51292-2992009 GeTe-Sb 2 Te 3,, Toshiyuki MATSUNAGA, Noboru YAMADA, Kouichi KIFUNE and Yoshiki KUBOTA: Crystal Structures of Phase-Change Recording Material, GeTe-Sb 2 Te 3 Pseudo-binary Compounds Crystal structures of the phase-change recording material, GeTe-Sb 2 Te 3, pseudo-binary compounds have been investigated over a decade using synchrotron radiation and the large Debye-Scherrer camera installed at SPring-8 s BL02B2 beamline. These compounds can be crystallized into metastable single phase with NaCl-type structure, for instance, by instantaneous laser irradiation; however, they are transformed into stable phases with long period trigonal structures characterized by the chemical formula,gete n Sb 2 Te 3 m n, m; integerafter sufficient heat treatments. These stable phases can be described as structure with cubic closepacking periodicity ABCABC where the stacking rules of the Ge/Sb and Te layers are different from each other. DVD-RAMRewritable DVD Blu-ray disc,., GeTe-Sb 2Te 3, ns,,.,,, 600 700 1 Blu-ray disc.sem image of recording marks on a phase-change optical recording disc., 1..,,, 400 500,.,,,. 1),,,,, ns,,.,, nm,,,., GeTe-Sb 2Te 3.,, 10,,,,,. 2),,,.,,,,, 0.2 0.3 mm X. SPring-8/BL02B2, 29.5 kev 292 51 5 2009
. 287 mm. 50 µm 2, 0.01., CeO 2 a 5.4111 Å,.,, N 2.,, SPring-8/BL47XU., Si111 Si444 7.94 kev., 10-5 Pa, VG R4000. GeTe-Sb 2Te 3 GST, NaCl 3),, c H. 4) NaCl Sb 2Te 3,.,,,. GeTe-Sb 2Te 3,,, GeTe, Sb 2Te 3-67 Ge 1Sb 4Te 7, NaCl.,, GeTe, 100 GeTe,, NaCl, GeTe,, NaCl., Sb 2Te 3,,,. 5),,.,,,, 1 SEM,,.,. 2. HOMOhighest occupied molecular orbital,. GeTe-Sb 2Te 3,, GeTe 51 5 2009 2 Ge 2Sb 2Te 5,.Photoemission spectra of the valence bands obtained for amorphous and crystalline Ge 2Sb 2Te 5 thin films. Sb 2Te 3 2 1 Ge 2Sb 2Te 5,,.,, Ge 2Sb 2Te 5, GeTe-Sb 2Te 3,,,. Ge 2Sb 2Te 5, Fm3 _ m NaCl 6) 4, 7., p Ge4s 2 4p 2, Sb5s 2 5p 3, Te5s 2 5p 4,,,. 3, Te 4a,, Ge, Sb 4b. 4b,,, 20 at.., 1 p 3,, p. 2,, 7),,, 2,,, Te, Sb, Ge s,,, 3 p. 8),,. 293
3 Ge 2Sb 2Te 5. Temperature dependence of the atomic displacement parameters for the metastable Ge 2Sb 2Te 5 phase.,.,, Ge-Te, Sb-Te 9)-12), 4, 7,, Ge-Te, Sb-Te 2,,. 12),,.,, 6, 8-N 13) N,,,,,. 3 2 B., 4a, 4b,,,.,,,,. 14),, B,,, 4b, T 0,,., 4b,,,., X LANSCE NPDF 15) PDFpair distribution function 16),,,. 17) X PDF,. 14) 4, 4a Te,,,, 4b, Ge,, 4 Ge 2Sb 2Te 5 PDF.Structures of the Ge 2Sb 2Te 5 metastable phase obtained by the PDF analysis. Ge Te, Sb Te.Ge Sb,,,., Ge/Sb 20. 5 Ge-Te Sb-Te Gr.Partial pair distribution functions Grfor Ge-Te and Sb-Te in a short r range.., 5,. Ge r., Ge,, 2,, GeTe,. 9),,. Ge-Te, Sb-Te,, 2.63 Å, 2.78 Å 10),,,,,,,,.,, 294 51 5 2009
. 18),.,,,. 2, NaCl, GeTe- Sb 2Te 3,,. Te,, Ge, Sb,, Ge/Sb,,,. GeTe, Ge, 2 Ge 2 Sb, 1,,, Ge 2Sb 2Te 5 NaCl. p,, 1, 3. 6, GeTe 1-xSb 2Te 3 x, 4a Te 100,, 4b g 19),20),. 8) 1g,, x/1 2x,.,, Sb 2Te 3, Sb, Te,.,,., Sb 2Te 3 NaCl,, 33., GeTe, NaCl,, 1 111, 7. 21),,, Fm3 _ m., Ge, Te, 111,., Ge, Te,,,., a, α,, C 3vO h. 22),,., GeTe 500, Sb 2Te 3, x 0.137Ge 8Sb 2Te 11 Ge 6Sb 2Te 9,. 21) 51 5 2009 6 GeTe-Sb 2Te 3 V 1/3 4b g.concentration dependence of the lattice parameterv 1/3 and atomic occupancy for the 4b site of the GeTe-Sb 2Te 3 pseudo-binary metastable phase. 7 NaCl.Crystal structures of low temperature rhombohedral phase having the NaCltype atomic arrangement.6 NaCl. Te, Ge/Sb/., GeTe-Sb 2Te 3,, Ge 2Sb 2Te 5, Ge 1Sb 2Te 4, Ge 1Sb 4Te 7, 3 8. 23), Ge 3Sb 2Te 6, Ge 1Sb 6Te 10, 9. 24),25), Ge, Sb, Te, 3 1., a-b,, N, Shelimova 30), 1,. GeTe C 3v, D 3d,, 22), 295
, 5) GeTe,,. 1,, GeTe Sb 2Te 3.,GeTe nsb 2Te 3 m,, 2n 5m n, m,2n 5m/3 2n 5m 3 0 N 2n 5m P, 0 N 32n 5mR.,,,. GeTe,, 6, Ge/Sb Te c H., Sb, NaCl,, Na Ge 2Sb 2Te 5 10 9. Na 1 GeTe nsb 2Te 3 m.crystal data forgete nsb 2Te 3 m homologous compounds. 8 GeTe-Sb 2Te 3.The existing phase diagram of the GeTe-Sb 2Te 3 pseudo-binary system. nm SG R R P R P R R N aå cå 9 GeTe-Sb 2Te 3.Crystal structures of GeTe-Sb 2Te 3 homologous phasesstable phases.ge, Sb,. Ge/Sb,.,,. 296 51 5 2009
, Te Te, Te. Te Te,. 28), Te-Te, NaCl. Ge 2Sb 2Te 5n 2, m 1, 2n 5m 9, 9 NaCl 9 S9-Te-Sb-Te-Ge- Te-Ge-Te-Sb-Te-.,2n 5m 3 0, 1 NaCl P. Ge/Sb Te, Te,,,,,,. 26), Ge 3Sb 2Te 6n 3, m 1, 2n 5m 11, 11 NaCl S11.,2n 5m 3 2, 3 NaCl,. 24), n m,,., Ge 1Sb 4Te 7n 1, m 2, 2n 5m 12, 12 NaCl,, 7 5, 2 NaCl S7 S5.2n 5m 3 0,, 12,. 28) Ge 1Sb 6Te 10n 1, m 3, 2n 5m 17, 5 7 5 3 NaCl S5 S7 S5, 2n 5m 3 2,,,. 25), n m, 5, 7 NaCl,.,, Te, 100, Te,, Ge Sb,,,., 7 1 NaCl, Ge,,, Sb.,,,,,.,,,, DFTdensity functional theory,. 10, 1,. GeTe,,,, NaCl 51 5 2009 10 GeTe-Sb 2Te 3, 1.Composition dependence of the mean volume per single atom for the metastable and stable GeTe-Sb 2Te 3 structures.., GeTe NaCl 6 2R., NaCl Ge 8Sb 2Te 11, 773 K 15,.,, 21P,, Ge 6Sb 2Te 9 17R. 21) 21P,.,, GeTe,,,.,,., 8, GeTe, Ge 2Sb 2Te 5,, GeTe Sb 2Te 3 3 1 Ge 3Sb 2Te 6,, Shelimova, 9 1,, Ge 9Sb 2Te 12,. 31) GeTe nsb 2Te 3 m,gete nbi 2Te 3 m, 32), Ge Sb 2 nsb 2Te 3 m, 33),34) Bi 2 nbi 2Te 3 m, 32) Bi 2 nbi 2Se 3 m, n, m, 2n 5m,.,, GeTe-Bi 2Te 3 GST GBT, 4 1 5 1 Ge 4Bi 2Te 713R, 35) Ge 5Bi 2Te 815P,.,,,., 3 -A-B-C-,, 36)., 297
c* sub,, 1 q γ c* sub γn, m, 1 γ 3n 3m/2n 5m,,. 1 γ,, 3/2, 18/11, 5/3, 12/7, 7/4, 30/17, 9/5.,, h k 0,,,.,, JANA2000 37) 20), γ. 25),, Bi-Te, 38) Bi-Se 39),,,.,, Sb 2 nsb 2Te 3 m,,.,,, γ,., GeTe-Sb 2Te 3,., NaCl,,,.., GeTe-Sb 2Te 3., NaCl.,,,,.,,,.,, Ge Sn, Sb Bi, Te Se,,,,, NaCl.,.,,,,,,,..,,., 1 PB, 10 15 Byte,,.,,,,,.,.,, 1 TB, 10 12 Byte, A4 2 kb, 1 TB 1, 5.,,,, CO 2.,,.,,,,..,.,. X,, SPring-8. 1,, 38, 5, 357 (2003). 2M. Wuttig and N. Yamada: Nat. Mater. 6, 824 (2007). 3,,, 1979. 4O. G. Karpinsky, L. E. Shelimova, M. A. Kretova and J-P. Fleurial: J. Alloys Compd. 268, 112 (1998). 5N. Yamada, E. Ohno, K. Nishiuchi and N. Akahira: J. Appl. Phys. 69, 2849 (1991). 6N. Yamada and T. Matsunaga: J. Appl. Phys. 88, 7020 (2000). 7J. J. Kim, K. Kobayashi, E. Ikenaga, M. Kobata, S. Ueda, T. Matsunaga, K. Kifune, R. Kojima and N. Yamada: Phys. Rev. B 75, 115124 (2007). 8T. Matsunaga, R. Kojima, N. Yamada, K. Kifune, Y. Kubota, Y. Tabata and M. Takata: Inorg. Chem. 45, 2235 (2006). 9A. V. Kolobov, P. Fons, A. I. Frenkel, A. L. Ankudinov, J. Tominaga and T. Uruga: Nat. Mater. 3, 703 (2004). 10M. A. Paesler, D. A. Baker, G. Lucovsky, A. E. Edwards and P. C. Taylor: J. Phys. Chem. Solids 68, 873 (2007). 11J. Akola and R. O. Jones: Phys. Rev. B 76, 235201 (2007). 12S. Kohara, K. Kato, T. Usuki, K. Suzuya, H. Tanaka, Y. Tanaka, S. Kimura, H. Tanaka, Y. Moritomo, T. Matsunaga, N. Yamada, H. Suematsu and M. Takata: Appl. Phys. Lett. 89, 201910 (2006). 13N. F. Mott: Philos. Mag. 19, 835 (1969) 14T. Matsunaga, N. Yamada, R. Kojima, S. Shamoto, M. Sato, H. Tanida, T. Uruga, S. Kohara, M. Takata, P. Zalden and M. Wuttig: Nat. Mater.under submission 15Th. Proffen, T. Egami, S. J. L. Billinge, A. K. Cheetham, D. Louca and R. B. Parise: Appl. Phys. A: Mater. Sci. Process. 74, S163 (2002). 16T. Egami and S. J. L. Billinge: Underneath the Bragg Peaks 298 51 5 2009
Structural Analysis of Complex MaterialsOxford Pergamon, Elsevier, 2003. 17S. Shamoto, N. Yamada, T. Matsunaga, T. Proffen, J. W. Richardson, J. H. Chung and T. Egami: Appl. Phys. Lett. 86, 081904 (2005). 18T. Matsunaga and N. Yamada: Jpn. J. Appl. Phys. 41, 1674 (2002). 19H. M. Rietveld: J. Appl. Cryst. 2, 65 (1969). 20, X,, 2002. 21T. Matsunaga, H. Morita, R. Kojima, N. Yamada, K. Kifune, Y. Kubota, Y. Tabata, J. -J. Kim, M. Kobata, E. Ikenaga and K. Kobayashi: J. Appl. Phys. 103, 093511 (2008). 22B. K. Vainshtein, V. M. Fridkin and V. L. Indenbom: Structure of CrystalsSpringer-Verlag, Berlin, 1995. 23N. Kh. Abrikosov and G. T. Danilova-Dobryakova: Izv. Akad. Auk. SSSR Neorg. Mater. 1, 204 (1965). 24T. Matsunaga, R. Kojima, N. Yamada, K. Kifune, Y. Kubota and M. Takata: Appl. Phys. Lett. 90, 161919 (2007). 25T. Matsunaga, R. Kojima, N. Yamada, K. Kifune, Y. Kubota and M. Takata: Acta Cryst. Bunder submission 26T. Matsunaga, N. Yamada and Y. Kubota: Acta Cryst. B 60, 685 (2004). 27T. Matsunaga and N. Yamada: Phys. Rev. B 69, 10, 104111 (2004). 28T. Matsunaga, R. Kojima, N. Yamada, K. Kifune, Y. Kubota and M. Takata: Chem. Mater. 20, 5750 (2008). 29R. W. G. Wyckoff: Crystal StructuresKrieger, Malabar, 1963 Vol.2. 30L. E. Shelimova, O. G. Karpinskii, P. P. Konstantinov, M. A. Kretova, E. S. Avilov and V. S. Zemskov: Inorg. Mater. 37, 342 (2001). 31L. E. Shelimova, O. G. Karpinsky, V. S. Zernskov and P. P. Konstantinov: Inorg. Mater. 36, 235 (2000). 32L. E. Shelimova, O. G. Karpinskii, M. A. Kretova, E. S. Avilov and G. U. Lubman: Inorg. Mater. 33, 453 (1997). 33K. Kifune, Y. Kubota, T. Matsunaga and N. Yamada: Acta Cryst. B 61, 492 (2005). 34P. F. P. Poudeu and M. G. Kanatzidis: Chem. Commun. 2672 (2005). 35T. Matsunaga, N. Yamada, K. Kifune, Y. Kubota: SPring-8 experiment report 2007B1730 (2007). 36 40, 161 (1998). 37V. Petříček and M. Dušek: Jana2000 Crystallographic Computing Program, Institute of Physics, Academy of Sciences of the Czech Republic, Praha (2000). 38J. W. G. Bos, H. W. Zandbergen, M. -H. Lee, N. P. Ong and R. J. Cava: Phys. Rev. B 75, 195203 (2007). 39H. Lind and S. Lidin: Solid State Sci. 5, 47 (2003). Toshiyuki MATSUNAGA Materials Science and Analysis Technology Center, Panasonic Corporation 570-8501 3-1-1 3-1-1 Yagumo-Nakamachi, Moriguchi, Osaka 570-8501, Japan, Noboru YAMADA Digital & Network Technology Development Center, Panasonic Corporation 570-8501 3-1-1 3-1-1 Yagumo-Nakamachi, Moriguchi, Osaka 570-8501, Japan Kouichi KIFUNE Faculty of Liberal Arts and Sciences, Osaka Prefecture University 599-8531 1-1 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan TEL. 072-254-9194, FAX. 072-254-9927 e-mail: kifune@las.osakafu-u.ac.jp Yoshiki KUBOTA Graduate School of Science, Osaka Prefecture University 599-8531 1-1 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8531, Japan TEL. 072-254-9193, FAX. 072-254-9193 e-mail: kubotay@p.s.osakafu-u.ac.jp 51 5 2009 299