IR operation by third harmonic generation of Tl4PbTe3 and Tl4SnS3 single crystals
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Compounds of the Tl4LnTe3 (Ln-Nd, Sm, Tb, Er, Tm) composition were synthesized by the direct interaction of stoichiometric amounts of thallium telluride Tl2Te elementary rare earth elements (REE) and tellurium in evacuated (10-2 Pa) quartz ampoules. The samples obtained were identified by differential thermal and X-ray phase analyses. Based on the data from the heating thermograms, it was shown that these compounds melt with decomposition by peritectic reactions. Analysis of powder diffraction patterns showed that they were completely indexed in a tetragonal lattice of the Tl5Te3 type (space group I4/mcm). Using the Le Bail refinement, the crystal lattice parameters of the synthesized compounds were calculated.It was found that when the thallium atoms located in the centres of the octahedra were substituted by REE atoms, there occurred a sharp decrease in the а parameter and an increase in the с parameter. This was due to the fact that the substitution of thallium atoms with REE cations led to the strengthening of chemical bonds with tellurium atoms. This was accompanied by some distortion of octahedra and an increase in the с parameter. A correlation between the parameters of the crystal lattices and the atomic number of the lanthanide was revealed: during the transition from neodymium to thulium, therewas an almost linear decrease in both parameters of the crystal lattice, which was apparently associated with lanthanide contraction. The obtained new compounds complement the extensive class of ternary compounds - structural analogues of Tl5Te3 and are of interest as potential thermoelectric and magnetic materials. References1. Berger L. I., Prochukhan V. D. Troinye almazopodobnyepoluprovodniki [Ternary diamond-like semiconductors].Moscow: Metallurgiya; 1968. 151 p. (In Russ.)2. Villars P, Prince A. Okamoto H. Handbook ofternary alloy phase diagrams (10 volume set). MaterialsPark, OH: ASM International; 1995. 15000 p.3. Tomashyk V. N. Multinary Alloys Based on III-VSemiconductors. CRC Press; 2018. 262 p. DOI: https://doi.org/10.1201/97804290553484. Babanly M. B., Chulkov E. V., Aliev Z. S. et al. Phasediagrams in materials science of topological insulatorsbased on metal chalkogenides. Russian Journal ofInorganic Chemistry. 2017;62(13): 1703–1729. DOI:https://doi.org/10.1134/S00360236171300345. Imamaliyeva S. Z., Babanly D. M., Tagiev D. B.,Babanly M. B. Physicochemical aspects of developmentof multicomponent chalcogenide phases having theTl5Te3 structure. A Review. Russian Journal of InorganicChemistry. 2018;63(13): 1703–1724 DOI: https://doi.org/10.1134/s00360236181300416. Asadov M. M., Babanly M. B., Kuliev A. A. Phaseequilibria in the system Tl–Te. Izvestiya Akademii NaukSSSR, Neorganicheskie Materialy. 1977;13(8): 1407–1410.7. Okamoto H. Te-Tl (Tellurium-Thallium). Journalof Phase Equilibria. 2001;21(5): 501. DOI: https://doi.org/10.1361/1054971007703398338. Schewe I., Böttcher P., Schnering H. G. The crystalstructure of Tl5Te3 and its relationship to the Cr5B3.Zeitschrift für Kristallographie. 1989;188(3-4): 287–298.DOI: https://doi.org/10.1524/zkri.1989.188.3-4.2879. Böttcher P., Doert Th., Druska Ch., Brandmöller S.Investigation on compounds with Cr5B3 and In5Bi3structure types. Journal of Alloys and Compounds.1997;246(1-2): 209–215. DOI: https://doi.org/10.1016/S0925-8388(96)02455-310. Imamalieva S. Z., Sadygov F. M., Babanly M. B.New thallium neodymium tellurides. InorganicMaterials. 2008;44(9): 935–938. DOI: https://doi. org/10.1134/s002016850809007011. Babanly M. B., Imamalieva S. Z., Babanly D. М.,Sadygov F. M. Tl9LnTe6 (Ln-Ce, Sm, Gd) novel structuralTl5Te3 analogues. Azerbaijan Chemical Journal. 2009(1):122–125. (In Russ., abstract in Eng.)12. Imamaliyeva S. Z., Tl4GdTe3 and Tl4DyTe3 –novel structural Tl5Te3 analogues. Physics andChemistry of Solid State. 2020;21(3): 492–495. DOI:https://doi.org/10.15330/pcss.21.3.492-49513. Wacker K. Die kristalstrukturen von Tl9SbSe6und Tl9SbTe6. Z. Kristallogr. Supple. 1991;3: 281.14. Doert T., Böttcher P. Crystal structure ofbismuthnonathalliumhexatelluride BiTl9Te6. Zeitschrift für Kristallographie - Crystalline Materials. 1994;209(1):95. DOI: https://doi.org/10.1524/zkri.1994.209.1.9515. Bradtmöller S., Böttcher P. Darstellung undkristallostructur von SnTl4Te3 und PbTl4Te3. Zeitschriftfor anorganische und allgemeine Chemie. 1993;619(7):1155–1160. DOI: https://doi.org/10.1002/zaac.1993619070216. Voroshilov Yu. V., Gurzan M. I., Kish Z. Z.,Lada L. V. Fazovye ravnovesiya v sisteme Tl-Pb-Te ikristallicheskaya struktura soedinenii tipa Tl4BIVX3 iTl9BVX6 [Phase equilibria in the Tl-Pb-Te system andthe crystal structure of Tl4BIVX3 and Tl9BVX6 compounds].Izvestiya Akademii nauk SSSR. Neorganicheskiematerialy. 1988;24: 1479–1484. (In Russ.)17. Bradtmöller S., Böttcher P. Crystal structure ofcopper tetrathallium tritelluride, CuTl4Te3. CuTl4Te3.Zeitschrift für Kristallographie - Crystalline Materials.1994;209(1): 97. DOI: https://doi.org/10.1524/zkri.1994.209.1.9718. Bradtmöller S., Böttcher P. Crystal structure ofmolybdenum tetrathallium tritelluride, MoTl4Te3.Zeitschrift für Kristallographie – Crystalline Materials.1994;209(1): 75. DOI: https://doi.org/10.1524/zkri.1994.209.1.7519. Babanly M. B., Imamalieva S. Z., Sadygov F. M.New thallium tellurides with indium and aurum.Chemical Problems (Kimya Problemlәri). 2009; 171–174.(In Russ., abstract in Eng.)20. Guo Q., Chan M., Kuropatwa B. A., Kleinke H.Enhanced thermoelectric properties of variants ofTl9SbTe6 and Tl9BiTe6. Chemistry of Materials.2013;25(20): 4097–4104. DOI: https://doi.org/10.1021/cm402593f21. Guo Q., Assoud A., Kleinke H. Improved bulkmaterials with thermoelectric figure-of-merit greaterthan 1: Tl10–xSnxTe6 and Tl10–xPbxTe6. Advanced EnergyMaterials. 2014;4(14): 1400348-8. DOI: https://doi.org/10.1002/aenm.20140034822. Bangarigadu-Sanasy S., Sankar C. R., SchlenderP., Kleinke H. Thermoelectric properties of Tl10-xLnxTe6, with Ln = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Hoand Er, and 0.25<x<1.32. Journal of Alloys andCompounds. 2013;549: 126–134. DOI: https://doi.org/10.1016/j.jallcom.2012.09.02323. Shi Y., Sturm C., Kleinke H. Chalcogenides asthermoelectric materials. Journal of Solid StateChemistry. 2019; 270: 273–279. DOI: https://doi.org/10.1016/j.jssc.2018.10.04924. Piasecki M., Brik M. G., Barchiy I. E., Ozga K.,Kityk I. V., El-Naggar A. M., Albassam A. A.,Malakhovskaya T. A., Lakshminarayana G. Bandstructure, electronic and optical features of Tl4SnX3(X= S, Te) ternary compounds for optoelectronicapplications. Journal of Alloys and Compounds.2017;710: 600–607. DOI: https://doi.org/10.1016/j.jallcom.2017.03.28025. Reshak A. H., Alahmed Z. A., Barchij I. E.,Sabov M. Yu., Plucinski K. J., Kityk I. V., Fedorchuk A. O.The influence of replacing Se by Te on electronicstructure and optical properties of Tl4PbX3 (X = Se orTe): experimental and theoretical investigations. RSCAdvances. 2015;5(124): 102173–102181. DOI: https://doi.org/10.1039/C5RA20956K26. Malakhovskay-Rosokha T. A., Filep M. J.,Sabov M. Y., Barchiy I. E., Fedorchuk A. O. Plucinski K. J.IR operation by third harmonic generation of Tl4PbTe3and Tl4SnS3 single crystals. Journal of Materials Science:Materials in Electronics. 2013;24(7): 2410–2413. DOI:https://doi.org/10.1007/s10854-013-1110-927. Isaeva A., Schoenemann R., Doert T. Syntheses,crystal structure and magnetic properties of Tl9RETe6(RE = Ce, Sm, Gd). Crystals. 2020;10(4): 277–11. DOI:https://doi.org/10.3390/cryst1004027728. Bangarigadu-Sanasy S., Sankar C. R., Dube P. A.,Greedan J. E., Kleinke H. Magnetic properties ofTl9LnTe6, Ln = Ce, Pr, Tb and Sm. Journal of Alloys andCompounds. 2014;589: 389–392. DOI: https://doi.org/10.1016/j.jallcom.2013.11.22929. Arpino K. E., Wasser B. D., and McQueen T. M.Superconducting dome and crossover to an insulatingstate in [Tl4]Tl1-xSnxTe3. APL Materials. 2015;3(4):041507. DOI: https://doi.org/10.1063/1.491339230. Arpino K. E., Wallace D. C., Nie Y. F., Birol T.,King P. D. C., Chatterjee S., Uchida M., Koohpayeh S.M., Wen J.-J., Page K., Fennie C. J., Shen K. M.,McQueen T. M. Evidence for topologically protectedsurface states and a superconducting phase in [Tl4](Tl1-xSnx)Te3 using photoemission, specific heat, andmagnetization measurements, and density functionaltheory. Physical Review Letters. 2014;112(1): 017002-5.DOI: https://doi.org/10.1103/physrevlett.112.01700231. Niu C., Dai Y., Huang B. et al. Natural threedimensionaltopological insulators in Tl4PbTe3 andTl4SnTe3. Frühjahrstagung der Deutschen PhysikalischenGesellschaft. Dresden, Germany, 30 Mar 2014 – 4 Apr2014.32. Imamalieva S. Z. Phase diagrams in thedevelopment of thallium-REE tellurides with Tl5Te3structure and multicomponent phases based on them.Overview. Kondensirovannye sredy i mezhfaznye granitsy =Condensed Matter and Interphases. 2018;20(3): 332–347.DOI: https://doi.org/10.17308/kcmf.2018.20/57033. Jia Y.Q. Crystal radii and effective ionic radii ofthe rare earth ions. Journal of Solid State Chemistry.1991; 95(1): 184-187. DOI: https://doi.org/10.1016/0022-4596(91)90388-X
Compounds of the Tl4LnTe3 (Ln-Nd, Sm, Tb, Er, Tm) composition were synthesized by the direct interaction of stoichiometric amounts of thallium telluride Tl2Te elementary rare earth elements (REE) and tellurium in evacuated (10-2 Pa) quartz ampoules. The samples obtained were identified by differential thermal and X-ray phase analyses. Based on the data from the heating thermograms, it was shown that these compounds melt with decomposition by peritectic reactions. Analysis of powder diffraction patterns showed that they were completely indexed in a tetragonal lattice of the Tl5Te3 type (space group I4/mcm). Using the Le Bail refinement, the crystal lattice parameters of the synthesized compounds were calculated.It was found that when the thallium atoms located in the centres of the octahedra were substituted by REE atoms, there occurred a sharp decrease in the а parameter and an increase in the с parameter. This was due to the fact that the substitution of thallium atoms with REE cations led to the strengthening of chemical bonds with tellurium atoms. This was accompanied by some distortion of octahedra and an increase in the с parameter. A correlation between the parameters of the crystal lattices and the atomic number of the lanthanide was revealed: during the transition from neodymium to thulium, therewas an almost linear decrease in both parameters of the crystal lattice, which was apparently associated with lanthanide contraction. The obtained new compounds complement the extensive class of ternary compounds - structural analogues of Tl5Te3 and are of interest as potential thermoelectric and magnetic materials. References1. Berger L. I., Prochukhan V. D. Troinye almazopodobnyepoluprovodniki [Ternary diamond-like semiconductors].Moscow: Metallurgiya; 1968. 151 p. (In Russ.)2. Villars P, Prince A. Okamoto H. Handbook ofternary alloy phase diagrams (10 volume set). MaterialsPark, OH: ASM International; 1995. 15000 p.3. Tomashyk V. N. Multinary Alloys Based on III-VSemiconductors. CRC Press; 2018. 262 p. DOI: https://doi.org/10.1201/97804290553484. Babanly M. B., Chulkov E. V., Aliev Z. S. et al. Phasediagrams in materials science of topological insulatorsbased on metal chalkogenides. Russian Journal ofInorganic Chemistry. 2017;62(13): 1703–1729. DOI:https://doi.org/10.1134/S00360236171300345. Imamaliyeva S. Z., Babanly D. M., Tagiev D. B.,Babanly M. B. Physicochemical aspects of developmentof multicomponent chalcogenide phases having theTl5Te3 structure. A Review. Russian Journal of InorganicChemistry. 2018;63(13): 1703–1724 DOI: https://doi.org/10.1134/s00360236181300416. Asadov M. M., Babanly M. B., Kuliev A. A. Phaseequilibria in the system Tl–Te. Izvestiya Akademii NaukSSSR, Neorganicheskie Materialy. 1977;13(8): 1407–1410.7. Okamoto H. Te-Tl (Tellurium-Thallium). Journalof Phase Equilibria. 2001;21(5): 501. DOI: https://doi.org/10.1361/1054971007703398338. Schewe I., Böttcher P., Schnering H. G. The crystalstructure of Tl5Te3 and its relationship to the Cr5B3.Zeitschrift für Kristallographie. 1989;188(3-4): 287–298.DOI: https://doi.org/10.1524/zkri.1989.188.3-4.2879. Böttcher P., Doert Th., Druska Ch., Brandmöller S.Investigation on compounds with Cr5B3 and In5Bi3structure types. Journal of Alloys and Compounds.1997;246(1-2): 209–215. DOI: https://doi.org/10.1016/S0925-8388(96)02455-310. Imamalieva S. Z., Sadygov F. M., Babanly M. B.New thallium neodymium tellurides. InorganicMaterials. 2008;44(9): 935–938. DOI: https://doi. org/10.1134/s002016850809007011. Babanly M. B., Imamalieva S. Z., Babanly D. М.,Sadygov F. M. Tl9LnTe6 (Ln-Ce, Sm, Gd) novel structuralTl5Te3 analogues. Azerbaijan Chemical Journal. 2009(1):122–125. (In Russ., abstract in Eng.)12. Imamaliyeva S. Z., Tl4GdTe3 and Tl4DyTe3 –novel structural Tl5Te3 analogues. Physics andChemistry of Solid State. 2020;21(3): 492–495. DOI:https://doi.org/10.15330/pcss.21.3.492-49513. Wacker K. Die kristalstrukturen von Tl9SbSe6und Tl9SbTe6. Z. Kristallogr. Supple. 1991;3: 281.14. Doert T., Böttcher P. Crystal structure ofbismuthnonathalliumhexatelluride BiTl9Te6. Zeitschrift für Kristallographie - Crystalline Materials. 1994;209(1):95. DOI: https://doi.org/10.1524/zkri.1994.209.1.9515. Bradtmöller S., Böttcher P. Darstellung undkristallostructur von SnTl4Te3 und PbTl4Te3. Zeitschriftfor anorganische und allgemeine Chemie. 1993;619(7):1155–1160. DOI: https://doi.org/10.1002/zaac.1993619070216. Voroshilov Yu. V., Gurzan M. I., Kish Z. Z.,Lada L. V. Fazovye ravnovesiya v sisteme Tl-Pb-Te ikristallicheskaya struktura soedinenii tipa Tl4BIVX3 iTl9BVX6 [Phase equilibria in the Tl-Pb-Te system andthe crystal structure of Tl4BIVX3 and Tl9BVX6 compounds].Izvestiya Akademii nauk SSSR. Neorganicheskiematerialy. 1988;24: 1479–1484. (In Russ.)17. Bradtmöller S., Böttcher P. Crystal structure ofcopper tetrathallium tritelluride, CuTl4Te3. CuTl4Te3.Zeitschrift für Kristallographie - Crystalline Materials.1994;209(1): 97. DOI: https://doi.org/10.1524/zkri.1994.209.1.9718. Bradtmöller S., Böttcher P. Crystal structure ofmolybdenum tetrathallium tritelluride, MoTl4Te3.Zeitschrift für Kristallographie – Crystalline Materials.1994;209(1): 75. DOI: https://doi.org/10.1524/zkri.1994.209.1.7519. Babanly M. B., Imamalieva S. Z., Sadygov F. M.New thallium tellurides with indium and aurum.Chemical Problems (Kimya Problemlәri). 2009; 171–174.(In Russ., abstract in Eng.)20. Guo Q., Chan M., Kuropatwa B. A., Kleinke H.Enhanced thermoelectric properties of variants ofTl9SbTe6 and Tl9BiTe6. Chemistry of Materials.2013;25(20): 4097–4104. DOI: https://doi.org/10.1021/cm402593f21. Guo Q., Assoud A., Kleinke H. Improved bulkmaterials with thermoelectric figure-of-merit greaterthan 1: Tl10–xSnxTe6 and Tl10–xPbxTe6. Advanced EnergyMaterials. 2014;4(14): 1400348-8. DOI: https://doi.org/10.1002/aenm.20140034822. Bangarigadu-Sanasy S., Sankar C. R., SchlenderP., Kleinke H. Thermoelectric properties of Tl10-xLnxTe6, with Ln = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Hoand Er, and 0.25<x<1.32. Journal of Alloys andCompounds. 2013;549: 126–134. DOI: https://doi.org/10.1016/j.jallcom.2012.09.02323. Shi Y., Sturm C., Kleinke H. Chalcogenides asthermoelectric materials. Journal of Solid StateChemistry. 2019; 270: 273–279. DOI: https://doi.org/10.1016/j.jssc.2018.10.04924. Piasecki M., Brik M. G., Barchiy I. E., Ozga K.,Kityk I. V., El-Naggar A. M., Albassam A. A.,Malakhovskaya T. A., Lakshminarayana G. Bandstructure, electronic and optical features of Tl4SnX3(X= S, Te) ternary compounds for optoelectronicapplications. Journal of Alloys and Compounds.2017;710: 600–607. DOI: https://doi.org/10.1016/j.jallcom.2017.03.28025. Reshak A. H., Alahmed Z. A., Barchij I. E.,Sabov M. Yu., Plucinski K. J., Kityk I. V., Fedorchuk A. O.The influence of replacing Se by Te on electronicstructure and optical properties of Tl4PbX3 (X = Se orTe): experimental and theoretical investigations. RSCAdvances. 2015;5(124): 102173–102181. DOI: https://doi.org/10.1039/C5RA20956K26. Malakhovskay-Rosokha T. A., Filep M. J.,Sabov M. Y., Barchiy I. E., Fedorchuk A. O. Plucinski K. J.IR operation by third harmonic generation of Tl4PbTe3and Tl4SnS3 single crystals. Journal of Materials Science:Materials in Electronics. 2013;24(7): 2410–2413. DOI:https://doi.org/10.1007/s10854-013-1110-927. Isaeva A., Schoenemann R., Doert T. Syntheses,crystal structure and magnetic properties of Tl9RETe6(RE = Ce, Sm, Gd). Crystals. 2020;10(4): 277–11. DOI:https://doi.org/10.3390/cryst1004027728. Bangarigadu-Sanasy S., Sankar C. R., Dube P. A.,Greedan J. E., Kleinke H. Magnetic properties ofTl9LnTe6, Ln = Ce, Pr, Tb and Sm. Journal of Alloys andCompounds. 2014;589: 389–392. DOI: https://doi.org/10.1016/j.jallcom.2013.11.22929. Arpino K. E., Wasser B. D., and McQueen T. M.Superconducting dome and crossover to an insulatingstate in [Tl4]Tl1-xSnxTe3. APL Materials. 2015;3(4):041507. DOI: https://doi.org/10.1063/1.491339230. Arpino K. E., Wallace D. C., Nie Y. F., Birol T.,King P. D. C., Chatterjee S., Uchida M., Koohpayeh S.M., Wen J.-J., Page K., Fennie C. J., Shen K. M.,McQueen T. M. Evidence for topologically protectedsurface states and a superconducting phase in [Tl4](Tl1-xSnx)Te3 using photoemission, specific heat, andmagnetization measurements, and density functionaltheory. Physical Review Letters. 2014;112(1): 017002-5.DOI: https://doi.org/10.1103/physrevlett.112.01700231. Niu C., Dai Y., Huang B. et al. Natural threedimensionaltopological insulators in Tl4PbTe3 andTl4SnTe3. Frühjahrstagung der Deutschen PhysikalischenGesellschaft. Dresden, Germany, 30 Mar 2014 – 4 Apr2014.32. Imamalieva S. Z. Phase diagrams in thedevelopment of thallium-REE tellurides with Tl5Te3structure and multicomponent phases based on them.Overview. Kondensirovannye sredy i mezhfaznye granitsy =Condensed Matter and Interphases. 2018;20(3): 332–347.DOI: https://doi.org/10.17308/kcmf.2018.20/57033. Jia Y.Q. Crystal radii and effective ionic radii ofthe rare earth ions. Journal of Solid State Chemistry.1991; 95(1): 184-187. DOI: https://doi.org/10.1016/0022-4596(91)90388-X
Bicolour illumination by 1.54/0.77 lm 20 ns pulsed Er:glass laser beams leads to enhancement of the initial effective piezoelectric coefficients for Ag 0.5 Pb 1.75 GeS 4 and Ag 0.5 Pb 1.75 GeS 3 Se crystals in a different way. The contribution of the photo-thermal effect did not exceed 4 %. The relaxation processes last up to 50 ms and are completely reversible with respect to piezoelectricity. The effect is reproducible even after more than 100 cycles of the photoinduced laser treatment. The use only of the mopnochromatic wavelengths 1.54 lm (0.77 lm) did not show sufficient enhancement of the effect, and the changes were commensurable with the background. The efficiency of the laser photoinduced treatment depends on the angle between the bicolour photoinducing beams, ratio of their intensities and their relaxation behaviour is a slightly different. However, at at 50 ms the photoinduced piezoelectric signal disappears for the both samples. It is crucial that laser polarizations of the photoinducing beams do not play important role.
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