Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter June 11, 2013

Thermodynamics of reactions and phase transformations at interfaces and surfaces

Lars P. H. Jeurgens, Zumin Wang and Eric J. Mittemeijer


Recent advances in the thermodynamic description of reactions and phase transformations at interfaces between metals, semiconductors, oxides and the ambient have been reviewed. Unanticipated nanostructures, characterized by the presence of phases at interfaces and surfaces which are unstable as bulk phases, can be thermodynamically stabilized due to the dominance of energy contributions of interfaces and surfaces in the total Gibbs energy of the system. The basic principles and practical guidelines to construct realistic, practically and generally applicable thermodynamic model descriptions of microstructural evolutions at interfaces and surfaces have been outlined. To this end, expressions for the estimation of the involved interface and surface energies have been dealt with extensively as a function of, e. g., the film composition and the growth temperature. Model predictions on transformations at interfaces (surfaces) in nanosized systems have been compared with corresponding experimental observations for, in particular, ultrathin (< 5 nm) oxide overgrowths on metal surfaces, as well as the metal-induced crystallization of semi-conductors in contact with various metals.

* Correspondence address, Dr. Lars P.H. Jeurgens Max Planck Institute for Metals Research Heisenbergstrasse 3, 70569 Stuttgart, Germany Tel.: +49 711 689 3485 Fax: +49 711 689 3312 E-mail:


[1] R.Benedictus, A.Bottger, E.J.Mittemeijer: Phys. Rev. B54 (1996) 9109.10.1103/PhysRevB.54.9109Search in Google Scholar

[2] L.P.H.Jeurgens, W.G.Sloof, F.D.Tichelaar, E.J.Mittemeijer: Phys. Rev. B62 (2000) 4707.10.1103/PhysRevB.62.4707Search in Google Scholar

[3] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Acta Mater.56 (2008) 659.10.1016/j.actamat.2007.10.023Search in Google Scholar

[4] Z.M.Wang, J.Y.Wang, L.P.H.Jeurgens, E.J.Mittemeijer: Phys. Rev. Lett.100 (2008) 125503.10.1103/PhysRevLett.100.125503Search in Google Scholar

[5] E.Arzt: Acta Mater.46 (1998) 5611.10.1016/S1359-6454(98)00231-6Search in Google Scholar

[6] X.Batlle, A.Labarta: J. Phys. D. Appl. Phys.35 (2002) R 15.Search in Google Scholar

[7] A.D.Yoffe: Adv. Phys.51 (2002) 799.10.1080/00018730110117451Search in Google Scholar

[8] U.Dahmen, S.Hagège, F.Faudot, T.Radetic, E.Johnson: Philos. Mag.84 (2003) 2651.10.1080/14786430410001671403Search in Google Scholar

[9] Q.S.Mei, K.Lu: Prog. Mater. Sci.52 (2007) 1175.10.1016/j.pmatsci.2007.01.001Search in Google Scholar

[10] Z.M.Wang, J.Y.Wang, L.P.H.Jeurgens, E.J.Mittemeijer: Scripta Mater.55 (2006) 987.10.1016/j.scriptamat.2006.08.029Search in Google Scholar

[11] P.Lejcek, S.Hofmann: Crit. Rev. Solid State Mat. Sci.33 (2008) 133.10.1080/10408430801907649Search in Google Scholar

[12] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Phys. Rev. B73 (2006) 024103.10.1103/PhysRevB.73.024103Search in Google Scholar

[13] H.Over: Prog. Surf. Sci.58 (1998) 249.10.1016/S0079-6816(98)00029-XSearch in Google Scholar

[14] G.A.Somorjai, M.A.Vanhove: Prog. Surf. Sci.30 (1989) 201.10.1016/0079-6816(89)90009-9Search in Google Scholar

[15] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Acta Mater.56 (2008) 2897.10.1016/j.actamat.2008.02.031Search in Google Scholar

[16] G.A.Lopez, E.J.Mittemeijer, B.B.Straumal: Acta Mater.52 (2004) 4537.10.1016/j.actamat.2004.06.011Search in Google Scholar

[17] Z.M.Wang, J.Y.Wang, L.P.H.Jeurgens, E.J.Mittemeijer: Phys. Rev. B77 (2008) 045424.10.1103/PhysRevB.77.045424Search in Google Scholar

[18] J.Y.Wang, D.He, Y.H.Zhao, E.J.Mittemeijer: Appl. Phys. Lett.88 (2006) 061910.10.1063/1.2172707Search in Google Scholar

[19] L.Cha, C.Scheu, G.Richter, T.Wagner, S.Sturm, M.Rühle: Int. J. Mater. Res.98 (2007) 692.Search in Google Scholar

[20] E.Pagounis, M.Talvitie, V.K.Lindroos: Composites Sci. Techn.56 (1996) 1329.10.1016/S0266-3538(96)00101-7Search in Google Scholar

[21] C.T.Campbell: Surf. Sci. Rep.27 (1997) 1.10.1016/S0167-5729(96)00011-8Search in Google Scholar

[22] S.B.Sinnott, E.C.Dickey: Mater. Sci. Eng. R43 (2003) 1.10.1016/j.mser.2003.09.001Search in Google Scholar

[23] V.Da Costa, C.Tiusan, T.Dimopoulos, K.Ounadjela: Phys. Rev. Lett.85 (2000) 876.10.1103/PhysRevLett.85.876Search in Google Scholar

[24] A.Gupta, X.W.Li, G.Xiao: Appl. Phys. Lett.78 (2001) 1894.10.1063/1.1356726Search in Google Scholar

[25] G.Hu, Y.Suzuki: Phys. Rev. Lett.89 (2002) 4.10.1103/PhysRevLett.89.276601Search in Google Scholar

[26] A.Atkinson: Rev. Mod. Phys.57 (1985) 437.10.1103/RevModPhys.57.437Search in Google Scholar

[27] L.P.H.Jeurgens, W.G.Sloof, F.D.Tichelaar, E.J.Mittemeijer: J. Appl. Phys.92 (2002) 1649.10.1063/1.1491591Search in Google Scholar

[28] E.Comini, G.Faglia, G.Sberveglieri, Z.W.Pan, Z.L.Wang: Appl. Phys. Lett.81 (2002) 1869.10.1063/1.1504867Search in Google Scholar

[29] Z.R.Dai, Z.W.Pan, Z.L.Wang: Adv. Funct. Mater.13 (2003) 9.10.1002/adfm.200390013Search in Google Scholar

[30] J.Gustafson, R.Westerstroem, A.Mikkelsen, X.Torrelles, O.Balmes, N.Bovet, J.N.Andersen, C.J.Baddeley, E.Lundgren: Phys. Rev. B78 (2008) 6.10.1103/PhysRevB.78.045423Search in Google Scholar

[31] C.R.Henry: Surf. Sci. Rep.31 (1998) 235.10.1016/S0167-5729(98)00002-8Search in Google Scholar

[32] M.A.Hollanders, B.J.Thijsse, E.J.Mittemeijer: Phys. Rev. B42 (1990) 5481.10.1103/PhysRevB.42.5481Search in Google Scholar PubMed

[33] B.X.Liu, W.S.Lai, Z.J.Zhang: Adv. Phys.50 (2001) 367.10.1080/00018730110096112Search in Google Scholar

[34] H.D.Ackler, Y.M.Chiang: J. Am. Ceram. Soc.80 (1997) 1893.Search in Google Scholar

[35] M.Bobeth, D.R.Clarke, P.Wolfgang: J. Am. Ceram. Soc.82 (1999) 1537.Search in Google Scholar

[36] D.R.Clarke: J. Am. Ceram. Soc.70 (1987) 15.10.1111/j.1151-2916.1987.tb04846.xSearch in Google Scholar

[37] D.R.Clarke, T.M.Shaw, A.P.Philipse, R.G.Horn: J. Am. Ceram. Soc.76 (1993) 1201.10.1111/j.1151-2916.1993.tb03741.xSearch in Google Scholar

[38] J.Luo, Y.M.Chiang: Annu. Rev. Mater. Res.38 (2008) 227.10.1146/annurev.matsci.38.060407.132431Search in Google Scholar

[39] A.Subramaniam, C.T.Koch, R.M.Cannon, M.Rühle: Mater. Sci. Eng. A422 (2006) 3.10.1016/j.msea.2006.01.004Search in Google Scholar

[40] I.J.Bennett, J.M.Kranenburg, W.G.Sloof: J. Am. Ceram. Soc.88 (2005) 2209.Search in Google Scholar

[41] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Phys. Rev. B74 (2006) 144103.10.1103/PhysRevB.74.144103Search in Google Scholar

[42] F.Reichel, L.P.H.Jeurgens, G.Richter, P.A.van Aken, E.J.Mittemeijer: Acta Mater.55 (2007) 6027.10.1016/j.actamat.2007.07.011Search in Google Scholar

[43] F.Sommer, R.N.Singh, E.J.Mittemeijer: J. Alloys Compnd467 (2009) 142.10.1016/j.jallcom.2007.11.106Search in Google Scholar

[44] Boer, R.Boom, W.C.M.Mattens, A.R.Miedema: Cohesion in Metals: Transition Metals Alloys, Elsevier Science, Amsterdam, North Holland (1989).Search in Google Scholar

[45] A.R.Miedema, F.J.A.Denbroeder: Z. Metallkd70 (1979) 14.Search in Google Scholar

[46] H.Bakker: Enthalpies in Alloys: Miedema's Semi-Empirical model, Trans Tech, Uetikon-Zürich (1988).Search in Google Scholar

[47] L.P.H.Jeurgens, A.Lyapin, E.J.Mittemeijer: Acta Mater.53 (2005) 4871.10.1016/j.actamat.2005.06.028Search in Google Scholar

[48] C.Bos, F.Sommer, E.J.Mittemeijer: Acta Mater.53 (2005) 5333.10.1016/j.actamat.2005.08.010Search in Google Scholar

[49] R.Hultgren, P.D.Desai, D.T.Hawkins, M.Gleiser, K.K.Kelly: Selected Values of the Thermodynamic Properties of Binary Alloys, American Society of Metals, Metals Park, Ohio (1973).Search in Google Scholar

[50] B.Predel, in: O.Madelung (Ed.), Numerical data and functional relationships in science and technology, Springer, Berlin (1992–1998).Search in Google Scholar

[51] J.O.Andersson, T.Helander, L.H.Hoglund, P.F.Shi, B.Sundman: Calphad-Comput. Coupling Ph. Diagrams Thermochem.26 (2002) 273.Search in Google Scholar

[52] R.Benedictus, K.Han, C.Traeholt, A.Bottger, E.J.Mittemeijer: Acta Mater.46 (1998) 5491.10.1016/S1359-6454(98)00191-8Search in Google Scholar

[53] L.P.H.Jeurgens, F.Reichel, S.Frank, G.Richter, E.J.Mittemeijer: Surf. Interf. Anal.40 (2008) 259.10.1002/sia.2688Search in Google Scholar

[54] P.C.Snijders, L.P.H.Jeurgens, W.G.Sloof: Surf. Sci589 (2005) 98.10.1016/j.susc.2005.05.051Search in Google Scholar

[55] M.W.Chase: J. Phys. Chem. Ref. Data28 (1998).Search in Google Scholar

[56] F.Reichel, L.P.H.Jeurgens, G.Richter, J.Mittemeijer: J. Appl. Phys.103 (2008) 093515.10.1063/1.2913505Search in Google Scholar

[57] F.P.Fehlner: Low-Temperature Oxidation: The Role of Vitreous Oxides, Wiley-Interscience, New York (1989).Search in Google Scholar

[58] A.R.Miedema, R.Boom: Z. Metallkd.69 (1978) 183.Search in Google Scholar

[59] A.R.Miedema: Z. Metallkd.69 (1978) 287.10.1515/ijmr-1978-690501Search in Google Scholar

[60] M.Green: Solid State Surface Science, Marcel Dekker, New-York (1973).Search in Google Scholar

[61] K.Kendall, N.M.Alford, J.D.Birchall: Nature325 (1987) 794.10.1038/325794a0Search in Google Scholar

[62] V.K.Kumikov, K.B.Khokonov: J. Appl. Phys.54 (1983) 1346.10.1063/1.332209Search in Google Scholar

[63] S.H.Overbury, P.A.Bertrand, G.A.Somorjai: Chem. Rev.75 (1975) 547.10.1021/cr60297a001Search in Google Scholar

[64] J.S.Vermaak, C.W.Mays, D.Kuhlmann: Surf. Sci12 (1968) 128.10.1016/0039-6028(68)90118-0Search in Google Scholar

[65] R.G.Linford: Chem. Soc. Rev1 (1972) 445.10.1039/cs9720100445Search in Google Scholar

[66] P.R.Couchman, W.A.Jesser: Surf. Sci34 (1973) 212.10.1016/0039-6028(73)90116-7Search in Google Scholar

[67] A.P.Sutton, R.W.Balluffi: Interfaces in Crystalline Materials, Clarendon Press, Oxford (2006).Search in Google Scholar

[68] N.Eustathopoulos, B.Drevet, E.Ricci: J. Cryst. Growth191 (1998) 268.10.1016/S0022-0248(98)00012-8Search in Google Scholar

[69] Q.Jiang, H.M.Lu: Surf. Sci. Rep.63 (2008) 427.10.1016/j.surfrep.2008.07.001Search in Google Scholar

[70] T.Tanaka, K.Hack, T.Iida, S.Hara: Z. Metallkd.87 (1996) 380.Search in Google Scholar

[71] M.Methfessel, D.Hennig, M.Scheffler: Phys. Rev. B46 (1992) 4816.10.1103/PhysRevB.46.4816Search in Google Scholar

[72] N.Ikemiya, J.Umemoto, S.Hara, K.Ogino: ISIJ Int.33 (1993) 156.10.2355/isijinternational.33.156Search in Google Scholar

[73] J.M.McHale, A.Auroux, A.J.Perrotta, A.Navrotsky: Science277 (1997) 788.10.1126/science.277.5327.788Search in Google Scholar

[74] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Acta Mater.56 (2008) 5894.10.1016/j.actamat.2008.09.006Search in Google Scholar

[75] J.J.Gilman: J. Appl. Phys.31 (1960) 2208.10.1063/1.1735524Search in Google Scholar

[76] G.Jura, C.W.Garland: J. Am. Chem. Soc.74 (1952) 6033.10.1021/ja01143a062Search in Google Scholar

[77] P.G.Shewmon, W.M.Robertson: Metal surfaces: structure, energetics and kinetics., Metals Park, Ohio (1963) 67.Search in Google Scholar

[78] J.M.Howe: Int. Mater. Rev.38 (1993) 257.10.1179/imr.1993.38.5.257Search in Google Scholar

[79] L.S.Penn, E.Defex: J. Mater. Sci.37 (2002) 505.10.1023/A:1013709305846Search in Google Scholar

[80] Y.Wei, J.W.Hutchinson: Int. J. Fracture93 (1998) 315.10.1023/A:1007545200315Search in Google Scholar

[81] S.Kamiya, H.Furuta, M.Omiya, H.Shimomura: Eng. Fract. Mech.75 (2008) 5007.10.1016/j.engfracmech.2008.06.011Search in Google Scholar

[82] H.M.Pollock, P.Shufflebottom, J.Skinner: J. Phys. D. Appl. Phys.10 (1977) 127.10.1088/0022-3727/10/1/014Search in Google Scholar

[83] H.M.Pollock: J. Phys. D. Appl. Phys.11 (1978) 39.10.1088/0022-3727/11/1/007Search in Google Scholar

[84] M.W.Finnis: J Phys.-Cond. Mat.8 (1996) 5811.10.1088/0953-8984/8/32/003Search in Google Scholar

[85] J.M.Howe: Int. Mater. Rev.38 (1993) 233.10.1179/imr.1993.38.5.233Search in Google Scholar

[86] J.G.Li: J. Am. Ceram. Soc.75 (1992) 3118.10.1111/j.1151-2916.1992.tb04396.xSearch in Google Scholar

[87] J.G.Li: Mater. Chem. Phys.47 (1997) 126.10.1016/S0254-0584(97)80041-7Search in Google Scholar

[88] W.Lojkowski, H.J.Fecht: Prog. Mater. Sci.45 (2000) 339.10.1016/S0079-6425(99)00008-0Search in Google Scholar

[89] W.Zhang, J.R.Smith, A.G.Evans: Acta Mater.50 (2002) 3803.10.1016/S1359-6454(02)00177-5Search in Google Scholar

[90] Y.Zhang, Y.G.Yao: Mod. Phys. Lett. B22 (2008) 3135.10.1142/S0217984908017667Search in Google Scholar

[91] M.Rühle: J. Eur. Ceram. Soc.16 (1995) 353.10.1016/0955-2219(95)00194-8Search in Google Scholar

[92] A.Hashibon, C.Elsässer, M.Rühle: Acta Mater.53 (2005) 5323.10.1016/j.actamat.2005.07.036Search in Google Scholar

[93] M.P.Rosenblum, F.Spaepen, D.Turnbull: Appl. Phys. Lett.37 (1980) 184.10.1063/1.91818Search in Google Scholar

[94] J.E.Houser, K.R.Hebert: Nature Mater.8 (2009) 420.10.1038/nmat2423Search in Google Scholar

[95] D.M.Lipkin, J.N.Israelachvili, D.R.Clarke: Philos. Mag. A76 (1997) 715.10.1080/01418619708214205Search in Google Scholar

[96] J.V.Naidich, V.S.Zhuravljov, N.I.Frumina: J. Mater. Sci.25 (1990) 1895.10.1007/BF01045739Search in Google Scholar

[97] F.Sommer, R.N.Singh, V.Witusiewicz: J. Alloys Compnd.325 (2001) 118.10.1016/S0925-8388(01)01272-5Search in Google Scholar

[98] R.H.Ewing: Philos. Mag.25 (1972) 779.10.1080/14786437208229303Search in Google Scholar

[99] F.Spaepen: Acta Metall.23 (1975) 729.10.1016/0001-6160(75)90056-5Search in Google Scholar

[100] F.Spaepen, R.B.Meyer: Scripta Metall.10 (1976) 257.10.1016/0036-9748(76)90374-4Search in Google Scholar

[101] S.H.Oh, Y.Kauffmann, C.Scheu, W.D.Kaplan, M.Rühle: Science310 (2005) 661.10.1126/science.1118611Search in Google Scholar

[102] E.Panda, L.P.H.Jeurgens, E.J.Mittemeijer: submitted (2009).Search in Google Scholar

[103] G.V.Samsonov: The Oxide Handbook, Plenum Press, New York (1973).10.1007/978-1-4615-9597-7Search in Google Scholar

[104] F.Reichel, L.P.H.Jeurgens, E.J.Mittemeijer: Thin Solid Films516 (2006) 1457.10.1016/j.tsf.2007.07.171Search in Google Scholar

[105] D.Turnbull: Impurities and Imperfections, American Society of Metals, Cleveland (1955) 121.Search in Google Scholar

[106] J.H.Van der Merwe: Surf. Sci31 (1972) 198.10.1016/0039-6028(72)90261-0Search in Google Scholar

[107] L.E.Murr: Interfacial Phenomena in Metals and Alloys, Addison-Wesley Publ. Comp., London (1975).Search in Google Scholar

[108] K.R.Lawless: Rep. Prog. Phys.37 (1974) 231.10.1088/0034-4885/37/2/002Search in Google Scholar

[109] G.Skandan, C.M.Foster, H.Frase, M.N.Ali, J.C.Parker, H.Hahn: Nanostruct. Mater.1 (1992) 313.10.1016/0965-9773(92)90038-YSearch in Google Scholar

[110] R.C.Garvie: J. Phys. Chem.82 (1978) 218.10.1021/j100491a016Search in Google Scholar

[111] N.Cabrera, N.F.Mott: Rep. Prog. Phys.12 (1948) 163.10.1088/0034-4885/12/1/308Search in Google Scholar

[112] F.P.Fehlner, N.F.Mott: Science2 (1970) 59.Search in Google Scholar

[113] A.G.Revesz, F.P.Fehlner: Ox. Met.15 (1981) 297.10.1007/BF01058831Search in Google Scholar

[114] H.J.Freund: Surf. Sci601 (2007) 1438.10.1016/j.susc.2007.01.025Search in Google Scholar

[115] A.Johansson, G.Sambandamurthy, D.Shahar, N.Jacobson, R.Tenne: Phys. Rev. Lett.95 (2005) 4.Search in Google Scholar

[116] C.J.Forst, C.R.Ashman, K.Schwarz, P.E.Blochl: Microelectr. Eng.80 (2005) 402.10.1016/j.mee.2005.04.100Search in Google Scholar

[117] A.T.Fromhold, M.H.Anderson: Ox. Met.62 (2004) 237.10.1007/s11085-004-7810-zSearch in Google Scholar

[118] K.R.Lawless, A.T.Gwathmey: Acta Metall.4 (1956) 153.10.1016/0001-6160(56)90133-XSearch in Google Scholar

[119] C.Leygraf, S.Ekelund: Surf. Sci40 (1973) 609.10.1016/0039-6028(73)90148-9Search in Google Scholar

[120] H.Ma, Y.Berthier, P.Marcus: Appl. Surf. Sci.153 (1999) 40.10.1016/S0169-4332(99)00321-9Search in Google Scholar

[121] P.Michel, C.Jardin: Surf. Sci36 (1973) 478.10.1016/0039-6028(73)90396-8Search in Google Scholar

[122] A.Stierle, P.Bodeker, H.Zabel: Surf. Sci327 (1995) 9.10.1016/0039-6028(94)00830-2Search in Google Scholar

[123] J.B.Wagner, K.R.Lawless, A.T.Gwathmey: Trans. Metall. Soc. Aime221 (1961) 257.Search in Google Scholar

[124] S.Blonski, S.H.Garofalini: Surf. Sci295 (1993) 263.10.1016/0039-6028(93)90202-USearch in Google Scholar

[125] T.J.Konno, R.Sinclair: Philos. Mag. B66 (1992) 749.10.1080/13642819208220126Search in Google Scholar

[126] M.Seibt, S.Buschbaum, U.Gnauert, W.Schroter, D.Oelgeschlager: Phys. Rev. Lett.80 (1998) 774.10.1103/PhysRevLett.80.774Search in Google Scholar

[127] T.J.Konno, R.Sinclair: Philos. Mag. B71 (1995) 163.10.1080/01418639508240304Search in Google Scholar

[128] C.Hayzelden, J.L.Batstone: J. Appl. Phys.73 (1993) 8279.10.1063/1.353446Search in Google Scholar

[129] S.B.Lee, D.K.Choi, D.N.Lee: J. Appl. Phys.98 (2005) 114911.10.1063/1.2139835Search in Google Scholar

[130] S.W.Lee, Y.C.Jeon, S.K.Joo: Appl. Phys. Lett.66 (1995) 1671.10.1063/1.113888Search in Google Scholar

[131] F.Oki, Y.Ogawa, Y.Fujiki: Jpn. J. Appl. Phys.8 (1969) 1056.10.1143/JJAP.8.1056Search in Google Scholar

[132] Z.M.Wang, L.P.H.Jeurgens, J.Y.Wang, E.J.Mittemeijer: Adv. Engin. Mater.11 (2009) 131.10.1002/adem.200800340Search in Google Scholar

[133] A.Hiraki: Surf. Sci. Rep.3 (1983) 357.10.1016/0167-5729(84)90003-7Search in Google Scholar

[134] J.Luo: Crit. Rev. Solid State Mat. Sci.32 (2007) 67.10.1080/10408430701364388Search in Google Scholar

[135] T.J.Konno, R.Sinclair: Mater. Sci. Eng. A179 (1994) 426.10.1016/0921-5093(94)90240-2Search in Google Scholar

[136] Z.M.Wang, J.Y.Wang, L.P.H.Jeurgens, F.Phillipp, E.J.Mittemeijer: Acta Mater.56 (2008) 5047.10.1016/j.actamat.2008.06.026Search in Google Scholar

Received: 2008-7-14
Accepted: 2009-7-29
Published Online: 2013-06-11
Published in Print: 2009-10-01

© 2009, Carl Hanser Verlag, München