Abstract

Room-temperature absorption and reflectivity spectra of MnPSe3 seleniophosphate crystals have been analyzed from 1.0 to 5.5 eV. A general consistency has been found between the two types of data. From the absorption data an optical energy gap of 2.27 eV was deduced for this compound, in agreement with the literature. A weak and broad absorption band below the fundamental absorption edge was also observed. The reflectivity spectrum exhibits five structures, of which two are located below the fundamental absorption threshold, whereas the others are positioned at higher energies. Spectra have been found to be similar to those reported for the corresponding MnPS3 thiophosphate, with all the structures beyond the absorption edge shifted toward lower energies. For photon energies greater than absorption edge the MnPSe3 reflectivity spectrum also shows a similarity to those obtained for the cadmium and mercury seleniophosphates. With this resemblance taken into account, the observed structures have been interpreted in terms of both the so-called transition-metal weakly interacting model and the weak-crystal-field theory. A simplified energy-band diagram, in which the electronic transitions that are responsible for the noted absorption and reflectivity features are clearly indicated, is drawn.

© 1999 Optical Society of America

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  1. M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
    [CrossRef]
  2. A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
    [CrossRef]
  3. R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
    [CrossRef]
  4. O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
    [CrossRef]
  5. R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).
  6. G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
    [CrossRef]
  7. S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
    [CrossRef]
  8. R. Brec, Solid State Ion. 22, 3 (1986).
    [CrossRef]
  9. P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
    [CrossRef] [PubMed]
  10. I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
    [CrossRef]
  11. D. S. McClure, in Advances in Research and Applications, F. Seitz and D. Turnbull, eds., Vol. 9 of Solid State Physics (Academic, New York, 1959), p. 399.
  12. L. E. Orgel, J. Chem. Phys. 23, 1004 (1955).
    [CrossRef]
  13. B. Di Bartolo, Optical Interactions in Solids (Wiley, New York, 1968), pp. 362, 426.
  14. V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
    [CrossRef]
  15. J. W. Stout, J. Chem. Phys. 31, 709 (1959).
    [CrossRef]
  16. V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
    [CrossRef]
  17. M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
    [CrossRef]
  18. C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
    [CrossRef]
  19. C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
    [CrossRef]
  20. M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
    [CrossRef]

1997 (3)

I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
[CrossRef]

C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
[CrossRef]

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

1994 (1)

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

1991 (1)

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

1988 (1)

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

1986 (2)

R. Brec, Solid State Ion. 22, 3 (1986).
[CrossRef]

V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
[CrossRef]

1985 (1)

O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
[CrossRef]

1982 (3)

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

1981 (1)

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

1980 (1)

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

1979 (1)

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

1978 (1)

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

1959 (1)

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

1955 (1)

L. E. Orgel, J. Chem. Phys. 23, 1004 (1955).
[CrossRef]

Anderegg, J. W.

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

Balkanski, M.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Benedek, G.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Bernasconi, M.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Brec, R.

R. Brec, Solid State Ion. 22, 3 (1986).
[CrossRef]

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

Calareso, C.

C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
[CrossRef]

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

Clement, R.

I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
[CrossRef]

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Grasso, V.

C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
[CrossRef]

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
[CrossRef]

Husser, O. E.

O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
[CrossRef]

Jouanne, M.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Julien, C.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Kanamaru, F.

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

Khumalo, F. S.

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

Koizumi, M.

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

Lacroix, P. G.

I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
[CrossRef]

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Ladoux, I.

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Lagadic, I.

I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
[CrossRef]

Le Flem, G.

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

Leveque, G.

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

Levy, F.

O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
[CrossRef]

Louisy, A.

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

Lynch, D. W.

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

Marra, G. L.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Miglio, L.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Nakatani, K.

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Neri, F.

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

Olson, C. G.

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

Orgel, L. E.

L. E. Orgel, J. Chem. Phys. 23, 1004 (1955).
[CrossRef]

Otani, S.

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

Ouvrard, G.

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

Piacentini, M.

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
[CrossRef]

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

Rossat-Mignad, J.

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

Rouxel, J.

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

Santangelo, S.

V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
[CrossRef]

Scagliotti, M.

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Schleich, D.

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

Schleich, D. M.

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

Segransan, P.

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

Shimada, M.

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

Silipigni, L.

C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
[CrossRef]

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

Stout, J. W.

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

von Kanel, H.

O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
[CrossRef]

Wiedenmann, A.

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

Zyss, J.

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Ann. Chim. (Paris) (1)

R. Brec, D. Schleich, A. Louisy, and J. Rouxel, Ann. Chim. (Paris) 3, 347 (1978).

Chem. Mater. (1)

I. Lagadic, P. G. Lacroix, and R. Clement, Chem. Mater. 9, 2004 (1997).
[CrossRef]

Chem. Phys. (2)

M. Piacentini, F. S. Khumalo, G. Leveque, C. G. Olson, and D. W. Lynch, Chem. Phys. 72, 61 (1982).
[CrossRef]

M. Piacentini, F. S. Khumalo, C. G. Olson, J. W. Anderegg, and D. W. Lynch, Chem. Phys. 65, 289 (1982).
[CrossRef]

Inorg. Chem. (2)

S. Otani, M. Shimada, F. Kanamaru, and M. Koizumi, Inorg. Chem. 19, 1249 (1980).
[CrossRef]

R. Brec, D. M. Schleich, G. Ouvrard, A. Louisy, and J. Rouxel, Inorg. Chem. 18, 1814 (1979).
[CrossRef]

J. Appl. Phys. (1)

C. Calareso, V. Grasso, and L. Silipigni, J. Appl. Phys. 82, 6228 (1997).
[CrossRef]

J. Chem. Phys. (2)

L. E. Orgel, J. Chem. Phys. 23, 1004 (1955).
[CrossRef]

J. W. Stout, J. Chem. Phys. 31, 709 (1959).
[CrossRef]

J. Electrochem. Soc. (1)

O. E. Husser, H. von Kanel, and F. Levy, J. Electrochem. Soc. 132, 810 (1985).
[CrossRef]

J. Phys. Chem. Solids (1)

G. Le Flem, R. Brec, G. Ouvrard, A. Louisy, and P. Segransan, J. Phys. Chem. Solids 43, 455 (1982).
[CrossRef]

J. Phys. Condens. Matter (1)

C. Calareso, V. Grasso, F. Neri, and L. Silipigni, J. Phys. Condens. Matter 9, 4791 (1997).
[CrossRef]

Nuovo Cimento D (1)

V. Grasso, F. Neri, L. Silipigni, and M. Piacentini, Nuovo Cimento D 13, 633 (1991).
[CrossRef]

Phys. Rev. B (1)

M. Bernasconi, G. L. Marra, G. Benedek, L. Miglio, M. Jouanne, C. Julien, M. Scagliotti, and M. Balkanski, Phys. Rev. B 38, 12089 (1988).
[CrossRef]

Science (1)

P. G. Lacroix, R. Clement, K. Nakatani, J. Zyss, and I. Ladoux, Science 263, 658 (1994).
[CrossRef] [PubMed]

Solid State Commun. (1)

A. Wiedenmann, J. Rossat-Mignad, A. Louisy, R. Brec, and J. Rouxel, Solid State Commun. 40, 1067 (1981).
[CrossRef]

Solid State Ion. (1)

R. Brec, Solid State Ion. 22, 3 (1986).
[CrossRef]

Solid State Ionics (1)

V. Grasso, S. Santangelo, and M. Piacentini, Solid State Ionics 20, 9 (1986).
[CrossRef]

Other (2)

B. Di Bartolo, Optical Interactions in Solids (Wiley, New York, 1968), pp. 362, 426.

D. S. McClure, in Advances in Research and Applications, F. Seitz and D. Turnbull, eds., Vol. 9 of Solid State Physics (Academic, New York, 1959), p. 399.

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Figures (3)

Fig. 1
Fig. 1

Room-temperature MnPSe3 optical absorption spectrum in the region of the Mn 3d3d transitions (open circles). Solid curve, best-fit calculated absorption spectrum; dashed curve, the Gaussian curve. The inset shows the room-temperature MnPS3 absorption spectrum for comparison.

Fig. 2
Fig. 2

Room-temperature MnPSe3 reflectivity spectrum. The inset compares the room-temperature reflectivity spectra of some MPX3 compounds, such as MnPS3 [curve (a)], CdPSe3 [curve (b)], and HgPSe3 [curve (c)].

Fig. 3
Fig. 3

Simplified energy-band diagram that we have adopted to describe the electronic structure of MnPSe3. It is derived from the semiempirical energy-level scheme formulated by Piacentini et al.17 for NiPS3 and similar compounds. Arrows, the electronic transitions responsible for the observed absorption and reflectivity structures (transitions I–IV) and for the absorption edge (transition II).

Tables (1)

Tables Icon

Table 1 Height of the Absorption Maximum (in arbitrary units) A, Its Energy E0, and the Half-Width σ of the Gaussian Curve A(exp{-log(2)[(ω-E0)/σ]2}) Used To Fit the Absorption Band Associated with the First Mn 3d3d Transition in the MnPSe3 Room-Temperature Absorption Spectruma

Metrics