The chalcogenides of p-block elements constitute a significant category of materials with substantial potential for advancing the field of electronic and optoelectronic devices. This is attributed to their exceptional characteristics, including elevated carrier mobility and the ability to fine-tune band gaps through solid solution formation. These compounds exhibit diverse structures, encompassing both three-dimensional and two-dimensional configurations, the latter exemplified by the compound In2Se3. Sesqui-chalcogenides were synthesized through the direct reaction of highly pure elements within a quartz ampoule. Their single-phase composition was confirmed using X-ray diffraction, and the morphology and chemical composition were characterized using scanning electron microscopy. The compositions of all six materials were also confirmed using X-ray photoelectron spectroscopy and Raman spectroscopy. This investigation delves into the thermodynamic properties of indium and gallium sesqui-chalcogenides. It involves low-temperature heat capacity measurements to evaluate standard entropies and Tian-Calvet calorimetry to elucidate the temperature dependence of heat capacity beyond the reference temperature of 298.15 K, as well as the enthalpy of formation assessed from DFT calculations.

Department of Inorganic Chemistry Faculty of Chemical Technology University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

Department of Physical Chemistry Faculty of Chemical Engineering University of Chemistry and Technology Prague Technická 5 166 28 Prague Czech Republic

Institute of Macromolecular Chemistry Czech Academy of Sciences Heyrovského Nám 2 162 06 Prague Czech Republic

See more in PubMed

Chhowalla M., Jena D., Zhang H. Two-dimensional semiconductors for transistors. Nat. Rev. Mater. 2016;1:16052. doi: 10.1038/natrevmats.2016.52. DOI

Zhang Y., Rubio A., Lay G.L. Emergent elemental two-dimensional materials beyond graphene. J. Phys. D Appl. Phys. 2017;50:053004. doi: 10.1088/1361-6463/aa4e8b. DOI

Ponraj J.S., Xu Z.-Q., Dhanabalan S.C., Mu H., Wang Y., Yuan J., Li P., Thakur S., Ashrafi M., McCoubrey K., et al. Photonics and optoelectronics of two-dimensional materials beyond graphene. Nanotechnology. 2016;27:462001. doi: 10.1088/0957-4484/27/46/462001. PubMed DOI

Browning R., Kuperman N., Moon B., Solanki R. Atomic Layer Growth of InSe and Sb2Se3 Layered Semiconductors and Their Heterostructure. Electronics. 2017;6:27. doi: 10.3390/electronics6020027. DOI

Tabernor J., Christian P., O’Brien P. A general route to nanodimensional powders of indium chalcogenides. J. Mater. Chem. 2006;16:2082–2087. doi: 10.1039/b600921b. DOI

Mancini A.M., Micocci G., Rizzo A. New materials for optoelectronic devices: Growth and characterization of indium and gallium chalcogenide layer compounds. Mater. Chem. Phys. 1983;9:29–54. doi: 10.1016/0254-0584(82)90006-2. DOI

Tan C.K.Y., Fu W., Loh K.P. Polymorphism and Ferroelectricity in Indium(III) Selenide. Chem. Rev. 2023;123:8701–8717. doi: 10.1021/acs.chemrev.3c00129. PubMed DOI

Aksimentyeva O.I., Demchenko P.Y., Savchyn V.P., Balitskii O.A. The chemical exfoliation phenomena in layered GaSe-polyaniline composite. Nanoscale Res. Lett. 2013;8:29. doi: 10.1186/1556-276X-8-29. PubMed DOI PMC

Mudd G.W., Svatek S.A., Ren T., Patanè A., Makarovsky O., Eaves L., Beton P.H., Kovalyuk Z.D., Lashkarev G.V., Kudrynskyi Z.R., et al. Tuning the Bandgap of Exfoliated InSe Nanosheets by Quantum Confinement. Adv. Mater. 2013;25:5714–5718. doi: 10.1002/adma.201302616. PubMed DOI PMC

Sfuncia G., Nicotra G., Giannazzo F., Pécz B., Gueorguiev G.K., Kakanakova-Georgieva A. 2D graphitic-like gallium nitride and other structural selectivity in confinement at the graphene/SiC interface. CrystEngComm. 2023;25:5810–5817. doi: 10.1039/D3CE00515A. DOI

Sangiovanni D.G., Faccio R., Gueorguiev G.K., Kakanakova-Georgieva A. Discovering atomistic pathways for supply of metal atoms from methyl-based precursors to graphene surface. Phys. Chem. Chem. Phys. 2023;25:829–837. doi: 10.1039/D2CP04091C. PubMed DOI

Sedmidubský D., Sofer Z., Huber Š., Luxa J., Točík R., Mahnel T., Růžička K. Chemical bonding and thermodynamic properties of gallium and indium monochalcogenides. J. Chem. Thermodyn. 2019;128:97–102. doi: 10.1016/j.jct.2018.08.013. DOI

Julien C., Barnier S., Massot M., Pardo M.P. Vibrational studies of solid solutions formed in the gallium-cadmium-sulphur system. Mater. Res. Bull. 1994;29:785–794. doi: 10.1016/0025-5408(94)90204-6. DOI

Krost A., Richter W., Zahn D.R.T., Hingerl K., Sitter H. Chemical reaction at the ZnSe/GaAs interface detected by Raman spectroscopy. Appl. Phys. Lett. 1990;57:1981–1982. doi: 10.1063/1.104149. DOI

Halsall M.P., Wolverson D., Davies J.J., Lunn B., Ashenford D.E. Ga2Te3 and tellurium interfacial layers in ZnTe/GaSb heterostructures studied by Raman scattering. Appl. Phys. Lett. 1992;60:2129–2131. doi: 10.1063/1.107085. DOI

Tao H., Mao S., Dong G., Xiao H., Zhao X. Raman scattering studies of the Ge–In sulfide glasses. Solid State Commun. 2006;137:408–412. doi: 10.1016/j.ssc.2005.12.032. DOI

Lewandowska R., Bacewicz R., Filipowicz J., Paszkowicz W. Raman scattering in α-In2Se3 crystals. Mater. Res. Bull. 2001;36:2577–2583. doi: 10.1016/S0025-5408(01)00746-2. DOI

Zahn D.R.T., Mackey K.J., Williams R.H., Münder H., Geurts J., Richter W. Formation of interfacial layers in InSb-CdTe heterostructures studied by Raman scattering. Appl. Phys. Lett. 1987;50:742–744. doi: 10.1063/1.98085. DOI

Höhne G.W.H., Hemminger W.F., Flammersheim H.-J. Differential Scanning Calorimetry. 2nd ed. Springer; Berlin/Heidelberg, Germany: 2003.

Štejfa V., Fulem M., Růžička K., Červinka C. Thermodynamic study of selected monoterpenes III. J. Chem. Thermodyn. 2014;79:280–289. doi: 10.1016/j.jct.2014.04.022. DOI

Pokorný V., Štejfa V., Havlín J., Fulem M., Růžička K. Heat Capacities of L-Cysteine, L-Serine, L-Threonine, L-Lysine, and L-Methionine. Molecules. 2023;28:451. doi: 10.3390/molecules28010451. PubMed DOI PMC

Mahnel T., Pokorný V., Fulem M., Sedmidubský D., Růžička K. Measurement of low-temperature heat capacity by relaxation technique: Calorimeter performance testing and heat capacity of benzo[b]fluoranthene, benzo[k]fluoranthene, and indeno[1,2,3-cd]pyrene. J. Chem. Thermodyn. 2020;142:105964. doi: 10.1016/j.jct.2019.105964. DOI

Suzuki Y.T., Yamamura Y., Sumita M., Yasuzuka S., Saito K. Neat liquid consisting of hydrogen-bonded tetramers: Dicyclohexylmethanol. J. Phys. Chem. B. 2009;113:10077–10080. doi: 10.1021/jp9048764. PubMed DOI

Archer D.G. Thermodynamic Properties of the NaCl+H2O System l. Thermodynamic Properties of NaCl(cr) J. Phys. Chem. Ref. Data. 1992;21:1–21. doi: 10.1063/1.555913. DOI

Kresse G., Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B. 1999;59:1758–1775. doi: 10.1103/PhysRevB.59.1758. DOI

Perdew J.P., Burke K., Ernzerhof M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 1996;77:3865–3868. doi: 10.1103/PhysRevLett.77.3865. PubMed DOI

Knacke O., Kubaschewski O., Hesselmann K. Thermochemical Properties of Inorganic Substances. 2nd ed. Springer; Berlin/Heidelberg, Germany: 1991.

Tyurin A.V., Gavrichev K.S., Golushina L.N., Gorbunov V.E., Zlomanov V.P. Heat Capacity and Thermodynamic Functions of Ga2Se3 from 14 to 320 K. Inorg. Mater. 2005;41:1139–1143. doi: 10.1007/s10789-005-0275-x. DOI

Tyurin A.V., Gavrichev K.S., Zlomanov V.P., Bykova T.A. Low-temperature heat capacity and thermodynamic functions of Ga2Te3. Inorg. Mater. 2006;42:954–957. doi: 10.1134/S0020168506090056. DOI

Koshchenko V.I., Grinberg Y.K., Demidenko A.F., Zhegalina V.A. Temperature dependence of thermodynamic properties of indium selenide in the 5–300 K range. Izv. Akad. Nauk SSSR Neorg. Mater. 1981;17:1979–1982.

Boehnke U.C., Kühn G., Berezovski G.A., Spassov T. Some aspects of the thermal behaviour of In2Se3. J. Therm. Anal. 1987;32:115–120. doi: 10.1007/BF01914554. DOI

Mills K.C. Molar heat capacities and enthalpies of transition for the indium selenides, InSe(c), InSe1.2(c) and In2Se3(c) High Temp. High Press. 1976;8:225–230.

Zlomanov V.P., Sheiman M.S., Legendre B. Phase diagram and thermodynamic properties of phases in the In-Te system. J. Phase Equilib. 2001;22:339. doi: 10.1361/105497101770338851. DOI

Bale C.W., Bélisle E., Chartrand P., Decterov S.A., Eriksson G., Hack K., Jung I.H., Kang Y.B., Melançon J., Pelton A.D., et al. FactSage thermochemical software and databases—Recent developments. Calphad. 2009;33:295–311. doi: 10.1016/j.calphad.2008.09.009. DOI

Cox J.D., Wagman D.D., Medvedev V.A. CODATA Key Values for Thermodynamics. Hemisphere Publishing Corp.; New York, NY, USA: 1989.