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Optical properties of A2IVB2VC6VI  ferroelectrics-semiconductors: the effect of temperature and hydrostatic pressure. (Review)
Gerzanich E.I.

Uzhgorod National University, 52 Voloshyn St., 88000 Uzhgorod, Ukraine

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In this review the results of experimental studies for the influence of temperature and high pressure on the fundamental absorption edge, optical birefringence and vibrational spectra of  A2IVB2VC6VI-group crystals are presented. It is revealed that the high-energy part of the absorption edge is described by the Urbach rule, while its low-energy part is formed by indirect optical transitions. Violation of the Urbach rule is detected in the region of incommensurate phase. The temperature and baric coefficients of the forbidden gap in the ferroelectric, paraelectric and incommensurate phases are found to be negative. Electron-phonon interaction plays a major part in the temperature changes of the bandgap. According to the theory, the bandgap suffers characteristic anomalies that depend upon the phase transition order. The critical indices of the order parameter and heat capacity and the Landau-Ginzburg expansion coefficients derived from the baric studies of optical birefringence agree well with a presence of Lifshitz point at the p,T-diagrams of the crystals under test. Relative shift in the frequencies of the Raman spectra occurring under mechanical stresses testifies a notable nonequivalence of atomic bonds and a possibility of dividing the vibrations in Sn2P2S6 into the external and internal ones. The results of baric investigations of the Raman spectra show that the structural transformation in Sn2P2S6 is mainly linked to Sn-S bonds. The results analysed by us testify a possibility for practical applications of Sn2P2S6 ferroelectrics as a converter of coherent long-wave radiation into shorter-wave one.

Keywords: optical absorption, birefringence, phase diagram, ferroelectric crystals, incommensurate phase

PACS: 42.25.Bs, 78.20.Fm, 77.80.–e, 77.80.Bh
UDC : 535.341
Ukr. J. Phys. Opt. 9 129-163   doi: 10.3116/16091833/9/3/129/2008
Received: 19.12.2007

REFERENCES

1. Carpentier G and Nitsche R, 1974. Ferroelectricity in Sn2P2S6. Mat. Res. Bull. 9: 1097–1103.
        doi:10.1016/0025-5408(74)90023-3 http://dx.doi.org/10.1016/0025-5408(74)90023-3
2. Ditmar G and Shafer H, 1974. Die Structur des Di-Linn-Hexathiohipodiphosphats Sn2P2S6. Z. Naturforsch. 298: 312–317.
3. Nitsche R and Wild R, 1974. Crystal growth of metal-phosphorus-sulfur compounds by vapor transport. Mat. Res. Bull. 9: 419–424.
4. Carpentier C D and Nitsche R, 1974. Vapour growth and crystal data of thio(seleno)-hypodiphosphate Sn2P2S6, Sn2P2Se6, Pb2P2S6, Pb2P2Se6 and their mixed crystals. Mat. Res. Bull. 9: 401–410.
        doi:10.1016/0025-5408(74)90207-4 http://dx.doi.org/10.1016/0025-5408(74)90207-4
5. Klingen W, Ott R and Hahn H, 1973. Uber die Darstellung und Eigenschaften von Hexathio-und Hexaselenohypodiphosphaten. Z. Anorg. Allg. Chem. 396: 271–278.
        doi:10.1002/zaac.19733960305 http://dx.doi.org/10.1002/zaac.19733960305
6. Vysochanskii Yu M and Slivka V Yu, Ferroelectrics of Sn2P2S6 family: Properties in the vicinity of Lifshitz: Lvov: Nauchnoye Izdaniye, 1994. 264 p.
7. Slivka A G, Gerzanich E I, Tyagur Yu I and Yatskovich I I, 1986. Phase diagram of ferroelectric solid solutions Sn2P2(SexS1-x)6. Ukr. Fiz. Zhurn. 31: 1372–1374.
8. Shusta V S, Gerzanich E I, Slivka A G, Guranich P P and Bobela V A, 1993. Phase transitions and physical properties of (PbySn1-y)P2S6 crystals at high hydrostatic pressure. Ferroelectrics. 145: 61–71.
9. Guranich P P, Gerzanich E I, Slivka A G, Shusta V S and Bobela V A, 1992. Phase p,T,x-diagram and peculiarities of physical properties of (PbySn1-y)P2Se6 crystals with on incommensurate phase. Ferroelectrics. 132: 173–183.
        doi:10.1080/00150199208009082 http://dx.doi.org/10.1080/00150199208009082
10. Slivka A G, Gerzanich E I, Shusta V S and Guranich P P, 1999. Effect of isomorphous substitution and external hydrostatic pressure on the fundamental optical absorption edge of Sn(Pb)2P2 S(Se)6 crystals. Izv. Vuzov., Ser. Fiz. 9: 23–28.
11. Buturlakin A P, Gerzanich E I, Tyagur Yu I, Gurzan M I and Chepur D V, 1980. Influence of high hydrostatic pressure on the optical properties of ferroelectric-semiconductor Sn2P2S6. Materials of III Republic Seminar «High Pressure and Properties of Materials», Kyiv, Naukova Dumka. 2: 29–32.
12. Gerzanich E I, Buturlakin A P, Tyagur Yu I, Gurzan M I and Chepur D V, 1980. Studies of semiconducting properties of ferroelectric crystals Sn2P2S6 along their p,T-diagram. Izv. Vuzov, Ser. Fiz. 23: 93–96.
13. Slivka A G, Gerzanich E I, Studenyak I P, Kovach D Sh and Seykovskaya L A, 1987. Absorption edge of Sn2P2(Se0.30S0.70)6 crystals and its dependence on temperature and hydrostatic pressure. Ukr. Fiz. Zhurn. 32: 1819–1822.
14. Gerzanich E I, Slivka A G, Guranich P P and Shusta V S, 1992. Influence of anionic and cationic substitutions on the fundamental absorption in Sn2P2S6 crystals. Republican Scientific Technical Collection «Materials for Optoelectronics», Kyiv, Tekhnika. 1: 31–38.
15. Shusta V S, Gerzanich E I, Slivka A G, Guranich P P and Bobela V A, 1992. Urbach-like behaviour of the absorption edge of ferroelectric crystals (PbySn1-y)2P2S6. Ukr. Fiz. Zhurn. 37: 561–565.
16. Gerzanich E I, Guranich P P, Slivka A G, Shusta V S, Gurzan M I and Kedyulich V M, 1997. Baric dependence of fundamental absorption edge in the course of phase transitions in the proper ferroelectrics of Sn2P2S6 type. Izv. Vuzov., Ser. Fiz. 8: 82–85.
17. Studenyak I P, Mitrovcij V V, Kovach Gy Sh, Mykajlo O A, Gurzan M I and Vysochanskii Yu M, 2001. Temperature Variation of optical Absorption Edge in Sn2P2S6 and SnP2S6 crystals. Ferroelectrics. 254: 295–310.
        doi:10.1080/00150190108215009 http://dx.doi.org/10.1080/00150190108215009
18. Vlokh R O, Grabar A A and Kityk I V, 1991. Electronic structure of single crystals Sn2P2S6. Izv. FN SSSR., Ser. Neorg. Mat. 27: 2052–2054.
19. Yakubovskii M A, Zametin V I, Rabkin M M and Fesenko E G, 1980. Absorption edge of calcium titanate. Fiz. Tverd. Tela. 22: 3523–3528.
20. Sumi H and Toyozawa Y, 1971. Urbach-Martienssen rule and exciton trapped monentarily by lattice vibrations. J. Phys. Soc. Jap. 31: 342–358.
        doi:10.1143/JPSJ.31.342 http://dx.doi.org/10.1143/JPSJ.31.342
21. Skettrup T, 1978. Urbach’s rule derived from thermal fluctuations in the bang-gap energy. Phys. Rev. B. 18: 2622–2631.
        doi:10.1103/PhysRevB.18.2622 http://dx.doi.org/10.1103/PhysRevB.18.2622
22. Glebov L B and Tolstoy N N, 1975. Influence of temperature on the fundamental absorption spectrum of soda-lime glass. Fiz. Khim. Stekla. 1: 239–242.
23. Cody G D, Tiedje T, Abeles B. Brooks B and Goldstein Y, 1981. Disordering and the Optical-Absorption Edge of Hydrogenated Amorphous Silicon. Phys. Rev. Lett. 47: 1480–1483.
        doi:10.1103/PhysRevLett.47.1480 http://dx.doi.org/10.1103/PhysRevLett.47.1480
24. Zametin V I, Yakubovskii M A and Rabkin L I, 1979. Anomalies of the absorption edge caused by phase transitions. Fiz. Tverd. Tela. 21: 491–498.
25. Vlokh O G, Polovinko I I and Sveleba S A, 1988. Optical absorption of incommensurate crystals (N(CH3)4)2CuCl4. Opt. Spektr. 65: 1272–1275.
26. Strukov B A and Levanyuk A P, Physical basics of ferroelectric properties of crystals: Moscow: Nauka, 1983. 240 p.
27. Parsamyan T K, Khasanov S S, Shehtman V M, Vysochanskii Yu M and Slivka V Yu, 1985. Incommensurate phase in proper ferroelectrics Sn2P2Se6. Fiz. Tverd. Tela. 27: 3327–3331.
28. Vysochanskii Yu M, Slivka V Yu, Voroshylov Yu V and Gurzan M I, 1979. Model of phase transition in ferroelectric-semiconductor Sn2P2S6 and its lattice dynamics. Fiz. Tverd. Tela. 21: 2402–2408.
29. Slivka A G, 2001. Absorption edge of Sn(Pb)2P2S(Se)6 crystals under hydrostatic pressure. Ukr. J. Phys. Opt. 2: 171–178.
        doi:10.3116/16091833/2/4/171/2001 http://dx.doi.org/10.3116/16091833/2/4/171/2001
30. Slivka A G, Gerzanich E I, Tyagur Yu I and Korda N F, 1988. Splitting of phase transition in the ferroelectric solid solutions Sn2P2(SexS1-x)6 under high pressure. Izv. Vuzov, Ser. Fiz. 2: 28–32.
31. Guranich P P, Gerzanich E I, Shusta V S, Slivka A G, 1988. Phase p,T,x-diagram of ferroelectric crystals (PbySn1-y)P2Se6 with incommensurate phase. Fiz. Tverd. Tela. 30: 1189–1191.
32. Shusta V S, Tovt V V, Slivka A G, Guranich P P, Gerzanich E I and Kuritsa I Y, 2005. Temperature and pressure effect on absorption edge in (Zn0.05Sn0.95)2P2S6 crystal. Ferroelectrics. 317: 83–87.
        doi:10.1080/00150190590963499 http://dx.doi.org/10.1080/00150190590963499
33. Maclean T P, 1960. The absorption edge spectrum of semiconductors. Progress in Semiconductors. 5: 53–102.
34. Gerzanich E I, Bryzgalov I A, Rakcheev A D and Lyahovitskaya V A, 1968. Optical constants of single crystals SbSI. Kristallogr. 13: 898–900.
35. Patent No. 33019 (Ukraine). Express method for studying energetic structure of solids in the region of phase transitions / Shusta V S, Guranich P P, Gerzanich O I and Slivka O G, Bull. No. 5, 15.05.2003.
36. Guranich P P, Kabal R V, Slivka A G and Gerzanich E I, 2001. Pressure behaviour of the birefringence in Sn2P2(SexS1-x)6 crystals in the vicinity of the Lifshitz point. Ukr. J. Phys. Opt. 2: 179–181.
        doi:10.3116/16091833/2/4/179/2001 http://dx.doi.org/10.3116/16091833/2/4/179/2001
37. Isaverdiyev A A, Levanyuk A P, Lebedev N I, Sigov A S, 1989. Influence of point defects on the properties of ferroelectrics with a single axis of spontaneous polarization near the Lifshitz point. Fiz. Tverd. Tela. 31: 272–274.
38. Folk R and Moser G, 1993. Lifshitz point in uniaxial ferroelectrics. Phys. Rev. B. 47: 13992–13997.
        doi:10.1103/PhysRevB.47.13992 http://dx.doi.org/10.1103/PhysRevB.47.13992
39. Hasser I, Abdel-Hady A and Folk R, 1997. Specific-heat amplitude ratio near a Lifshitz point. Phys. Rev. B.56: 154–160.
        doi:10.1103/PhysRevB.56.154 http://dx.doi.org/10.1103/PhysRevB.56.154
40. Grabar A A, Vysochanskii Yu M, Melnik N N, Subbotin S I, Panfilov V V and Slivka V Yu, 1984. Influence of hydrostatic pressure on the vibrational spectra of Sn2P2S6 ferroelectrics. Fiz. Tverd. Tela. 26: 65–68.
41. Major M M, Koperlyos B M, Savchenko B A, Gurzan M I, Morozova O V and Korda N F, 1983. Heat capacity and linear expansion of Sn2P2(SexS1-x)6 crystals. Fiz. Tverd. Tela. 25: 214–223.
42. USSR Inventors Certificate No. 1329420 / Published 05.07.1982. Method for the conversion of coherent long-wave infrared radiation with increasing frequency / Vysochanskii Yu M, Slivka V Yu, Furtsev V G, Grabar A A and Chepur D V.

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