2S3 or ε-Lu2S3 Sulfide [22]
Ca3(BO3)2 Borate [23]
Sr3(BO3)2 Borate [24]
Eu3(BO3)2 Borate [25]
ScFeO3 Ferrite [26]
GaFeO3 Ferrite [27]
InFeO3 Ferrite [28]
CrTiO3 Titanate [29]
NiCrO3 Chromite [30]
InVO3 Vanadate [31]
Ni3TeO6 Double oxide [32]
Ni2InSbO6 Double oxide [33]
Ni2ScSbO6 Double oxide [33]
Mn2FeMoO6 Double oxide [34]
Mn2FeWO6 Double oxide [35]
Co4Ta2O9 Triple oxide [36][37]

See also


  1. 1.0 1.1 Pauling, Linus; Hendricks, Sterling B. (1925-03-05). "The crystal structures of hematite and corundum" (in en). Journal of the American Chemical Society 47 (3): 781–790. doi:10.1021/ja01680a027. ISSN 0002-7863. 
  2. 2.0 2.1 Tanaka, Arata (2002). "Electronic Structure and Phase Transition in V2O3 : Importance of 3 d Spin-Orbit Interaction and Lattice Distortion" (in en). Journal of the Physical Society of Japan 71 (4): 1091–1107. doi:10.1143/JPSJ.71.1091. ISSN 0031-9015. Bibcode2002JPSJ...71.1091T. 
  3. Ye, Meng; Vanderbilt, David (2016-04-04). "Ferroelectricity in corundum derivatives" (in en). Physical Review B 93 (13): 134303. doi:10.1103/PhysRevB.93.134303. ISSN 2469-9950. Bibcode2016PhRvB..93m4303Y. 
  4. 4.0 4.1 Cai, Guo-Hong; Greenblatt, Martha; Li, Man-Rong (2017-07-11). "Polar Magnets in Double Corundum Oxides" (in en). Chemistry of Materials 29 (13): 5447–5457. doi:10.1021/acs.chemmater.7b01567. ISSN 0897-4756. 
  5. P N, Ravi Shankar; Mishra, Swarnamayee; Athinarayanan, Sundaresan (2020-04-01). "Polar magnetic oxides from chemical ordering: A new class of multiferroics" (in en). APL Materials 8 (4): 040906. doi:10.1063/5.0003305. ISSN 2166-532X. Bibcode2020APLM....8d0906P. 
  6. Manjón, Francisco; Sans, Juan; Ibáñez, Jordi; Pereira, André (2019-11-28). "Pressure-Induced Phase Transitions in Sesquioxides" (in en). Crystals 9 (12): 630. doi:10.3390/cryst9120630. ISSN 2073-4352. 
  7. Sleight, Arthur W.; Prewitt, Charles T. (1968). "Crystal chemistry of the rare earth sesquisulfides" (in en). Inorganic Chemistry 7 (11): 2282–2288. doi:10.1021/ic50069a022. ISSN 0020-1669. 
  8. Vegas, Angel (2000). "Cations in Inorganic Solids" (in en). Crystallography Reviews 7 (3): 189–283. doi:10.1080/08893110008044245. ISSN 0889-311X. 
  9. 9.0 9.1 Höhn, Peter; Hoffmann, Stefan; Hunger, Jens; Leoni, Stefano; Nitsche, Fabian; Schnelle, Walter; Kniep, Rüdiger (2009-03-23). "β-Ca 3 N 2 , a Metastable Nitride in the System Ca-N" (in en). Chemistry - A European Journal 15 (14): 3419–3425. doi:10.1002/chem.200801857. PMID 19212988. 
  10. 10.0 10.1 10.2 Sato, Yosiko; Akimoto, Syun-iti (1979). "Hydrostatic compression of four corundum-type compounds: α-Al2O3, V2O3, Cr2O3, and α-Fe2O3" (in en). Journal of Applied Physics 50 (8): 5285. doi:10.1063/1.326625. Bibcode1979JAP....50.5285S. 
  11. Sinha, G.; Adhikary, K.; Chaudhuri, S. (2005). "Sol–gel derived phase pure α-Ga2O3 nanocrystalline thin film and its optical properties" (in en). Journal of Crystal Growth 276 (1–2): 204–207. doi:10.1016/j.jcrysgro.2004.11.375. Bibcode2005JCrGr.276..204S. 
  12. Gurlo, Aleksander; Kroll, Peter; Riedel, Ralf (2008-04-07). "Metastability of Corundum-Type In2O3" (in en). Chemistry - A European Journal 14 (11): 3306–3310. doi:10.1002/chem.200701830. PMID 18270987. 
  13. García-Domene, B.; Sans, J. A.; Manjón, F. J.; Ovsyannikov, Sergey V.; Dubrovinsky, L. S.; Martinez-Garcia, D.; Gomis, O.; Errandonea, D. et al. (2015-12-31). "Synthesis and High-Pressure Study of Corundum-Type In2O3" (in en). The Journal of Physical Chemistry C 119 (52): 29076–29087. doi:10.1021/acs.jpcc.5b06939. ISSN 1932-7447. 
  14. Rice, C. E.; Robinson, W. R. (1977-05-15). "High-temperature crystal chemistry of Ti2O3: structural changes accompanying the semiconductor–metal transition". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry 33 (5): 1342–1348. doi:10.1107/S0567740877006062. 
  15. Ovsyannikov, Sergey V.; Abakumov, Artem M.; Tsirlin, Alexander A.; Schnelle, Walter; Egoavil, Ricardo; Verbeeck, Jo; Van Tendeloo, Gustaaf; Glazyrin, Konstantin V. et al. (2013-01-28). "Perovskite-like Mn 2 O 3 : A Path to New Manganites" (in en). Angewandte Chemie International Edition 52 (5): 1494–1498. doi:10.1002/anie.201208553. PMID 23280731. 
  16. Coey, J. M. D. (1970-11-01). "The crystal structure of Rh 2 O 3". Acta Crystallographica Section B: Structural Crystallography and Crystal Chemistry 26 (11): 1876–1877. doi:10.1107/S0567740870005022. ISSN 0567-7408. 
  17. Kan, Shin-ichi; Takemoto, Shu; Kaneko, Kentaro; Takahashi, Isao; Sugimoto, Masahiro; Shinohe, Takashi; Fujita, Shizuo (2018-11-19). "Electrical properties of α-Ir2O3 /α-Ga2O3 pn heterojunction diode and band alignment of the heterostructure" (in en). Applied Physics Letters 113 (21): 212104. doi:10.1063/1.5054054. ISSN 0003-6951. Bibcode2018ApPhL.113u2104K. 
  18. Gomis, O.; Santamaría-Pérez, D.; Ruiz-Fuertes, J.; Sans, J. A.; Vilaplana, R.; Ortiz, H. M.; García-Domene, B.; Manjón, F. J. et al. (2014-10-07). "High-pressure structural and elastic properties of Tl2O3" (in en). Journal of Applied Physics 116 (13): 133521. doi:10.1063/1.4897241. ISSN 0021-8979. Bibcode2014JAP...116m3521G. 
  19. Range, Klaus-Jürgen; Zabel, Manfred (1978-04-01). "ε-In 2 S 3 , eine Hochdruckmodifikation mit Korundstruktur / ε-In 2 S 3 , a High Pressure Modification with Corundum Type Structure" (in en). Zeitschrift für Naturforschung B 33 (4): 463–464. doi:10.1515/znb-1978-0423. ISSN 1865-7117. 
  20. Range, K. J.; Drexler, H.; Gietl, A.; Klement, U.; Lange, K. G. (1990-03-15). "Tm2S3–V, a corundum-type modification of thulium sesquisulfide". Acta Crystallographica Section C: Crystal Structure Communications 46 (3): 487–488. doi:10.1107/S0108270189012035. 
  21. Schleid, Thomas; Lissner, Falk (1996-05-01). "A-Pr 2 S 3 , D-Ho 2 S 3 und E-Yb 2 S 3 :Synthese und Einkristallstrukturuntersuchungen / A-Pr 2 S 3 , D-Ho 2 S 3 and E-Yb 2 S 3 :Synthesis and Single Crystal Structure Investigations" (in en). Zeitschrift für Naturforschung B 51 (5): 733–738. doi:10.1515/znb-1996-0519. ISSN 1865-7117. 
  22. Range, Klaus-Jürgen; Leeb, Richard (1975-08-01). "Die Kristallstruktur von Lu2S3 / The Crystal Structure of Lu2S3" (in en). Zeitschrift für Naturforschung B 30 (7–8): 637–638. doi:10.1515/znb-1975-7-835. ISSN 1865-7117. 
  23. Vegas, A. (1985-11-15). "New description of the Ca3(BO3)2 structure". Acta Crystallographica Section C: Crystal Structure Communications 41 (11): 1689–1690. doi:10.1107/S0108270185009052. 
  24. Richter, L.; Müller, Franz (1980). "Zur Struktur von Sr3B2O6" (in de). Zeitschrift für anorganische und allgemeine Chemie 467 (1): 123–125. doi:10.1002/zaac.19804670114. ISSN 0044-2313. 
  25. Machida, Ken-ichi; Adachi, Gin-ya; Hata, Hajime; Shiokawa, Jiro (1981). "The Crystal Structure and Magnetic Property of Europium(II) Orthoborate" (in en). Bulletin of the Chemical Society of Japan 54 (4): 1052–1055. doi:10.1246/bcsj.54.1052. ISSN 0009-2673. 
  26. Li, Man-Rong; Adem, Umut; McMitchell, Sean R. C.; Xu, Zhongling; Thomas, Chris I.; Warren, John E.; Giap, Duong V.; Niu, Hongjun et al. (2012-02-29). "A Polar Corundum Oxide Displaying Weak Ferromagnetism at Room Temperature" (in en). Journal of the American Chemical Society 134 (8): 3737–3747. doi:10.1021/ja208395z. ISSN 0002-7863. PMID 22280499. 
  27. Niu, Hongjun; Pitcher, Michael J.; Corkett, Alex J.; Ling, Sanliang; Mandal, Pranab; Zanella, Marco; Dawson, Karl; Stamenov, Plamen et al. (2017-02-01). "Room Temperature Magnetically Ordered Polar Corundum GaFeO 3 Displaying Magnetoelectric Coupling" (in en). Journal of the American Chemical Society 139 (4): 1520–1531. doi:10.1021/jacs.6b11128. ISSN 0002-7863. PMID 28013545. 
  28. Prewitt, Charles T.; Shannon, Robert D.; Rogers, Donald Burl; Sleight, Arthur W. (1969). "C rare earth oxide-corundum transition and crystal chemistry of oxides having the corundum structure" (in en). Inorganic Chemistry 8 (9): 1985–1993. doi:10.1021/ic50079a033. ISSN 0020-1669. 
  29. Reid, A.F.; Sabine, T.M.; Wheeler, D.A. (1972). "Neutron diffraction and other studies of magnetic ordering in phases based on Cr2O3, V2O3 and Ti2O3" (in en). Journal of Solid State Chemistry 4 (3): 400–409. doi:10.1016/0022-4596(72)90155-7. Bibcode1972JSSCh...4..400R. 
  30. Chamberland, B. L.; Cloud, W. H. (1969). "Preparation and Properties of NiCrO 3" (in en). Journal of Applied Physics 40 (1): 434–435. doi:10.1063/1.1657087. ISSN 0021-8979. Bibcode1969JAP....40..434C. 
  31. Tan, Zhenhong; Lussier, Joey A.; Yamada, Takumi; Xu, Yuanhui; Saito, Takashi; Goto, Masato; Kosugi, Yoshihisa; Vrublevskiy, Dmitry et al. (2022-06-20). "LiNbO3‐Type Polar Antiferromagnet InVO3 Synthesized under High‐Pressure Conditions" (in en). Angewandte Chemie International Edition 61 (25): e202203669. doi:10.1002/anie.202203669. ISSN 1433-7851. PMID 35384197. 
  32. Newnham, R.E.; Meagher, E.P. (1967). "Crystal structure of Ni3TeO6" (in en). Materials Research Bulletin 2 (5): 549–554. doi:10.1016/0025-5408(67)90031-1. 
  33. 33.0 33.1 Ivanov, S. A.; Mathieu, R.; Nordblad, P.; Tellgren, R.; Ritter, C.; Politova, E.; Kaleva, G.; Mosunov, A. et al. (2013-03-26). "Spin and Dipole Ordering in Ni 2 InSbO 6 and Ni 2 ScSbO 6 with Corundum-Related Structure" (in en). Chemistry of Materials 25 (6): 935–945. doi:10.1021/cm304095s. ISSN 0897-4756. 
  34. Li, Man-Rong; Retuerto, Maria; Walker, David; Sarkar, Tapati; Stephens, Peter W.; Mukherjee, Swarnakamal; Dasgupta, Tanusri Saha; Hodges, Jason P. et al. (2014-09-26). "Magnetic-Structure-Stabilized Polarization in an Above-Room-Temperature Ferrimagnet" (in en). Angewandte Chemie International Edition 53 (40): 10774–10778. doi:10.1002/anie.201406180. PMID 25131837. 
  35. Li, Man-Rong; Croft, Mark; Stephens, Peter W.; Ye, Meng; Vanderbilt, David; Retuerto, Maria; Deng, Zheng; Grams, Christoph P. et al. (2015-02-11). "Mn2FeWO6 : A New Ni3TeO6-Type Polar and Magnetic Oxide" (in en). Advanced Materials 27 (13): 2177–2181. doi:10.1002/adma.201405244. PMID 25677612. 
  36. Bertaut, E.F.; Corliss, L.; Forrat, F.; Aleonard, R.; Pauthenet, R. (1961). "Etude de niobates et tantalates de metaux de transition bivalents" (in fr). Journal of Physics and Chemistry of Solids 21 (3–4): 234–251. doi:10.1016/0022-3697(61)90103-2. Bibcode1961JPCS...21..234B. 
  37. Chaudhary, S.; Srivastava, P.; Kaushik, S.D.; Siruguri, V.; Patnaik, S. (2019-04-01). "Nature of magnetoelectric coupling in corundum antiferromagnet Co4Ta2O9" (in en). Journal of Magnetism and Magnetic Materials 475: 508–513. doi:10.1016/j.jmmm.2018.09.071. Bibcode2019JMMM..475..508C.