Abstract
The nanospheres and nanowhiskers of ternary CuInS2 are synthesized by sonochemical and hydrothermal techniques, respectively. The energy dispersive X-rays showed the samples to be stoichiometric. The tetragonal unit cell structure of synthesized samples is characterized by X-ray diffraction. The corresponding morphology of the synthesized samples is studied by electron microscopy in scanning and transmission modes. The thermal investigation of the synthesized nanospheres and nanowhiskers is carried out by recording thermogravimetric (TG) and differential thermal analysis (DTA) curves. These simultaneous thermocurves are recorded in temperature range of ambient to 1253 K in an inert nitrogen atmosphere for three heating rates of 10, 15 and 20 K·min−1. The thermal study showed nanospheres to decompose by five steps and nanowhiskers to decompose in a single step. The kinetic parameters like activation energy, phonon frequency factor, activation enthalpy, activation entropy and Gibbs free energy change are determined for both samples. The kinetic parameters are evaluated from the thermocurves data using model-free isoconversion methods like Kissinger–Akahira–Sunose (KAS), Flynn–Wall–Ozawa (FWO) and Friedman (FR). All the obtained outcomes are investigated in details.
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H. Li, W. Li, W. Li, M. Chen, R. Snyders, C. Bittencourt, Z. Yuan, Engineering crystal phase of polytypic CuInS2nanosheets for enhanced photocatalytic and photoelectrochemical performance. Nano Res. 13, 583–590 (2020). https://doi.org/10.1007/s12274-020-2665-4
A. Anand, M.L. Zaffalon, G. Gariano, A. Camellini, M. Gandini, R. Brescia, C. Capitani, F. Bruni, V. Pinchetti, M. Zavelani-Rossi, F. Meinardi, S.A. Crooker, S. Brovelli, Evidence for the band-edge exciton of CuInS2nanocrystals enables record efficient large-area luminescent solar concentrators. Adv. Funct. Mater. 30, 1906629 (2020). https://doi.org/10.1002/adfm.201906629
W.-T. Huang, S.-Y. Yoon, B.-H. Wu, K.-M. Lu, C.-M. Lin, H. Yang, R.-S. Liu, Ultra-broadband near-infrared emission CuInS2/ZnS quantum dots with high power efficiency and stability for the theranostic applications of mini light-emitting diodes. Chem. Commun. 56, 8285–8288 (2020). https://doi.org/10.1039/D0CC03030A
Z. Peng, Y. Liu, K. Chen, G. Yang, W. Chen, Fabrication of the protonated pentatitanatenanobelts sensitized with CuInS2 quantum dots for photovoltaic applications. Chem. Eng. J. 244, 335–342 (2014). https://doi.org/10.1016/j.cej.2014.01.053
Y. Kim, H.S. Jang, H. Kim, S. Kim, D.Y. Jeon, Controlled synthesis of CuInS2/ZnSnanocubes and their sensitive photoluminescence response toward hydrogen peroxide. ACS Appl. Mater. Interfaces 9, 32097–32105 (2017). https://doi.org/10.1021/acsami.7b09388
J. Li, B. Kempken, V. Dzhagan, D.R.T. Zahn, J. Grzelak, S. Mackowski, J. Parisi, J. Kolny-Olesiak, Alloyed CuInS2–ZnSnanorods: synthesis, structure and optical properties. CrystEngComm 17, 5634–5643 (2015). https://doi.org/10.1039/C5CE00380F
J. Li, M. Bloemen, J. Parisi, J. Kolny-Olesiak, Role of copper sulfide seeds in the growth process of CuInS2nanorods and networks. ACS Appl. Mater. Interfaces 6, 20535–20543 (2014). https://doi.org/10.1021/am5061454
B. Chen, S. Chang, D. Li, L. Chen, Y. Wang, T. Chen, B. Zou, H. Zhong, A.L. Rogach, Template synthesis of CuInS2nanocrystals from in2s3nanoplates and their application as counter electrodes in dye-sensitized solar cells. Chem. Mater. 27, 5949–5956 (2015). https://doi.org/10.1021/acs.chemmater.5b01971
Q. Li, L. Zhai, C. Zou, X. Huang, L. Zhang, Y. Yang, X. Chen, S. Huang, Wurtzite CuInS2 and CuInxGa1−xS2nanoribbons: synthesis, optical and photoelectrical properties. Nanoscale 5, 1638–1648 (2013). https://doi.org/10.1039/C2NR33173J
X. Tu, M. Li, Y. Su, G. Yin, J. Lu, D. He, Self-templated growth of CuInS2nanosheet arrays for photoelectrochemical water splitting. J. Alloys Compd. 809, 151794 (2019). https://doi.org/10.1016/j.jallcom.2019.151794
M. Li, R. Zhao, Y. Su, J. Hu, Z. Yang, Y. Zhang, Synthesis of CuInS2 nanowire arrays via solution transformation of Cu2S self-template for enhanced photoelectrochemical performance. Appl. Catal. B Environ. 203, 715–724 (2016). https://doi.org/10.1016/j.apcatb.2016.10.051
Y. Luo, G. Chang, W. Lu, X. Sun, Synthesis and characterization of CuInS2nanoflowers. Colloid J. 72, 282–285 (2010). https://doi.org/10.1134/S1061933X10020201
J.-J. Wu, W.-T. Jiang, W.-P. Liao, CuInS2 nanotube array on indium tin oxide: synthesis and photoelectrochemical properties. Chem. Commun. 46, 5885–5887 (2010). https://doi.org/10.1039/C0CC01314E
H.M. Hu, C.H. Deng, Template-free synthesis of CuInS2 hollow nanospheres. Optoelectron. Mater. 663–665, 486–489 (2011)
M. Gromova, A. Lefrançois, L. Vaure, F. Agnese, D. Aldakov, A. Maurice, D. Djurado, C. Lebrun, A. de Geyer, T.U. Schülli, S. Pouget, P. Reiss, Growth mechanism and surface state of CuInS2nanocrystals synthesized with dodecanethiol. J. Am. Chem. Soc. 139, 15748–15759 (2017). https://doi.org/10.1021/jacs.7b07401
A. Tang, Z. Hu, Z. Yin, H. Ye, C. Yang, F. Teng, One-pot synthesis of CuInS2nanocrystals using different anions to engineer their morphology and crystal phase. Dalton Trans. 44, 9251–9259 (2015). https://doi.org/10.1039/C5DT01111F
L. Liu, H. Li, Z. Liu, Y.-H. Xie, Structure and band gap tunable CuInS2nanocrystal synthesized by hot-injection method with altering the dose of oleylamine. Mater. Des. 149, 145–152 (2018). https://doi.org/10.1016/j.matdes.2018.04.015
H. Liu, X. Yang, K. Wang, Y. Wang, M. Wu, X. Zuo, W. Yang, B. Zou, Pressure-induced multidimensional assembly and sintering of CuInS2 nanoparticles into lamellar nanosheets with band gap narrowing. ACS Appl. Nano Mater. 3, 2438–2446 (2020). https://doi.org/10.1021/acsanm.9b02550
B. Li, Y. Xie, J. Huang, Y. Qian, Synthesis by a solvothermal route and characterization of CuInSe2nanowhiskers and nanoparticles. Adv. Mater. 11, 1456–1459 (1999). https://doi.org/10.1002/(SICI)1521-4095(199912)11:17%3c1456::AID-ADMA1456%3e3.0.CO;2-3
C. Sun, Z. Cevher, J. Zhang, B. Gao, K. Shum, Y. Ren, One-pot synthesis and characterization of chalcopyrite CuInS2 nanoparticles. J. Mater. Chem. A 2, 10629–10633 (2014). https://doi.org/10.1039/C4TA01062K
Z.X. Chen, Y.Z. Ye, H.J. Huang, G.C. Xiao, Y.H. He, Hydrothermal synthesis of tetragonal phase CuInS2 nanoparticles. Adv. Mater. Res. 557–559, 489–492 (2012)
S.H. Chaki, A. Agarwal, Growth, surface microtopographic and thermal studies of CuInS2. J. Cryst. Growth 308, 176–179 (2007). https://doi.org/10.1016/j.jcrysgro.2007.07.031
M.K. Agarwal, P.D. Patel, S.H. Chaki, D. Lakshminarayana, Growth and properties of CuInS2 thin films. Bull. Mater. Sci. 21, 291–295 (1998). https://doi.org/10.1007/BF02744955
S.H. Chaki, Seebeck coefficient and optical studies of cadmium doped CuInS2 single crystal. Acta Phys. Pol. A 116, 221 (2009). https://doi.org/10.12693/APhysPolA.116.221
S.H. Chaki, Thermal decomposition studies of CuInS2. Front. Mater. Sci. China 2, 322–325 (2008). https://doi.org/10.1007/s11706-008-0041-5
Y. Li, Y. Wang, R. Tang, X. Wang, P. Zhu, X. Zhao, C. Gao, Structural phase transition and electrical transport properties of CuInS2nanocrystals under high pressure. J. Phys. Chem. C 119, 2963–2968 (2015). https://doi.org/10.1021/jp511684u
B.-B. Xie, B.-B. Hu, L.-F. Jiang, G. Li, Z.-L. Du, The phase transformation of CuInS2 from chalcopyrite to wurtzite. Nanoscale Res. Lett. 10, 86 (2015). https://doi.org/10.1186/s11671-015-0800-z
A.D.P. Leach, J.E. Macdonald, Optoelectronic properties of CuInS2nanocrystals and their origin. J. Phys. Chem. Lett. 7, 572–583 (2016). https://doi.org/10.1021/acs.jpclett.5b02211
R. Klenk, J. Klaer, R. Scheer, M. Lux-Steiner, I. Luck, N. Meyer, U. Ruhle, Solar cells based on CuInS2—an overview. Thin Solid Films 480, 509–514 (2005). https://doi.org/10.1016/j.tsf.2004.11.042
M. Dehghani, A. Behjat, F. Tajabadi, N. Taghavinia, Totally solution-processed CuInS2 solar cells based on chloride inks: reduced metastable phases and improved current density. J. Phys. D Appl. Phys. 48, 115304 (2015). https://doi.org/10.1088/0022-3727/48/11/115304
B. Fu, C. Deng, L. Yang, Efficiency enhancement of solid-state CuInS2 quantum dot-sensitized solar cells by improving the charge recombination. Nanoscale Res. Lett. 14, 198 (2019). https://doi.org/10.1186/s11671-019-2998-7
A.H. CheshmeKhavar, A.R. Mahjoub, F. Tajabadi, M. Dehghani, N. Taghavinia, Preparation of a CuInS2 nanoparticle Ink and application in a selenization-free, solution-processed superstrate solar cell. Eur. J. Inorg. Chem. 2015, 5793–5800 (2015). https://doi.org/10.1002/ejic.201500749
R. Scheer, T. Walter, H.W. Schock, M.L. Fearheiley, H.J. Lewerenz, CuInS2 based thin film solar cell with 10.2% efficiency. Appl. Phys. Lett. 63, 3294–3296 (1993). https://doi.org/10.1063/1.110786
D. Reishofer, T. Rath, H.M. Ehmann, C. Gspan, S. Dunst, H. Amenitsch, H. Plank, B. Alonso, E. Belamie, G. Trimmel, S. Spirk, Biobased cellulosic–CuInS2nanocomposites for optoelectronic applications. ACS Sustain. Chem. Eng. 5, 3115–3122 (2017). https://doi.org/10.1021/acssuschemeng.6b02871
H. Li, X. Jiang, A. Wang, X. Chu, Z. Du, Simple synthesis of CuInS2/ZnS core/shell quantum dots for white light-emitting diodes. Front. Chem. 8, 669 (2020). https://doi.org/10.3389/fchem.2020.00669
R. Jose Varghese, S. Parani, O.O. Adeyemi, V.R. Remya, E.H.M. Sakho, R. Maluleke, S. Thomas, O.S. Oluwanfemi, Green synthesis of sodium alginate capped -CuInS2 quantum dots with improved fluorescence properties. J. Fluoresc. (2020). https://doi.org/10.1007/s10895-020-02604-0
R. Maluleke, E.H.M. Sakho, O.S. Oluwafemi, Aqueous synthesis of glutathione-capped CuInS2/ZnS quantum dots-graphene oxide nanocomposite as fluorescence “switch OFF” for explosive detection. Mater. Lett. 269, 127669 (2020). https://doi.org/10.1016/j.matlet.2020.127669
M. Heydari, M. Rahman, R. Gupta, Kinetic study and thermal decomposition behavior of lignite coal. Int. J. Chem. Eng. 2015, 481739 (2015). https://doi.org/10.1155/2015/481739
N. Kongkaew, W. Pruksakit, S. Patumsawad, Thermogravimetric kinetic analysis of the pyrolysis of rice straw. Energy Proc. 79, 663–670 (2015). https://doi.org/10.1016/j.egypro.2015.11.552
M. Li, R. Zhao, Y. Su, J. Hu, Z. Yang, Y. Zhang, Hierarchically CuInS2nanosheet-constructed nanowire arrays for photoelectrochemical water splitting. Adv. Mater. Interfaces 3, 1600494 (2016). https://doi.org/10.1002/admi.201600494
M. Mousavi-Kamazani, M. Salavati-Niasari, H. Emadi, Synthesis and characterization of CuInS2 nanostructure by ultrasonic-assisted method and different precursors. Mater. Res. Bull. 47, 3983–3990 (2012). https://doi.org/10.1016/j.materresbull.2012.08.044
A.L. Patterson, The Scherrer formula for X-ray particle size determination. Phys. Rev. 56, 978–982 (1939). https://doi.org/10.1103/PhysRev.56.978
B. Wunderlich, Thermal Analysis, Elsevier Science, 2012. https://books.google.co.in/books?id=A7S-BOAiLg8C.
R.M. Flynn, J.H. Flynn, T.J. Bent, Comparison of temperature response within and between power compensated and differential temperature DSC instruments. Thermochim. Acta. 134, 401–406 (1988). https://doi.org/10.1016/0040-6031(88)85267-5
S.R. Sauerbrunn, B.S. Crowe, M. Reading, in 21st Proceedinds NATAS Conference in Atlanta, GA, Sept. 13–16. M. Reading, B. K. Hahn B. S. Crowe, US Pat. 5. 224, 775, 137–144 (1992)
H.E. Kissinger, Reaction kinetics in differential thermal analysis. Anal. Chem. 29, 1702–1706 (1957). https://doi.org/10.1021/ac60131a045
T. Akahira, Trans joint convention of four electrical institutes. Res. Rep. Chiba Inst. Technol. 16, 22–31 (1971)
A.W. Coats, J.P. Redfern, Kinetic parameters from thermogravimetric data. Nature 201, 68–69 (1964). https://doi.org/10.1038/201068a0
J.H. Flynn, L.A. Wall, A quick, direct method for the determination of activation energy from thermogravimetric data. J. Polym. Sci. Part B Polym. Lett. 4, 323–328 (1966). https://doi.org/10.1002/pol.1966.110040504
T. Ozawa, A new method of analyzingthermogravimetric data. Bull. Chem. Soc. Jpn. 38, 1881–1886 (1965). https://doi.org/10.1246/bcsj.38.1881
H.L. Friedman, Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J. Polym. Sci. Part C Polym. Symp. 6, 183–195 (1964). https://doi.org/10.1002/polc.5070060121
T. Ozawa, Estimation of activation energy by isoconversion methods. Thermochim. Acta 203, 159–165 (1992). https://doi.org/10.1016/0040-6031(92)85192-X
M. Muzayyin, S. Sukarni, R. Wulandari, Investigation on kinetic and thermodynamic parameters of Cerberamanghas de-oiled seed as renewable energy during the pyrolysis process. AIP Conf. Proc. 2228, 30012 (2020). https://doi.org/10.1063/5.0000900
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One of the authors, RKG is thankful to the Education Department, Govt. of Gujarat, India for providing Research Fellowship under SHODH (ScHeme Of Developing High quality research, Grant No. 201901640031) to carry out the research work.
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Giri, R.K., Chaki, S.H., Khimani, A.J. et al. Thermal investigation of nanospheres and nanowhiskers of CuInS2. Eur. Phys. J. Plus 136, 320 (2021). https://doi.org/10.1140/epjp/s13360-021-01241-1
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DOI: https://doi.org/10.1140/epjp/s13360-021-01241-1