Hostname: page-component-76fb5796d-25wd4 Total loading time: 0 Render date: 2024-04-26T03:36:00.366Z Has data issue: false hasContentIssue false
  • English
  • Français

Interpretation of Valence Band X-Ray Spectra

Published online by Cambridge University Press:  06 March 2019

David J. Nagel
David J. Nagel*
Affiliation:
Naval Research Laboratory Washington, D. C. 20390
Get access

Abstract

X -ray spectra arising from the valence bands of solids are useful for basic studies of the electronic structure of most materials and for practical measurements of unknowns to obtain information on local atomic structure and material properties as well as chemical composition. Understanding the characteristics of valence band spectra is prerequisite to their fullest use. One-electron and many-body aspects of the x-ray emission process, and the effects of experimental conditions, must be understood and are reviewed. Interpretation of spectral features and determination of electronic structure are complementary parts of one procedure which is based on the use of bonding theory. The various band and bond theories which are finding use for spectral interpretation are briefly reviewed. Calculation of the electronic structure of aluminum metal and quartz, and interpretation of their x-ray spectra, are examples which illustrate basic work with valence band spectra.

Type
Research Article
Information
Advances in X-Ray Analysis , Volume 13: Eighteenth Annual Conference on Applications of X-ray Analysis, August 6-8, 1969 , 1969 , pp. 182 - 236
Copyright
Copyright © International Centre for Diffraction Data 1969

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Rooke, G. A., “The Interpretation of X-Ray Band Spectra”, in Fabian, D. J., Editor, Soft X-Ray Band Spectra, Academic Press, New York, 1968, p. 3.Google Scholar
2. Nikiforov, I. Ya. and Blokhin, M. A., “Concerning the Shape of the Kẞ5 Emission Band of Iron”, Bull. Ac, Sci. USSR Translation, 27, 323 (1963).Google Scholar
3. Batyrev, V. A. and Shatunova, A. V., “Procedure for Investigating the Influence of Chemical Bonds on the Fine Sturcture of X - Ray Emission Spectra in Microvolumes”, Bull. Ac. Sci. USSR Translation, 31, 896 (1967).Google Scholar
4. Fischer, D. W. and Baun, W. L., “Self Absorption Effects in the Soft X - Ray Mα and Mβ Emission Spectra of the Rare Earth Elements”, J. Appl. Phys., 38, 4830 (1967).Google Scholar
5. Liefeld, R. J., “Soft X - Ray Emission Spectra at Threshold Excitation”, in Fabian, D. J., Editor, Soft X - Ray Band Spectra, Academic Press, New York, 1968, p. 133.Google Scholar
6. Demekhin, V. F. and Kudraytsev, I. Ya.,”Shape of the Kβx Band of of Al Metal”, Phys, Metals and Metallography Translation 26, 174 (1968).Google Scholar
7. Bethe, H. A., “Intermediate Quantum Mechanics, Beniamin, New York, 1964, p. 143.Google Scholar
8. Fabian, D. F., Editor, “Soft X - Ray Band Spectra”, Academic Press, New York, 1968.Google Scholar
9. Hermann, F. and Skillman, S., “Atomic Structure Calculations”, Prentice-Hall, Englewood Cliffs, 1963.Google Scholar
10. Formichev, V. A.. “Investigation of the Energy Structure of B and BN and Ultrasoft X - Ray Spectros copy”, Bull. Ac. Sci, USSR Translation, 31, 972 (1967).Google Scholar
11. Bagus, P. S., “SCF Excited States and Transition Probabilities of Neon-and Argon-Like Ions”, Argonne Nat. Lab. Rpt. 6959 (1964).Google Scholar
12. Friedel, J. and Guinier, A., Editors, Metallic Solid Solutions, Benjamin, New York, 1963,Google Scholar
13. Ershov, O. A., Goganov, D. A., and Lukirskii, A. P., “X-Ray Spectra of Si in Crystalline and Glassy Quartz and in Li Silicate Glasses”, Sov. Phys,-Solid State, Translation 7, 1903 (1966).Google Scholar
14. Segall, B., “Energy Bands of Aluminum”, Phys. Rev., 124, 1797 (1961).Google Scholar
15. Rooke, G. A., “Interpretation of A1 X - Ray Band Spectra. I. Density Distribution”, J. Phys, C (Proc. Phys, Soc.), Ser, 2, 1, 767 (1968).Google Scholar
16. Reilly, M. H., “Temperature Dependence of Short Wavelength Transmittance Limits of Vacuum Ultraviolet Windows”, J. Phys, Chem. Solids, to be published.Google Scholar
17. Seka, W., Ph.D. Dissertation, Univ. of Texas (1965).Google Scholar
18. Glen, G. L. and Dodd, C. G., “Use of Molecular Orbital Theory to Interpret X - Ray Absorption Spectral Data”, J. Appl. Phys. 39, 5372 (1968).Google Scholar
19. Best, P. E., “Electronic Structure of MnO4 -, Cro4 2- and VO4 3- Ions From Metal K X - Ray Spectra”, J. Chem. Phys., 44, 3248 (1966).Google Scholar
20. Best, P. E., “Electronic Structures from X - Ray Spectra, II. Mostly Clo3 - “ and Clo4 - ”, J. Chem. Phys.,49, 2797 (1968).Google Scholar
21. Dodd, C. G. and Glen, G. L., “Chemical Bonding Studies of Silicates and Oxides by X - Ray Emission Spectroscopy”, J. Appl. Phys., 39, 5377 (1968).and references therein.Google Scholar
22. Urch, D. S., “The Origin of Low Energy Satellite Lines in X - Ray Emission Spectra; A Molecular Orbital Interpretation”, to be published.Google Scholar
23. Urch, D. S., “The Intensities of Low Energy Satellite Lines in X - Ray Emission Spectra”, to be published.Google Scholar
24. Urch, D. S., “Direct Evidence for 3d-2pπ Bonding in Oxy-Anions”, to be published.Google Scholar
25. Lawrence, D. F. and Urch, D. S., “ Low Energy Satellites in X - Ray Fluorescence Spectrum of Fluoro-Anions ”, Spectrochem. Acta, to be published.Google Scholar
26. Siegbahn, K., Nordling, C., Fahlman, A., et al., “Electron Spectroscopy for Chemical Analysis”, Tech. Rpt. AFMLTR-68-189, 1968, p. 1 and 66.Google Scholar
27. Freeman, A. J., “Band Structure in Metals and Alloys II: Symposium on Experimental Methods”, J. Appl. Phys, 40, 1386 (1969).Google Scholar
28. Abeles, F., “Review of Optical Properties of Metals and Alloys Due to Interband Transitions”, in ref. 8, p. 191.Google Scholar
29. Spicer, W. E., “The Band Structure of Noble and Transition Metals; Photoemission Studies” in Abeles, F., Editor, Optical Properties and Electronic Structure of Metals and Alloys, Wiley and Sons, New York, 1966, p. 296.Google Scholar
30. Rooke, G. A., “Interpretation of Aluminum X-Ray Band Spectra II. Determination of Effective Potentials from L2, 3 Emission Spectra” J. Phys. C. (Proc. Phys. Soc.), Ser. 2, 1, p 776 (1968).Google Scholar
31. Wiech, G., “Soft X-Ray Emission Spectra and Valence Band Structure of Be, Al, Si, and some Si Compounds”, in ref. 8, p. 59.Google Scholar
32. Fischer, W., “Chemical Bonding and Valence State—Nonmetals”, this volume.Google Scholar
33. Reilly, M. H. and Nagel, D. J., in preparation.Google Scholar
34. Ruffa, A. R., “The Valence Bond Approximation in Crystals - Application to Analysis of Ultraviolet Spectrum of Quartz”, Phys. Stat. Sol. 29, 605 (1968).Google Scholar
35. Ruffa, A. R., private communication.Google Scholar
36. Shuvaev, A. T., “Concerning the Interpretation of X-Ray Spectra”, Bull. Ac, Sci. USSR Translation, 24, 434 (1960).Google Scholar
37. Blokhin, M. A. and Shuvaev, A. T., “Concerning the Influence of Chemical Bonds on the X-Ray Emission Spectra of Titanium Compounds”, Bull. Ac. Sci. USSR Translation, 26, 429 (1962).Google Scholar
38. Korsunskii, M. I. and Genkin, Ya. E., “The Interpretation of the Lβ2 Emission Band of Niobium”, Sov. Phys. Doklady Translation, 7, 141 (1962).Google Scholar
39. Men'shikov, A. Z. and Nemnonov, S. A., “Influence of the Chemical Bonds on the Valence State of Cr in Different Compounds”, Bull. Ac. Sci. USSR Translation, 27, 402 (1963).Google Scholar
40. Cuthill, J. R., McAlister, A. J., and Williams, M. L., “Soft X-Ray Spectroscopy of Alloys: Ti-Ni and the Ni-Al System”, J. Appl. Phys., 39, 2204 (1968).Google Scholar
41. Holliday, J. E., “The Use of Soft X-Ray Fine Structure in Bonding Determination and Light Element Analysis”, Norelco Reporter, 14, 84 (1967).Google Scholar
42. Faessler, A., “Roentgenspektrum and Bindung Zustand”, in Landolt Bornstein Tables, Springer-Verlag, Berlin, Vol. 1/4, p. 769.Google Scholar
43. White, E. W. and Gibbs, G. V., “Structure and Chemical Effects of the AIKβ X-Ray Line for Silicates”, Am. Mineralogist, 52, 985 (1967).Google Scholar
44. White, E. W. and Gibbs, G. V., “Structural and Chemical Effects on the AIKβ X-Ray Emission Band Among Al-containing Silicates and Al Oxides”, Am. Mineralogist, 54, 931 (1969).Google Scholar
45. Arrhenius, G., “Chemical Bond Effects on Electron Transitions Between Inner Levels”, in Castaing, R. et al., Editors, X-Ray Optics and Microanalysis, Hermann, Paris, 1966, p. 328.Google Scholar
46. Baun, W. L. and Fischer, D. W., “The Effect of Valence and Coordination on K Series Diagram and Nondiagram Lines of Mg, Al, and Si”, in Meuller, W. M. et al., Editors, Advances in X-Ray Analysis, 8, Plenum Press, New York, 1965, p. 371.Google Scholar
47. Das Gupta, K., “The Soft X-Ray Valence Band Spectra and the Heat of Formation of Chemical Compounds and Alloys”, Phys, Rev. 80, 281 (1950).Google Scholar
48. Tomboulian, D. H., “Soft X-Ray Spectrometry”, Handbuch der Physik, 30, Springer-Verlag, Berlin, 1957, p. 246.Google Scholar
49. Korsunskii, M. I. and Genkin, Ya. E., “X-Ray Emission Bands and the Magnetic Properties of Nb”, Bull. Ac, Sci. USSR Translation, 27, 740 (1964).Google Scholar
50. Ovsyannikova, I. A. and Borovskii, I. B., “Investigation of the Fine Structure of the K Spectra of Some Sulphides”, Bull. Ac. Sci. USSR Translation, 24, 444 (1960).Google Scholar
51. White, E. W. and Roy, R., “Silicon Valence in SiO Films Studied by X-Ray Emission”, Sol. St. Comm., 2, 151 (1964).Google Scholar
52. Knausenberger, W. H., Yedam, K., White, E. W., and Ziegler, W., “Thin Film Characterization by Electron Microprobe and Ellipsometry: Sio2 Films on Silicon”, Appl. Phys. Ltrs. 14, 43,(1969).Google Scholar
53. Gigl, P. D., Savanick, G. A., and White, E. W., “Characterization of Corrosion Layers on Al by Shifts in Al and O Emission Bands”, submitted to J. Electrochemical Society.Google Scholar
54. Criss, J. W. and Birks, L. S., “Formulas for Specimens Containing Spherical Particles”, presented at 15th Colloq, Spect. Int., Madrid, Spain, 26-30 May 1969.Google Scholar
55. Baun, W. L. and Fischer, D. W., “Effect of Alloying on AIK and CuL Emission Spectra in the Al-Cu System”, J. Appl. Phys., 38, 2092 (1967).Google Scholar
56. Baun, W. L., “AlK X-Ray Emission Fine Features for Characterizing Al-Cu Films”, J. Appl. Phys., 40, 4210 (1969).Google Scholar
57. Dimond, R. K., “Self Absorption of Soft X-Ray Spectra of Alloys”, Phil. Mag., 15, 631 (1967).Google Scholar
58. Curry, C., “Soft X-Ray Emission Spectra of Alloys and Problems in Their Interpretation”, in Fabian, D. J., Editor, Soft X-Ray Band Spectra, Academic Press, New York, 1968, p, 173.Google Scholar
59. Marshall, C. A. W., Watson, L. M., Lindsay, G. M., Rooke, G. A., and Fabian, D. J., “Interpretation of Soft X-Ray Emission Spectra of Al-Ag Alloys”, Phys. Ltrs. 28A, 579 (1969).Google Scholar
60. Bolsaitis, P. and Skolnick, L. P., “Electron Cell Model of Alloys”, Trans. AIME, 242, 215 (1968).Google Scholar
61. Stern, E. A., “Requirements for a Theory of Disordered Alloys”, in Bennett, L. H. and Waber, J. T., Editors, Energy Bands in Metals and Alloys, Gordon Breach, New York, 1968, p. 151.Google Scholar
62. Birks, L. S., Electron Probe Microanalysis, Interscience, New York, 1963, p. 107ff. (Second Edition in preparation)Google Scholar
63. Baun, W. L., “Instrumentation, Spectral Characteristics, and Applications of Soft X-Ray Spectroscopy”, Appl. Spect. Rev., 1, 397 (1968).Google Scholar
64. Bearden, J. A. and Burr, A. F., “Reevaluation of X-Ray Atomic Energy Levels”, Rev. Mod. Phys., 39, 125 (1967).Google Scholar
65. Waber, J. T. and Cromer, D. T., “Orbital Radii of Atoms and Ions”, J. Chem. Phys., 42, 4116 (1961).Google Scholar
66. Parratt, L. G., “Electronic Band Structure of Solids by X-Ray Spectroscopy”, Rev. Mod. Phys., 31, 616 (1959).Google Scholar
67. Reference 26, p. 32.Google Scholar
68. Mahan, G. D., “Excitons in Metals: Infinite Hole Mass”, Phys. Rev., 163, 612 (1967).Google Scholar
69. Blokhin, M. A. and Demekhin, V. F., “Emission Spectrum of Sc in Sc2O3 ”, Bull. Ac. Sci. USSR Translation, 27, 738 (1964).Google Scholar
70. Hanzely, S., private communication.Google Scholar
71. Aberg, T. and Ultriainen, J., “Evidence for a Radiative Auger Effect in X-Ray Photon Emission”, Phys. Rev. Letters, 22, 1346 (1969).Google Scholar
72. Reference 9, Part 4.Google Scholar
73. Richard, P., Morgan, I. E., Furuta, T., and Burch, P., “Observed Kβ Shift in Cu and Ni”, Phys. Rev. Ltrs. 23, 1009 (1969).Google Scholar
74. Nozieres, P. and De Dominicos, C. T., “Singularities in X-Ray Absorption and Emission of Metals”, Phys. Rev. 178, 1097 (1969).Google Scholar
75. Glick, A. J., Longe, P., and Bose, S. M., “Effect of Electron Interactions on Soft X-Ray Emission Spectra in Metals”, in ref. 8, p. 319.Google Scholar
76. Birks, E. S., Seebold, R. E., Batt, A. P., and Grosso, J. S., “Ex-citation of Characteristic X-Rays by Protons, Electrons, and Primary X-Rays”, J. Appl. Phys. 35, 2578 (1964).Google Scholar
77. Sterk, A. A., “X-Ray Generation by Proton Bombardment” in Meuller, W. M. et al., Editors, Advances in X-Ray Analysis, 8, Plenum Press, New York, 1965, p. 189 and references therein.Google Scholar
78. Liefeld, R. J., Hanzely, S., Kerby, T. B., and Mott, D., “Soft X-Ray Spectrometric Properties of Potassium Acid Phthalate Crystals”, this volume.Google Scholar
79. Blokhin, M. A. and Sachenko, V. P., “Concerning the Shape of Energy Bands in Solids”, Bull. Ac. Sci. USSR Translation, 24, 410 (1960).Google Scholar
80. Slater, J. C., “Quantum Theory of Matter”, 2nd Edition, McGraw- Hill Book Co., New York, 1968.Google Scholar
81. Callaway, J., “Energy Band Theory”, Academic Press, New York 1964.Google Scholar
82. Bennett, L. H. and Waber, J. T., Editors, “Energy Bands in Metals and Alloys”, Gordon and Breach, New York, 1968.Google Scholar
83. Slater, J. C., “Review of the E nergy Band Problem with Recent Results'*, in ref. 82, p. 1.Google Scholar
84. Falicov, L. M., “Orthogonalized Plane Waves and Pseudo potentials; A Short Review”, in ref. 82, p. 73.Google Scholar
85. Cartrnell, E. and Fowles, G. W. A., “Valency and Molecular Structure”, 3rd Edition, Van Nostrand, Princeton, 1966.Google Scholar
86. Kittel, C., “Introduction to Solid State Physics”, 3rd. Edition, Wiley and Sons, New York, 1966, p. 89.Google Scholar
87. Figgis, B. N., “Introduction to Ligand Fields”, Interscience, New York, 1966.Google Scholar
88. Soven, P., “Coherent Potential Model of Disordered Substitutional Alloys”, in ref. 82, p. 139.Google Scholar
89. Velicky, B., Kirkpatrick, S., and Ehrenreich, H., “Single Site Approximation in the Electronic Theory of Simple Binary Alloys” Phys. Rev., 175, 747 (1968).and references therein.Google Scholar
90. Varley, J. H. O., “The Calculation of Heats of Formation of Binary Alloys”, Phil, Mag. 45, 887 (1954).Google Scholar
91. Hsieh, K. A., “The Cohesive and Elastic Properties of Noble Metals in Terms of the Electron Cell Model”, M. S. Thesis, University of Maryland, 1969.Google Scholar
92. Nagel, D. J., “Theoretical Extension and Application of the Electron Cell Model to Correlation and Alloy Problems”, unpublished.Google Scholar
93. Kohia, W., “Electronic Structure from the Standpoint of the Inhomogeneous Electron Gas”, in ref. 82, p. 65.Google Scholar
94. Yakowitz, H. and Cuthill, J. R., Nat. Bur. Stds. Mongraph 52 (1962).Google Scholar