A ten-year perspective on dilute magnetic semiconductors and oxides
Source abstract
Abstract
Over the past ten years, the search for compounds combining the properties of semiconductors and ferromagnets has evolved into an important field of materials science. This endeavour has been fuelled by many demonstrations of remarkable low-temperature functionalities in the ferromagnetic structures (Ga,Mn)As and p-(Cd,Mn)Te, and related compounds, and by the theoretical prediction that magnetically doped, p-type nitride and oxide semiconductors might support ferromagnetism mediated by valence-band holes to above room temperature. Indeed, ferromagnetic signatures persisting at high temperatures have been detected in a number of non-metallic systems, even under conditions in which the presence of spin ordering was not originally anticipated. Here I review recent experimental and theoretical developments, emphasizing that they not only disentangle many controversies and puzzles accumulated over the past decade but also offer new research prospects.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: ZnO doping and properties · Electronic and Structural Properties of Oxides · Magnetic and transport properties of perovskites and related materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (100+)
Show source-provided references
1. Story, T., Galazka, R. R., Frankel, R. B. & Wolff, P. A. Carrier-concentration-induced ferromagnetism in PbSnMnTe. Phys. Rev. Lett. 56, 777–779 (1986).10.1103/PhysRevLett.56.777 ↗
2. Ohno, H., Munekata, H., Penney, T., von Molnàr, S. & Chang, L. L. Magnetotransport properties of p-type (In, Mn)As diluted magnetic III-V semiconductors. Phys. Rev. Lett. 68, 2664–2667 (1992).10.1103/PhysRevLett.68.2664 ↗
3. Ohno, H. et al. (Ga, Mn)As: a new diluted magnetic semiconductor based on GaAs. Appl. Phys. Lett. 69, 363–365 (1996).10.1063/1.118061 ↗
4. Van Esch, A. et al. Interplay between the magnetic and transport properties in the III-V diluted magnetic semiconductor Ga1−xMnxAs. Phys. Rev. B 56, 13103–13112 (1997).10.1103/PhysRevB.56.13103 ↗
5. Haury, A. et al. Observation of a ferromagnetic transition induced by two-dimensional hole gas in modulation-doped CdMnTe quantum wells. Phys. Rev. Lett. 79, 511–514 (1997).10.1103/PhysRevLett.79.511 ↗
6. Ferrand, D. et al. Carrier-induced ferromagnetic interactions in p-doped Zn1−xMnxTe epilayers. J. Cryst. Growth 214–215, 387–390 (2000).10.1016/S0022-0248(00)00114-7 ↗
7. Awschalom, D. D. & Flatté, M. E. Challenges for semiconductor spintronics. Nature Phys. 3, 153–159 (2007).10.1038/nphys551 ↗
8. Dietl, T., Awschalom, D. D., Kaminska, M. & Ohno, H. (eds) Spintronics (Semiconductors and Semimetals 82, Elsevier, 2008).
9. Ohno, Y. et al. Electrical spin injection in a ferromagnetic semiconductor heterostructure. Nature 402, 790–792 (1999).10.1038/45509 ↗
10. Ohno, H. et al. Electric-field control of ferromagnetism. Nature 408, 944–946 (2000).10.1038/35050040 ↗
11. Chiba, D. et al. Magnetization vector manipulation by electric fields. Nature 455, 515–518 (2008).10.1038/nature07318 ↗
12. Chernyshov, A. et al. Evidence for reversible control of magnetization in a ferromagnetic material by means of spin–orbit magnetic field. Nature Phys. 5, 656–659 (2009).10.1038/nphys1362 ↗
13. Gould, C. et al. Tunnelling anisotropic magnetoresistance: a spin-valve like tunnel magnetoresistance using a single magnetic layer. Phys. Rev. Lett. 93, 117203 (2004).10.1103/PhysRevLett.93.117203 ↗
14. Wunderlich, J. et al. Coulomb blockade anisotropic magnetoresistance effect in a (Ga, Mn)As single-electron transistor. Phys. Rev. Lett. 97, 077201 (2006).10.1103/PhysRevLett.97.077201 ↗
15. Yamanouchi, M., Chiba, D., Matsukura, F. & Ohno, H. Current-induced domain-wall switching in a ferromagnetic semiconductor structure. Nature 428, 539–541 (2004).10.1038/nature02441 ↗
16. Matsumoto, Y. et al. Room temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science 291, 854–856 (2001).10.1126/science.1056186 ↗
17. Bonanni, A. & Dietl, T. A story of high-temperature ferromagnetism in semiconductors. Chem. Soc. Rev. 39, 528–539 (2010).10.1039/B905352M ↗
18. Sheu, B. L. et al. Onset of ferromagnetism in low-doped Ga1−xMnxAs. Phys. Rev. Lett. 99, 227205 (2007).
19. Sawicki, M. et al. Experimental probing of the interplay between ferromagnetism and localization in (Ga,Mn)As. Nature Phys. 6, 22–25 (2010).10.1038/nphys1455 ↗
20. Richardella, A. et al. Visualizing critical correlations near the metal-insulator transition in Ga1−xMnxAs. Science 327, 665–669 (2010).10.1126/science.1183640 ↗
21. Dietl, T., Ohno, H., Matsukura, F., Cibert, J. & Ferrand, D. Zener model description of ferromagnetism in zinc-blende magnetic semiconductors. Science 287, 1019–1022 (2000).10.1126/science.287.5455.1019 ↗
22. Matsukura, F., Ohno, H., Shen, A. & Sugawara, Y. Transport properties and origin of ferromagnetism in (Ga,Mn)As. Phys. Rev. B 57, R2037–R2040 (1998).10.1103/PhysRevB.57.R2037 ↗
23. Okabayashi, J. et al. Core-level photoemission study of Ga1−xMnxAs. Phys. Rev. B 58, R4211–R4214 (1998).10.1103/PhysRevB.58.R4211 ↗
24. Linnarsson, M., Janzén, E., Monemar, B., Kleverman, M. & Thilderkvist, A. Electronic structure of the GaAs:MnGa center. Phys. Rev. B 55, 6938–6944 (1997).10.1103/PhysRevB.55.6938 ↗
25. Zener, C. Interaction between the d shells in the transition metals. Phys. Rev. 81, 440–444 (1951).10.1103/PhysRev.81.440 ↗
26. Dietl, T., Haury, A. & d'Aubigne, Y. M. Free carrier-induced ferromagnetism in structures of diluted magnetic semiconductors. Phys. Rev. B 55, R3347–R3350 (1997).10.1103/PhysRevB.55.R3347 ↗
27. Jungwirth, T., Atkinson, W. A., Lee, B. & MacDonald, A. H. Interlayer coupling in ferromagnetic semiconductor superlattices. Phys. Rev. B 59, 9818–9821 (1999).10.1103/PhysRevB.59.9818 ↗
28. Fukuma, Y. et al. Carrier-induced ferromagnetism in Ge0.92Mn0.08Te epilayers with a Curie temperature up to 190 K. Appl. Phys. Lett. 93, 252502 (2008).10.1063/1.3052081 ↗
29. Olejník, K. et al. Enhanced annealing, high Curie temperature and low-voltage gating in (Ga,Mn)As: a surface oxide control study. Phys. Rev. B 78, 054403 (2008).10.1103/PhysRevB.78.054403 ↗
30. Wang, M. et al. Achieving high Curie temperature in (Ga,Mn)As. Appl. Phys. Lett. 93, 132103 (2008).10.1063/1.2992200 ↗
31. Chen, L. et al. Low-temperature magnetotransport behaviors of heavily Mn-doped (Ga,Mn)As films with high ferromagnetic transition temperature. Appl. Phys. Lett. 95, 182505 (2009).10.1063/1.3259821 ↗
32. Akai, H. Ferromagnetism and its stability in the diluted magnetic semiconductor (In,Mn)As. Phys. Rev. Lett. 81, 3002–3005 (1998).10.1103/PhysRevLett.81.3002 ↗
33. Sato, K., Dederichs, P. H. & Katayama-Yoshida, H. Curie temperatures of III-V diluted magnetic semiconductors calculated from first principles. Europhys. Lett. 61, 403–408 (2003).10.1209/epl/i2003-00191-8 ↗
34. Mahadevan, P. & Zunger, A. Trends in ferromagnetism, hole localization, and acceptor level depth for Mn substitution in GaN, GaP, GaAs, GaSb. Appl. Phys. Lett. 85, 2860–2862 (2004).10.1063/1.1799245 ↗
35. Burch, K., Awschalom, D. & Basov, D. Optical properties of III-Mn-V ferromagnetic semiconductors. J. Magn. Magn. Mater. 320, 3207–3228 (2008).10.1016/j.jmmm.2008.08.060 ↗
36. Alberi, K. et al. Formation of Mn-derived impurity band in III-Mn-V alloys by valence band anticrossing. Phys. Rev. B 78, 075201 (2008).10.1103/PhysRevB.78.075201 ↗
37. Liu, C., Yun, F. & Morkoç, H. Ferromagnetism of ZnO and GaN: a review. J. Mater. Sci. Mater. Electron. 16, 555–597 (2005).10.1007/s10854-005-3232-1 ↗
38. Coey, J. M. D. Dilute magnetic oxides. Curr. Opin. Solid State Mater. Sci. 10, 83–92 (2006).10.1016/j.cossms.2006.12.002 ↗
39. Bonanni, A. Ferromagnetic nitride-based semiconductors doped with transition metals and rare earths. Semicond. Sci. Technol. 22, R41–R56 (2007).10.1088/0268-1242/22/9/R01 ↗
40. Sato, K. et al. First-principles theory of dilute magnetic semiconductors. Rev. Mod. Phys. 82, 1633–1690 (2010).10.1103/RevModPhys.82.1633 ↗
41. Blinowski, J., Kacman, P. & Majewski, J. A. Ferromagnetic superexchange in Cr-based diluted magnetic semiconductors. Phys. Rev. B 53, 9524–9527 (1996).10.1103/PhysRevB.53.9524 ↗
42. Walsh, A., Da Silva, J. L. F. & Wei, S-H. Theoretical description of carrier mediated magnetism in cobalt doped ZnO. Phys. Rev. Lett. 100, 256401 (2008).10.1103/PhysRevLett.100.256401 ↗
43. Coey, J. M. D., Venkatesan, M. & Fitzgerald, C. B. Donor impurity band exchange in dilute ferromagnetic oxides. Nature Mater. 4, 173–179 (2005).10.1038/nmat1310 ↗
44. Wang, Q., Sun, Q., Jena, P. & Kawazoe, Y. Magnetic properties of transition-metal-doped Zn1− xTxO (T = Cr, Mn, Fe, Co, and Ni) thin films with and without intrinsic defects: a density functional study. Phys. Rev. B 79, 115407 (2009).10.1103/PhysRevB.79.115407 ↗
45. Park, C. H. & Chadi, D. J. Hydrogen-mediated spin-spin interaction in ZnCoO. Phys. Rev. Lett. 94, 127204 (2005).10.1103/PhysRevLett.94.127204 ↗
46. Coey, J. M. D., Wongsaprom, K., Alaria, J. & Venkatesan, M. Charge-transfer ferromagnetism in oxide nanoparticles. J. Phys. D 41, 134012 (2008).10.1088/0022-3727/41/13/134012 ↗
47. Dietl, T. Dilute magnetic semiconductors: functional ferromagnets. Nature Mater. 2, 646–648 (2003).10.1038/nmat989 ↗
48. Cho, Y. J., Yu, K. M., Liu, X., Walukiewicz, W. & Furdyna, J. K. Effects of donor doping on Ga1−xMnxAs. Appl. Phys. Lett. 93, 262505 (2008).10.1063/1.3063046 ↗
49. Mayer, M. A. et al. Electronic structure of Ga1−xMnxAs analyzed according to hole-concentration-dependent measurements. Phys. Rev. B 81, 045205 (2010).10.1103/PhysRevB.81.045205 ↗
50. Jungwirth, T. et al. Character of states near the Fermi level in (Ga,Mn)As: impurity to valence band crossover. Phys. Rev. B 76, 125206 (2007).10.1103/PhysRevB.76.125206 ↗
51. Dietl, T. Interplay between carrier localization and magnetism in diluted magnetic and ferromagnetic semiconductors. J. Phys. Soc. Jpn 77, 031005 (2008).10.1143/JPSJ.77.031005 ↗
52. Altshuler, B. L. & Aronov, A. G. in Electron-Electron Interactions in Disordered Systems (eds Efros, A. L. & Pollak, M.) 1–153 (North Holland, 1985).10.1016/B978-0-444-86916-6.50007-7 ↗
53. Lee, P. A. & Ramakrishnan, T. V. Disordered electronic systems. Rev. Mod. Phys. 57, 287–337 (1985).10.1103/RevModPhys.57.287 ↗
54. Belitz, D. & Kirkpatrick, T. R. The Anderson-Mott transition. Rev. Mod. Phys. 66, 261–380 (1994).10.1103/RevModPhys.66.261 ↗
55. Edwards, P. P. & Sienko, M. J. Universality aspects of the metal-nonmetal transition in condensed media. Phys. Rev. B 17, 2575–2581 (1978).10.1103/PhysRevB.17.2575 ↗
56. Dietl, T., Matsukura, F. & Ohno, H. Ferromagnetism of magnetic semiconductors: Zhang-Rice limit. Phys. Rev. B 66, 033203 (2002).10.1103/PhysRevB.66.033203 ↗
57. Dietl, T. Hole states in wide band-gap diluted magnetic semiconductors and oxides. Phys. Rev. B 77, 085208 (2008).10.1103/PhysRevB.77.085208 ↗
58. Neumaier, D. et al. All-electrical measurement of the density of states in (Ga,Mn)As. Phys. Rev. Lett. 103, 087203 (2009).10.1103/PhysRevLett.103.087203 ↗
59. Boukari, H. et al. Light and electric field control of ferromagnetism in magnetic quantum structures. Phys. Rev. Lett. 88, 207204 (2002).10.1103/PhysRevLett.88.207204 ↗
60. Nishitani, Y. et al. Curie temperature versus hole concentration in field-effect structures of Ga1−xMnxAs. Phys. Rev. B 81, 045208 (2010).10.1103/PhysRevB.81.045208 ↗
61. MacDonald, A. H., Schiffer, P. & Samarth, N. Ferromagnetic semiconductors: moving beyond (Ga,Mn)As. Nature Mater. 4, 195–202 (2005).10.1038/nmat1325 ↗
62. Edmonds, K. W. et al. High Curie temperature GaMnAs obtained by resistance-monitored annealing. Appl. Phys. Lett. 81, 4991–4993 (2002).10.1063/1.1529079 ↗
63. Cho, Y. J., Liu, X. & Furdyna, J. K. Collapse of ferromagnetism in (Ga,Mn)As at high hole concentrations. Semicond. Sci. Technol. 23, 125010 (2008).10.1088/0268-1242/23/12/125010 ↗
64. Furdyna, J. K. et al. Fermi level effects on Mn incorporation in modulation-doped ferromagnetic III1−xMnxV heterostructures. J. Phys. Condens. Matter 16, S5499–S5508 (2004).10.1088/0953-8984/16/48/004 ↗
65. Scarpulla, M. A. et al. Ferromagnetism in Ga1−xMnxP: evidence for inter-Mn exchange mediated by localized holes within a detached impurity band. Phys. Rev. Lett. 95, 207204 (2005).10.1103/PhysRevLett.95.207204 ↗
66. Schallenberg, T. & Munekata, H. Preparation of ferromagnetic (In,Mn)As with a high Curie temperature of 90 K. Appl. Phys. Lett. 89, 042507 (2006).10.1063/1.2236210 ↗
67. Abe, E., Matsukura, F., Yasuda, H., Ohno, Y. & Ohno, H. Molecular beam epitaxy of III-V diluted magnetic semiconductor (Ga,Mn)Sb. Physica E 7, 981–985 (2000).10.1016/S1386-9477(00)00100-4 ↗
68. Wojtowicz, T. et al. In1−xMnxSb — a new narrow gap ferromagnetic semiconductor. Appl. Phys. Lett. 82, 4310–4312 (2003).10.1063/1.1583142 ↗
69. Jungwirth, T., König, J., Sinova, J., Kučera, J. & MacDonald, A. H. Curie temperature trends in (III,Mn)V ferromagnetic semiconductors. Phys. Rev. B 66, 012402 (2002).10.1103/PhysRevB.66.012402 ↗
70. Jungwirth, T., Sinova, J., Mašek, J., Kučera, J. & MacDonald, A. H. Theory of ferromagnetic (III,Mn)V semiconductors. Rev. Mod. Phys. 78, 809–864 (2006).10.1103/RevModPhys.78.809 ↗
71. Glunk, M. et al. Magnetic anisotropy in (Ga,Mn)As: influence of epitaxial strain and hole concentration. Phys. Rev. B 79, 195206 (2009).10.1103/PhysRevB.79.195206 ↗
72. Kodzuka, M., Ohkubo, T., Hono, K., Matsukura, F. & Ohno, H. 3DAP analysis of (Ga,Mn)As diluted magnetic semiconductor thin film. Ultramicroscopy 109, 644–648 (2009).10.1016/j.ultramic.2008.11.011 ↗
73. Yu, K. M. et al. Effect of the location of Mn sites in ferromagnetic Ga1−xMnxAs on its Curie temperature. Phys. Rev. B 65, 201303 (2002).
74. Wierzbowska, M., Sanchez-Portal, D. & Sanvito, S. Different origin of the ferromagnetic order in (Ga,Mn)As and (Ga,Mn)N. Phys. Rev. B 70, 235209 (2004).10.1103/PhysRevB.70.235209 ↗
75. Schulthess, T., Temmerman, W. M., Szotek, Z., Butler, W. H. & Stocks, G. M. Electronic structure and exchange coupling of Mn impurities in III-V semiconductors. Nature Mater. 4, 838–844 (2005).10.1038/nmat1509 ↗
76. Kitchen, D., Richardella, A., Tang, J-M., Flatte, M. E. & Yazdani, A. Atom-by-atom substitution of Mn in GaAs and visualization of their hole-mediated interactions. Nature 442, 436–439 (2006).10.1038/nature04971 ↗
77. Sarigiannidou, E. et al. Intrinsic ferromagnetism in wurtzite (Ga,Mn)N semiconductor. Phys. Rev. B 74, 041306 (2006).10.1103/PhysRevB.74.041306 ↗
78. Martinez-Criado, G. et al. Mn-rich clusters in GaN: hexagonal or cubic symmetry? Appl. Phys. Lett. 86, 131927 (2005).10.1063/1.1886908 ↗
79. Lipińska, A. et al. Ferromagnetic properties of p-(Cd,Mn)Te quantum wells: interpretation of magneto-optical measurements by Monte Carlo simulations. Phys. Rev. B 79, 235322 (2009).10.1103/PhysRevB.79.235322 ↗
80. Ferrand, D. et al. Carrier-induced ferromagnetism in p-Zn1−xMnxTe. Phys. Rev. B 63, 085201 (2001).
81. Andrearczyk, T. et al. in Proc. 25th Int. Conf. Phys. Semicond. (eds Miura, N. & Ando, T.) 234–235 (Springer, 2001).
82. Serrate, D., Teresa, J. M. D. & Ibarra, M. R. Double perovskites with ferromagnetism above room temperature. J. Phys. Condens. Matter 19, 023201 (2007).10.1088/0953-8984/19/2/023201 ↗
83. Park, J. H., Kim, M. G., Jang, H. M., Ryu, S. & Kim, Y. M. Co-metal clustering as the origin of ferromagnetism in Co-doped ZnO thin films. Appl. Phys. Lett. 84, 1338–1340 (2004).10.1063/1.1650915 ↗
84. Ney, A. et al. Advanced spectroscopic synchrotron techniques to unravel the intrinsic properties of dilute magnetic oxides: the case of Co:ZnO. N. J. Phys. 12, 013020 (2010).10.1088/1367-2630/12/1/013020 ↗
85. Bonanni, A. et al. Paramagnetic GaN:Fe and ferromagnetic (Ga,Fe)N: the relationship between structural, electronic, and magnetic properties. Phys. Rev. B 75, 125210 (2007).10.1103/PhysRevB.75.125210 ↗
86. Boeck, J. D. et al. Nanometer-scale magnetic MnAs particles in GaAs grown by molecular beam epitaxy. Appl. Phys. Lett. 68, 2744–2746 (1996).10.1063/1.115584 ↗
87. Moreno, M., Trampert, A., Jenichen, B., Däweritz, L. & Ploog, K. H. Correlation of structure and magnetism in GaAs with embedded Mn(Ga)As magnetic nanoclusters. J. Appl. Phys. 92, 4672–4677 (2002).10.1063/1.1506402 ↗
88. Rovezzi, M. et al. Local structure of (Ga,Fe)N and (Ga,Fe)N:Si investigated by X-ray absorption fine structure spectroscopy. Phys. Rev. B 79, 195209 (2009).10.1103/PhysRevB.79.195209 ↗
89. Bonanni, A. et al. Controlled aggregation of magnetic ions in a semiconductor: an experimental demonstration. Phys. Rev. Lett. 101, 135502 (2008).10.1103/PhysRevLett.101.135502 ↗
90. Tanaka, M., Yokoyama, M., Hai, P. N. & Ohya, S. in Spintronics (eds Dietl, T., Awschalom, D. D., Kaminska, M. & Ohno, H.) 455–485 (Semiconductors and Semimetals 82, Elsevier, 2008).
91. Kuroda, S. et al. Origin and control of high temperature ferromagnetism in semiconductors. Nature Mater. 6, 440–446 (2007).10.1038/nmat1910 ↗
92. Gu, L. et al. Characterization of Al(Cr)N and Ga(Cr)N dilute magnetic semiconductors. J. Magn. Magn. Mater. 290–291, 1395–1397 (2005).10.1016/j.jmmm.2004.11.446 ↗
93. Jamet, M. et al. High-Curie-temperature ferromagnetism in self-organized Ge1−xMnx nanocolumns. Nature Mater. 5, 653–659 (2006).10.1038/nmat1686 ↗
94. Nishio, Y., Ishikawa, K., Kuroda, S., Mitome, M. & Bando, Y. in Mater. Res. Soc. Symp. Proc. Vol. 1183-FF01-11 (Materials Research Society, 2009).
95. Katayama-Yoshida, H. et al. Theory of ferromagnetic semiconductors. Phys. Status Solidi A 204, 15–32 (2007).10.1002/pssa.200673021 ↗
96. Dietl, T. Self-organised growth controlled by charge states of magnetic impurities. Nature Mater. 5, 673 (2006).10.1038/nmat1721 ↗
97. Ye, L-H. Freeman, A. J. Defect compensation, clustering, and magnetism in Cr-doped anatase. Phys. Rev. B 73, 081304(R) (2006).
98. Straumal, B. B. et al. Magnetization study of nanograined pure and Mn-doped ZnO films: formation of a ferromagnetic grain-boundary foam. Phys. Rev. B 79, 205206 (2009).10.1103/PhysRevB.79.205206 ↗
99. Ney, A. et al. Absence of intrinsic ferromagnetic interactions of isolated and paired Co dopant atoms in Zn1−xCoxO with high structural perfection. Phys. Rev. Lett. 100, 157201 (2008).10.1103/PhysRevLett.100.157201 ↗
100. van Schilfgaarde, M. & Mryasov, O. N. Anomalous exchange interactions in III-V dilute magnetic semiconductors. Phys. Rev. B 63, 233205 (2001).10.1103/PhysRevB.63.233205 ↗