AMPC  Vol.5 No.3 , March 2015
Physical Properties of Some Stoichiometric Rare Earth Nitride Single Crystals
Author(s) Peter Wachter
ABSTRACT
The preparation and definition of large (3 - 5 mm edge length) single crystals of ScN, GdN, TbN, HoN, YbN and CeN is described. The Hall effect and the electrical conductivity are found to be metallic. The optical reflectivity between 30 meV (sometimes 1 meV) and 13 eV has been measured and the dielectric functions have been obtained. A plasma edge in the infrared confirms the metallic character. In GdN, a shift of this plasma edge with temperature through the magnetic ordering temperature has been observed as a new effect. GdN is in low magnetic fields antiferromagnetic, but becomes ferromagnetic in larger fields. The band structure is discussed. The magnetic exchange interactions have been derived. HoN in the relevant crystal directions has a spontaneous magnetic moment, but no saturation in fields up to 10 T. CeN is intermediate valent and exhibits a Pauli paramagnetism. The specific heat is measured down to 0.3 K and an enhanced γ value is observed.

Cite this paper
Wachter, P. (2015) Physical Properties of Some Stoichiometric Rare Earth Nitride Single Crystals. Advances in Materials Physics and Chemistry, 5, 96-131. doi: 10.4236/ampc.2015.53013.
References
[1]   Matthias, B.T., Bozorth, R.M. and van Vleck, J.H. (1961) Ferromagnetic Interaction in EuO. Physical Review Letters, 7, 160-161.
http://dx.doi.org/10.1103/PhysRevLett.7.160

[2]   Hulliger, F. (1979) Rare Earth Pnictides. In: Gschneidner Jr., K.A. and Eyring, L., Eds., Handbook on the Physics and Chemistry of Rare Earths, Vol. 4, Ch. 33, North-Holland Publishing, Amsterdam, 153-236.

[3]   Vogt, O. and Mattenberger, K. (1993) Magnetic Measurements on Rare Earth and Actinide Monopnictides and Mono-chalcogenides. In: Gschneidner Jr., K.A., Eyring, L., Lander, G.H. and Choppin, G.R., Eds., Handbook on the Physics and Chemistry of Rare Earths, Physics-I, Vol. 17, Ch. 1, Lanthanides/Actinides, North-Holland Publishing, Amsterdam, 14-407.

[4]   Vogt, O. and Mattenberger, K. (1995) The Magnetism of Localized or Nearly Localized 4f and 5f Shells. Journal of Alloys and Compounds, 223, 226-236.
http://dx.doi.org/10.1016/0925-8388(94)09005-X

[5]   Hirayama, Y., Nakagawa, T. and Yamamoto, T.A. (2011) Curie Temperatures and Modified de Gennes Factors of Rare Earth Nitrides. Solid State Communications, 151, 1602-1604.
http://dx.doi.org/10.1016/j.ssc.2011.07.021

[6]   Child, H.R., Wilkinson, M.K., Cable, J.W., Koehler, W.C. and Wollan, E.O. (1963) Neutron Diffraction Investigation of the Magnetic Properties of Compounds of Rare Earth Metals with Group V Anions. Physical Review, 131, 922-931.
http://dx.doi.org/10.1103/PhysRev.131.922

[7]   Sclar, N. (1964) Properties of Rare Earth Nitrides. Journal of Applied Physics, 35, 1534-1538.
http://dx.doi.org/10.1063/1.1713662

[8]   Busch, G., Junod, P., Vogt, O. and Hulliger, F. (1963) Ferro- and Metamagnetism of Rare Earth Compounds. Physics Letters, 6, 79-80.

[9]   Busch, G., Kaldis, E., Schaufelberger-Teker, E. and Wachter, P. (1970) Synthesis, Crystal Growth and Physical Properties of Rare Earth Nitride Phases. Colloques Internationaux du CNRS, 1, 359-373.

[10]   Kaldis, E. (1974) Principles of the Vapour Growth of Single Crystals. In: Goldman, C.H.L., Ed., Crystal Growth: Theory and Techniques, Vol. 1, Plenum Press, New York, 49-192.

[11]   Kaldis, E. and Zürcher, Ch. (1976) Solid State Chemistry and Physics of the Monopnictides and Monochalcogenides of some Trivalent Rare Earths. In: Lundin, C.E., Ed., Proceedings of the 12th Rare Earth Research Conference, Denver Research Inst., Denver, 915-934.

[12]   Cho, S.J. (1967) Spin Polarized Electronic Energy-Band Structure in EuS. Physical Review, 157, 632-640.
http://dx.doi.org/10.1103/PhysRev.157.632

[13]   Busch, G., Junod, P. and Wachter, P. (1964) Optical Absorption of Ferro- and Antiferromagnetic Europium Chalcogenides. Physics Letters, 12, 11-12.
http://dx.doi.org/10.1016/0031-9163(64)91155-2

[14]   Busch, G. and Wachter, P. (1966) Einfluß der magnetischen Ordnung auf die optische Absorption von ferro-oder antiferromagnetischen Halbleitern. Physik der kondensierten Materie, 5, 232-242.

[15]   Urban, P., Davidov, D., Elschner, B., Piefka, T. and Sperlich, G. (1975) Narrowing Effects in the ESR Spectra of Gd in Metals: Application to LaSb:Gd. Physical Review B, 12, 72.
http://dx.doi.org/10.1103/PhysRevB.12.72

[16]   Petit, L., Tyer, R., Szotek, Z., Temmerman, W.M. and Svane, A. (2010) Rare Earth Monopnictides and Monochalcogenides from First Principles: Towards an Electronic Phase Diagram of Strongly Correlated Materials. New Journal of Physics, 12, 113041-113061.
http://dx.doi.org/10.1088/1367-2630/12/11/113041

[17]   Neckel, A., Rastl, P., Eibler, R., Weinberger, P. and Schwarz, K. (1976) Results of Self-Consisted Band-Structure Calculations for ScN, ScO, TiC, TiN, VC, VN and VO. Journal of Physics C, 9, 579-592.

[18]   Monnier, R., Rhyner, J., Rice, T.M. and Koelling, D.D. (1985) Electron-Hole Liquid as a True Ground State. Physical Review B, 31, 5554-5556.
http://dx.doi.org/10.1103/PhysRevB.31.5554

[19]   Harbeke, G., Meier, E. and Dismukes, J.P. (1972) Electron Effective Mass in ScN. Optics Communications, 4, 335-338.
http://dx.doi.org/10.1016/0030-4018(72)90071-5

[20]   Travaglini, G., Marabelli, F., Monnier, R., Kaldis, E. and Wachter, P. (1968) Electronic Structure of ScN. Physical Review B, 34, 3876-3882.
http://dx.doi.org/10.1103/PhysRevB.34.3876

[21]   Dismukes, J.P., Yim, W.M. and Ban, V.S. (1971) Optical Properties of ScN. Proceedings of 3rd International Conference on Crystal Growth, Marseille, 536-538.

[22]   Wachter, P. (1972) The Optical Electrical and Magnetic Properties of the Europium Chalcogenides and the Rare Earth Pnictides. CRC Critical Reviews in Solid State Sciences, 3, 189-241.

[23]   Busch, G., Junod, P., Vogt, O. and Hulliger, F. (1963) Ferro- and Metamagnetism of Rare Earth Compounds. Physics Letters, 6, 79-80.
http://dx.doi.org/10.1016/0031-9163(63)90228-2

[24]   Busch, G., Vogt, O. and Schwob, P. (1967) Les Champs Magnétiques Intenses. CNRS (Colloques International du Centre National de Research Scientifique) No. 166, 401-407.

[25]   Junod, P., Menth, A. and Vogt, O. (1969) Revue des Propriétés Magnétiques et électroniques des Composés des Terres Rares avec les Anions du 5ième Groupe du Système Périodique. Physik der kondensierten Materie, 8, 323-370.

[26]   McGuire, T.R., Gambino, S.J., Pickart, S.J. and Alperin, H.A. (1969) Magnetic Structure and Exchange Interac-tions in Cubic Gadolinium Compounds. Journal of Applied Physics, 40, 1009-1010.
http://dx.doi.org/10.1063/1.1657506

[27]   Gambino, R.J., McGuire, T.R., Alperin, H.A. and Pickart, S.J. (1970) Exchange Interaction in GdN. Journal of Applied Physics, 41, 933-934.

[28]   Li, D.X., Haga, Y., Shida, H. and Suzuki, T. (1994) Magnetic Properties of Ferromagnetic GdN. Physica B, 199-200, 631-633.
http://dx.doi.org/10.1016/0921-4526(94)91928-3

[29]   Wachter, P. and Kaldis, E., Solid State Commun. (1980) Magnetic Interaction and Carrier Concentration in GdN and GdN1-xOx. Solid State Communications, 34, 241-244.
http://dx.doi.org/10.1016/0038-1098(80)90401-9

[30]   Wachter, P. and Kaldis, E. (1980) Magnetic Interaction in GdN and GdN1-xOx. Journal of Magnetism and Magnetic Materials, 15-18, 305-306.
http://dx.doi.org/10.1016/0304-8853(80)91062-8

[31]   Wachter, P. (2012) Physical Properties of Stoichiometric GdN Single Crystals. Results in Physics, 2, 90-96.
http://dx.doi.org/10.1016/j.rinp.2012.07.003

[32]   Leuenberger, F., Parge, A., Felsch, W., Fauth, K. and Hessler, M. (2005) GdN Thin Films: Bulk and Local Electronic and Magnetic Properties. Physical Review B, 72, Article ID: 014427.
http://dx.doi.org/10.1103/PhysRevB.72.014427

[33]   Hasegawa, A. and Yanase, A. (1977) Energy Band Structure of Gd Pnictides. Journal of the Physical Society of Japan, 42, 492-498.
http://dx.doi.org/10.1143/JPSJ.42.492

[34]   Wachter, P. (1978) Electronic Structure, Magnetic Exchange and Electrical Transport Properties of the Magnetic Compounds EuS, GdS and GdP. Physics Reports, 44, 159-186.
http://dx.doi.org/10.1016/0370-1573(78)90001-7

[35]   Campagna, M., Wertheim, G.K. and Baer, Y. (1979) Unfilled Inner Shells: Rare Earths and Their Compounds. In: Ley, L. and Cardona, M., Eds., Topics in Applied Physics, Vol. 27, Photoemission in Solids II, Case Studies, Springer Verlag, Berlin, 217-260.

[36]   Kasuya, T. and Yanase, A. (1968) Anomalous Transport Phenomena in Eu Chalcogenide Alloys. Reviews of Modern Physics, 40, 684-695.
http://dx.doi.org/10.1103/RevModPhys.40.684

[37]   Li, D.X., Haga, Y., Shida, H., Suzuki, T. and Kwon, Y.S. (1996) Electrical Transport Properties of Semimetallic GdX Single Crystals (X=P, As, Sb and Bi). Physical Review B, 54, 10483-10491.
http://dx.doi.org/10.1103/PhysRevB.54.10483

[38]   Berton, A., Chaussy, J. and Veyssie, J.J. (1966) Ann. Acad. Sci. Fennicae A. VI., 210, 233.

[39]   Stutius, W. (1969) Spezifische Warme der Nitride Seltener Erden. Physik der Kondensierten Materie, 10, 152-185.

[40]   Schlegel, A. (1979) Optical Properties and Electronic Structure of Some Rare Earth Monopnictides. Thesis, ETH Zürich, Zürich.

[41]   Wachter, P. (1964) Messung der optischen Absorption an Ferround Antiferromagnetischen Verbindungen Seltener Erden. Helvetica Physica Acta, 37, 637.

[42]   The Author Is Very Grateful to Dr. N. Zhigadlo, Lab. für Festkorperphysik, ETH Zürich, Switzerland, for This Measurement.

[43]   Goodenough, J.B. (1963) Magnetism and the Chemical Bond. Interscience Monographs on Chemistry, Vol. I, John Wiley, New York 1-385.

[44]   Wachter, P., Kaldis, E. and Hauger, R. (1978) Magnetic Exchange Interaction in the System GdP-GdS. Physical Review Letters, 40, 1404-1407.
http://dx.doi.org/10.1103/PhysRevLett.40.1404

[45]   Bommeli, F., Degiorgi, L. and Wachter, P. (1995) Optical Properties of TbN. Journal of Magnetism and Magnetic Materials, 140-144, 1159-1160.
http://dx.doi.org/10.1016/0304-8853(94)00753-5

[46]   Kaldis, E., Schlegel, A., Wachter, P. and Zürcher, Ch. (1976) Electronic Structure of Divalent-, Trivalent- and Mixed Valent Rare Earth Compounds. Journal of Magnetism and Magnetic Materials, 3, 1-3.

[47]   Klaase, J.C.P. (1998) Private Communication. Natuurkundig Laboratorium, University of Amsterdam, Amsterdam.

[48]   Degiorgi, L., Teraoka, S., Compagnini, G. and Wachter, P. (1993) Optical and Raman Investigation of Yb Pnictide Compounds. Physical Review B, 47, 5715-5720.
http://dx.doi.org/10.1103/PhysRevB.47.5715

[49]   Degiorgi, L., Bacsa, W. and Wachter, P. (1990) Electronic Structure of YbN. Physical Review B, 42, 530-539.
http://dx.doi.org/10.1103/PhysRevB.42.530

[50]   Wouilloud, E. (1986) Thesis, University of Neuchatel, Neuchatel.

[51]   Mendik, M. and Wachter, P. (1993) Brillouin Scattering from Single Crystals YbX (X = N,P,As). Physical Review B, 47, 6110-6113.
http://dx.doi.org/10.1103/PhysRevB.47.6110

[52]   Ott, H.R., Rudigier, H. and Hulliger, F. (1985) Low-Temperature Phase Transitions in Yb Monopnictides. Solid State Communications, 55, 113-116.
http://dx.doi.org/10.1016/0038-1098(85)90259-5

[53]   Wachter, P. (1994) Intermediate Valence and Heavy Fermions. In: Gschneidner Jr., K.A., Eyring, L., Lander, G.H. and Choppin, G.R., Eds., Handbook on the Physics and Chemistry of Rare Earths, Vol. 19, Lanthanides and Actinides: Physics—II, Ch. 132, North-Holland Publishing, Amsterdam, 177-382.

[54]   Takagi, S., Oyamada, A. and Kasuya, T.J. (1988) 31P NMR Studies of the Magnetically Ordered Heavy Electron Compound YbP. Journal of the Physical Society of Japan, 57, 1456-1465.

[55]   Didchenko, R. and Gortsema, F.P. (1963) Some Electric and Magnetic Properties of Rare Earth Monosulfides and Nitrides. Journal of Physics and Chemistry of Solids, 24, 863-870.
http://dx.doi.org/10.1016/0022-3697(63)90062-3

[56]   Danan, J., de Novion, C. and Lallement, R. (1969) Proprietes Magnetiques Du Nitrure De Cerium: Centre d’Etudes Nucléaires de Fontenayaux-Roses, S.E.C.P.E.R., Section d’Etudes des Céramiques à base de Plutonium. Solid State Communications, 7, 1103-1107.
http://dx.doi.org/10.1016/0038-1098(69)90494-3

[57]   Kaldis, E., Steinmann, B., Fritzler, B., Jilek, E. and Wisard, A. (1982) CeN: Phase Relationships and Enthalpies of Solution. In: McCarthy, G., Silber, H., Rhyne, J. and Kalina, F.M., Eds., The Rare Earths in Modern Science and Technology, Vol. 3, Plenum Publishing Corp., New York, 227-236.

[58]   Baer, Y. and Zürcher, Ch. (1977) Electronic Structure of CeN Studied by X-Ray—Photoemission Spectroscopy. Physical Review Letters, 39, 956-959.
http://dx.doi.org/10.1103/PhysRevLett.39.956

[59]   Wuilloud, E., Delley, B., Schneider, W.D. and Baer, Y. (1985) Spectroscopic Study of Localized and Extended F-Symmetry States in CeO2, CeN and CeSi2. Journal of Magnetism and Magnetic Materials, 47-48, 197-199.

[60]   Patthey, F., Imer, J.M., Schneider, W.D., Beck, H., Baer, Y. and Delley, B. (1990) High Resolution Photoemission Study of the Low-Energy Excitations in 4f-Electron Systems. Physical Review B, 42, 8864-8881.
http://dx.doi.org/10.1103/PhysRevB.42.8864

[61]   Mattenberger, K. and Vogt, O. (1992) Magnetism of Monochalcogenides and Monopnictides of the Actinides. Physica Scripta T, 1992, 103.
http://dx.doi.org/10.1088/0031-8949/1992/T45/022

[62]   Stewart, G.R. (1984) Heavy Fermion Systems. Reviews of Modern Physics, 56, 755-787.
http://dx.doi.org/10.1103/RevModPhys.56.755

[63]   Delin, A., Oppeneer, P.M., Brooks, M.S.S., Kraft, T., Wills, J.M., Johansson, B. and Erikson, O. (1997) Optical Evidence of 4f-Band Formation in CeN. Physical Review B, 55, R10173-R10176.
http://dx.doi.org/10.1103/PhysRevB.55.R10173

[64]   Larson, P., Lambrecht, W.R.L., Chantis, A. and van Schilfgaarde, M. (2002) Electrical Properties of Rare Earth Nitrides Using the LSDA-U Approach: Importance of Allowing 4f Orbitals to Break the Cubic Crystal System. Physical Review B, 75, 045114-1-045114-14.

[65]   Kanchana, V., Vaitheeswaran, G., Zhang, X., Ma, Y., Svane, A. and Erikson, O. (2011) Lattice Dynamics and Elastic Properties of the 4f Electron System: CeN. Physical Review B, 84, 205135-1-205135-7.
http://dx.doi.org/10.1103/PhysRevB.84.205135

[66]   Landrum, G.A., Dronskowski, R., Niewa, R. and DiSalvo, F. (1999) Electronic Structure and Bonding in Cerium (Nitride) Compounds: Trivalent versus Tetravalent Cerium. Chemistry—A European Journal, 5, 515-522.
http://dx.doi.org/10.1002/(SICI)1521-3765(19990201)5:2<515::AID-CHEM515>3.0.CO;2-Y

[67]   Litsarev, M.S., Di Marco, I., Thunstrom, P. and Erikson, O. (2012) Correlated Electronic Structure and Chemical Bonding of Cerium Pnictides and γ-Ce. Physical Review B, 86, 115116-1-115116-7.
http://dx.doi.org/10.1103/PhysRevB.86.115116

[68]   Marabelli, F., Travaglini, G. and Wachter, P. (1986) Electronic Structure of UPt3 in the Vicinity of the Fermi Energy. Solid State Communications, 59, 381-384.
http://dx.doi.org/10.1016/0038-1098(86)90567-3

[69]   Marabelli, F. and Wachter, P. (1990) Temperature Dependence of the Optical Conductivity of the Heavy-Fermion System CeCu6. Physical Review B, 42, 3307-3311.
http://dx.doi.org/10.1103/PhysRevB.42.3307

[70]   Marabelli, F. and Wachter, P. (1988) Far Infrared Optical Study of the Heavy Fermion CeCu6. Solid State Communications, 67, 931-934.
http://dx.doi.org/10.1016/0038-1098(88)90459-0

[71]   Marabelli, F. and Wachter, P. (1990) Optical Study of U2PTC2: Evidence of Heavy Fermion Behavior. Solid State Communications, 74, 1075-1078.
http://dx.doi.org/10.1016/0038-1098(90)90713-L

[72]   Awasthi, A.M., Degiorgi, L., Grüner, G., Dalichaouch, Y. and Maple, M.B. (1993) Complete Optical Spectrum of CeAl3. Physical Review B, 48, 10692-10700.
http://dx.doi.org/10.1103/PhysRevB.48.10692

[73]   Gunnarson, O. and Schonhammer, K. (1983) Photoemission from Ce Compounds: Exact Model Calculation in the Limit of Large Degeneracy. Physical Review Letters, 50, 604-610.
http://dx.doi.org/10.1103/PhysRevLett.50.604

[74]   Martin, R.M. (1982) Fermi-Surface Sum Rule and Its Consequences for Periodic Kondo and Mixed Valence Systems. Physical Review Letters, 48, 362-365.
http://dx.doi.org/10.1103/PhysRevLett.48.362

[75]   Schlegel, A., Wachter, P., Nickl, J.J. and Lingg, H. (1977) Optical Properties of TiN and ZrN. Journal of Physics C: Solid State Physics, 10, 4889-4895.
http://dx.doi.org/10.1088/0022-3719/10/23/022

[76]   Schlegel, A., Kaldis, E., Wachter, P. and Zürcher, Ch. (1978) Optical Properties and Valence Mixing in CeN. Physics Letters A, 66, 125-128.
http://dx.doi.org/10.1016/0375-9601(78)90015-4

[77]   Wachter, P. and Zhigadlo, N.D. (2013) Physical Properties of Stoichiometric CeN Single Crystals. Results in Physics, 3, 235-240.
http://dx.doi.org/10.1016/j.rinp.2013.09.007

 
 
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