Abstract
A defect has negative-U properties if it can trap two electrons (or holes) with the second bound more strongly than the first. The system can be thought of as an extrinsic Cooper pair, the defect providing an environment in which a net attraction can develop between the otherwise Coulombically repulsive carriers. Evidence previously cited for this behavior in selected liquid and solid state systems will be reviewed. Recently, the first direct and unambiguous demonstration of the phenomenon in a solid has been supplied for two simple point defects in crystalline silicon—the lattice vacancy and interstitial boron. The experiments leading to this identification are described and mechanisms for this remarkable phenomenon are discussed.
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References
J. Hubbard, Proc. Roy. Soc. A276, 238 (1963).
H. J. Hoffmann, Appl. Phys. A27, 39 (1982). In this paper Hoffmann notes subtle differences between the Hall properties for normal and negative-U levels that he argues should be detectable under careful analysis.
L. N. Cooper, Phys. Rev., 104, 1189 (1956).
See, for example, John Burgess, Metal Ions in Solution, Chichester, Ellis Horwood Ltd., 1978.
G. Milazzo and S. Caroli, Table of Standard Electrode Potentials, New York, Wiley, 1978.
Handbook of Chemistry and Physics, 60th edn., Boca Raton, CRC Press, 1980, pgs. D-155-160.
W. Weyl, Pogg. Ann. 121, 601 (1863).
The recent evolution of this fascinating topic is chronicled in the published proceedings of the international “Colloque Weyl” conferences: I. Metal Ammonia Solutions, ed. by G. Lepourtre and M. J. Sienko, N. Y., Benjamin, 1964; II. Metal Ammonia Solutions, ed. by J. J. Lagowski and M. J. Sienko, London, Butterworths 1970; III. Electrons in Fluids, ed. by J. Jortner and N. R. Kastner, Berlin, Springer-Verlag 1973; IV. J. Phys. Chem. 79, 2789–3079 (1975); V. J. Phys. Chem. 84, 1065–1298 (1980). See also M. H. Cohen and J. C. Thompson, Adv. Phys. 18, 665 (1969).
R. A. Ogg. Jr., J. Am. Chem. Soc. 68, 155 (1946).
R. A. Ogg. Jr., J. Chem. Phys. 14, 114 (1946).
R. A. Ogg. Jr., J. Chem. Phys. 14, 295 (1946).
S. Freed and N. Sugarman, J. Chem. Phys. 11, 354 (1943).
J. Kaplan and C. Kittel, J. Chem. Phys. 21, 1429 (1953).
R. H. Land and D. E. O’Reilly, J. Chem. Phys. 46, 4496 (1967).
M. D. Newton, J. Phys. Chem. 79, 2795 (1975).
J. L. Dye, C. W. Andrews and J. M. Ceraso, J. Phys. Chem. 79, 3076 (1975).
P. W. Anderson, Phys. Rev. Lett. 34, 953 (1975).
V. L. Vinetskii, Zh. Eksp. Teor. Fiz. 40, 1459 (1961) [Sov. Phys. JETP 13, 1023 (1961)].
T. D. Shultz, in Polarons and Excitons, ed. by C. G. Kuper and G. D. Whitfield, New York, Plenum 1962, p. 110.
S. Laskis, C. Schlenker, B. K. Chakraverty, R. Buder and M. Marezio, Phys. Rev. B14, 1429 (1976).
C. Schlenker, S. Ahmed, R. Buder and M. Gourmala, J. Phys. C 12, 3503 (1979).
O. F. Schirmer and E. Salje, J. Phys. C13, L1067 (1980).
T. M. Rice and L. Sneddon, Phys. Rev. Lett. 47, 689 (1981).
M. Peo, S. Roth, K. Dransfeld, B. Tieke, J. Hocker, H. Gross, A. Grupp and H. Sixl, Sol. St. Comm. 35, 119 (1980).
J. L. Bredas, R. R. Chance and R. Silbey, Phys. Rev. B26, 5843 (1982).
C. Crecelius, M. Stamm, J. Fink and J. J. Ritsko, Phys. Lett. 50, 1498 (1983).
N. A. Cade and B. Movaghar, J. Phys. C 16, 539 (1983).
J. C. Scott, P. Pfluger, M. T. Krounbi and G. B. Street, Phys. Rev. B28, 2140 (1983).
A. Alexandrov and J. Ranninger, Phys. Rev. B24, 1164 (1981).
B. K. Chakraverty, J. Physique 42, 1351 (1981).
S. A. Brazovskii and N. N. Kirova, Pis. Zh. Eksp. Teor. Fiz. 33, 6 (1981) [JETP Lett. 33, 4 (1981)].
R. A. Street and N. F. Mott, Phys. Rev. Lett. 35, 1293 (1975).
M. Kastner, D. Adler and H. Fritzsche, Phys. Rev. Lett. 37, 1504 (1976).
Kastner et al. originally suggested that the neutral state would also be threefold coordinated. Subsequently, more detailed calculations by Vanderbilt and Joannopoulos [35] concluded that it would be singly coordinated.
D. Vanderbilt and J. D. Joannopoulos, Phys. Rev. B27, 6311 (1983).
D. C. Licciardello, D. L. Stein and F. D. M. Haldane, Phil. Mag. B43, 189 (1981).
D. Emin, Comments Sol. St. Phys. 11, 35 and 59 (1983).
See recent reviews by J. Robertson, Phys. and Chem. of Glasses 23, 1 (1982) and Adv. in Phys. 32, 361 (1983).
H. Fritzsche, J. Phys. Soc. Japan 49, suppl. A, 39 (1980).
S. G. Bishop, U. Strom and P. C. Taylor, Phys. Rev. B15, 2278 (1977).
G. Pfister, K. S. Liang, M. Morgan, P. C. Taylor, E. J. Friebele, and S. G. Bishop, Phys. Rev. Lett. 41, 1318 (1978).
D. K. Biegelsen and R. A. Street, Phys. Rev. Lett. 44, 803 (1980).
Y. V. Andreev, K. I. Geiman, I. A. Drabkin, A. V. Matveenko, E. A. Mozhaev, and B. Y. Moizhes, Fiz. Tekh. Poluprovodn. 9, 1873 (1975); [Sov. Phys. Semic. 9, 1235 (1975)].
I. A. Drabkin and B. Y. Moizhes, Fiz. Tekh. Poluprovodn. 15, 625 (1981); [Sov. Phys. Semic. 15, 357 (1981)]. This also provides a good review of evidence for negative-U behavior of impurities in other systems. An interesting suggestion is made, for instance, that the MXWO3 tungsten bronzes are examples of negative-U behavior of the alkali (M) ion dopant.
K. Weiser, Phys. Rev. B25, 1408 (1982).
A. A. Averkin, V. I. Kaidanov and R. B. Mel’nik, Fiz. Tekh. Poluprovodn. 5, 91 (1971); [Sov. Phys. Semic. 5, 75 (1971)].
Y. Kagan and K. A. Kikoin, Pis. Eksp. Teor. Fiz. 31, 367 (1980) [JETP Lett. 31, 335 (1980)].
I. A. Drabkin, M. A. Kvantov, V. V. Kompaniets and Y. P. Kostikov, Fiz. Tekh. Poluprovodn. 16, 1276 (1982); [Sov. Phys. Semic. 16, 815 (1982)].
G. D. Watkins and J. R. Troxell, Phys. Rev. Lett. 44, 593 (1980).
J. R. Troxell and G. D. Watkins, Phys. Rev. B22, 921 (1980).
G. D. Watkins, A. P. Chatterjee, and R. D. Harris, in Defects and Radiation Effects in Semiconductors, ed. by R. Hasiguti, London, Inst. of Phys. (Conf. Se. No. 59) 1981, p. 199.
G. D. Watkins, in Defects in Semiconductors, ed. by J. Narayan and T. Y. Tan, New York, North-Holland 1981, p. 21.
R. D. Harris, J. L. Newton and G. D. Watkins, Phys. Rev. Lett. 48, 1271 (1982).
R. D. Harris, J. L. Newton and G. D. Watkins, Phys. Rev. Lett. 51, 1722 (1983).
J. L. Newton, A. P. Chatterjee, R. D. Harris and G. D. Watkins, Physica 116B, 219 (1983).
G. D. Watkins, Phys. Rev. B12, 5824 (1975).
After correction for the T2 temperature dependence of the combined free carrier thermal velocity and density of states.
G. L. Miller, D. V. Lang and L. C. Kimerling, Ann. Rev. Mater. Sci. 7, 377 (1977).
G. D. Watkins, in Lattice Defects in Semiconductors 1974, ed. by F. A. Huntley, London, Inst. of Phys. (Conf. Se. No. 23) 1975, p. 1.
L. C. Kimerling, in Radiation Effects in Semiconductors, ed. by F. A. Huntley, London, Inst. of Phys. (Conf. Se. No. 31) 1977, p. 221.
J. Frenkel, Tech. Phys. USSR 5, 685 (1938) and Phys. Rev. 54, 647 (1938).
A. R. Williams, P. J. Feibelman and N. D. Lang, Phys. Rev. B26, 5433 (1982).
G. A. Baraff and M. Schluter, Phys. Rev. B28, 2296 (1983).
R. Car, P. J. Kelly, A. Oshijama, and S. T. Pantelides, to be published.
G. A. Baraff, E. O. Kane, and M. Schluter, Phys. Rev. Lett. 43, 956 (1979).
G. A. Baraff, E. O. Kane and M. Schluter, Phys. Rev. B21, 3563 (1980).
G. A. Baraff, E. O. Kane and M. Schluter, Phys. Rev. B22, 5662 (1980).
G. D. Watkins, J. R. Troxell and A. P. Chatterjee, in Defects and Radiation Effects in Semiconductors 1978, ed. by J. H. Albany, London, Inst. of Phys. (Conf. Se. No. 46) 1979, p. 16.
G. D. Watkins, Phys. Rev. B12, 4383 (1975).
B. N. Mukashev, V. V. Frolov and L. G. Kolodin, Physics Letters 91A, 358 (1982).
B. N. Mukashev, L. G. Kolodin, K. H. Nussupov, A. V. Spitsyn and V. S. Vavilov, Radiat. Eff. 46, 79 (1980).
H. J. Hoffmann, Physics Letters 98A, 444 (1983).
G. D. Watkins, A. P. Chatterjee, R. D. Harris and J. R. Troxell, Semic. and Ins. 5, 321 (1983).
E. Simanek, Sol. St. Comm. 32, 731 (1979).
C. S. Ting, D. N. Talwar and K. L. Ngai, Phys. Rev. Lett. 45, 1213 (1980).
I. A. Chernik and S. N. Likhov, Fiz. Tverd. Tela 23, 1400 (1981) [Sov. Phys. Sol. St. 23, 817 (1981)].
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© 1984 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH
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Watkins, G.D. (1984). Negative-U properties for defects in solids. In: Grosse, P. (eds) Advances in Solid State Physics. Advances in Solid State Physics, vol 24. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0107450
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DOI: https://doi.org/10.1007/BFb0107450
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