Abstract
The effect of pseudovacancies on the density of electronic states of valence electrons in AgGaS2, CdGa2S4, and InPS4 is studied both experimentally, by means of X-ray spectroscopy, and theoretically, by calculating the partial densities of electronic states using the local coherent potential. The compounds under study are the derivatives of the sphalerite structural type (doubled cell) with gradually increasing deficiency of metals from \(Ag_4^I Ga_4^{III} S_8 \) to \(\square _2^{II} Cd_2^{II} Ga_4^{III} S_8 \) and further to \(\square _2^{III} In_2^{III} \square _2^V P_2^V S_8 \), where \(\square \) is a vacancy. The environment of the metal atoms remains tetrahedral, while that of the sulfur atoms changes with increasing number of vacancies from four (AgGaS2) to three (CdGa2S4) and two (InPS4). For the compounds under study, SK and PK X-ray emission and absorption spectra were recorded at a resolution of about 0.2 eV, and the local partial densities of states were calculated for all components of the compounds. The theoretical curves practically coincide in shape and energy position of fine structure elements with the corresponding experimental curves. This allowed reliable conclusions about the energy positions of electronic states at the top of the valence band and about the dependence of the SK emission and absorption spectra in the series of compounds under study on variation of the crystal structure and on the chemical composition of the nearest surroundings of sulfur atoms.
Similar content being viewed by others
REFERENCES
Yu. V. Voroshilov and V. Yu. Slivka, Anoxide Materials for Electronics [in Russian], Vishcha Shkola, Lvov (1989).
Yu. A. Khazitarkhanov, L. M. Suslikov, Z. P. Gadmashi, and V. Yu. Slivka, Kvant. Élektr. (Kiev), 44, No. 24, 24-38 (1993).
S. C. Abrahams and J. L. Bernstein, J. Chem. Phys., 59, No. 4, 1625-1629 (1973).
S. T. Kshirsagar and A. P. B. Sinha, J. Mater. Sci.,12, No. 12, 2441-2446 (1977).
R. Diehl and C. D. Carpentier, Acta Crystallogr., 334, No. 4, 1097-1105 (1978).
A. Baldereschi, F. Meloni, F. Aymerich, and G. Mula, Solid State Commun., 21, No. 1, 113-116 (1977).
G. Margaritondo, A. D. Katnani, and F. Levy, Phys. Status Solidi (b), 103, No. 2, 725-731 (1981).
M. A. Blokhin and I. G. Shveitser, X-Ray Spectroscopy. Handbook [in Russian], Nauka, Moscow (1982).
B. L. Gyorffy and M. J. Stott, Band Structure Spectroscopy of Metals and Alloys, D. Fabian (ed.), New York (1973), pp. 385-403.
G. V. Volf, V. V. Dyakin, and V. P. Shirokovskii, Fiz. Met. Materialoved., 38, No. 6, 949-956 (1974).
A. Kisel, G. Dalba, P. Fornasini, et al., Phys. Rev. B, 39, No. 11, 7895-7904 (1989).
I. Ya. Nikiforov and A. V. Kolpachev, Phys. Status Solidi (b), 148, No. 2, 205-211 (1988).
A. A. Lavrentiev, B. V. Gabrel'yan, and I. Ya. Nikiforov, Zh. Strukt. Khim., 39, No. 6, 1076-1082 (1998).
M. J. Luciano and C. J. Vesely, Appl. Phys. Lett., 23, No. 2, 60-61 (1973).
J. H. Scofield, J. Electr. Spectrosc., 8, 129-137 (1976).
E. P. Domasheskaya and V. A. Terekhov, Phys. Status Solidi (b), 105, No. 2, 121-127 (1981).
E. P. Domasheskaya, L. N. Marshakova, V. A. Terekhov, et al., ibid., 106, No. 2, 429-435 (1981).
A. A. Lavrentiev, A. N. Gusatinskii, A. V. Soldatov, et al., J. Phys. C: Solid State Phys., 20, 3445-3452 (1987).
A. A. Lavrentiev, B. V. Gabrel'yan, and I. Ya. Nikiforov, Zh. Strukt. Khim., 41, No. 3, 515-524 (2000).
A. V. Novoselov and V. B. Lazarev (eds.), Physicochemical Properties of Semiconductors. Handbook [in Russian], Nauka, Moscow (1979).
A. N. Gusatinskii, A. A. Lavrentiev, M. A. Blokhin, and V. Yu. Slivka, Solid State Commun., 57, No. 6, 389-393 (1986).
B. F. Ormont, Introduction to Physical Chemistry and Crystal Chemistry of Semiconductors [in Russian], Vysshaya Shkola, Moscow (1982).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lavrentiev, A.A., Gabrelyan, B.V., Dubeiko, V.A. et al. Electronic Energy Structure of a Series of Chalcopyrite-Like Compounds AgGaS2–CdGa2S4–InPS4. Journal of Structural Chemistry 43, 69–79 (2002). https://doi.org/10.1023/A:1016021832411
Issue Date:
DOI: https://doi.org/10.1023/A:1016021832411