Chalcopyrite CuFeS2 , a semiconductor with applications in chemical sector and energy conversion engineering, was synthetized in a planetary mill from elemental precursors. The synthesis is environmentally friendly, waste-free and inexpensive. The synthesized nano-powders were characterized by XRD, SEM, EDX, BET and UV/Vis techniques, tests of chemical reactivity and, namely, thermoelectric performance of sintered ceramics followed. The crystallite size of ∼13 nm and the strain of ∼17 were calculated for CuFeS2 powders milled for 60, 120, 180 and 240 min, respectively. The evolution of characteristic band gaps, Eg, and the rate constant of leaching, k, of nano-powders are corroborated by the universal evolution of the parameter SBET /X (SBET -specific surface area, X-crystallinity) introduced for complex characterization of mechanochemically activated solids in various fields such as chemical engineering and/or energy conversion. The focus on non-doped semiconducting CuFeS2 enabled to assess the role of impurities, which critically and often negatively influence the thermoelectric properties.

Institute of Geotechnics Slovak Academy of Sciences Watsonova 45 04001 Košice Slovakia

Institute of Materials Research Slovak Academy of Sciences Watsonova 47 04001 Košice Slovakia

Institute of Physics of the Czech Academy of Sciences Cukrovarnická 10 16200 Prague Czech Republic

Zobrazit více v PubMed

Habashi F., Chalcopyrite its Chemistry and Metallurgy, McGraw-Hill, New York: 1978, p. 165.

Engin T. E., Powell A. V., Hull S., J. Solid State Chem. 2011, 184, 2272–2277;

Powell A. V., J. Appl. Phys. 2019, 126;

Wen T., Wang Y. G., Li N. N., Zhang Q., Zhao Y. S., Yang W. E., Zhao Y. S., Mao H. K., J. Am. Chem. Soc. 2019, 141, 505–510. PubMed

Li Y. L., Zhang T. S., Qin Y. T., Day T., Snyder G. J., Shi X., Chen L. D., J. Appl. Phys. 2014, 116, 203705.

Teranishi T., J. Phys. Soc. Jpn. 1961, 16, 1881–1887.

Vaqueiro P., Powell A. V., J. Mater. Chem. 2010, 20, 10950–10950;

Suekuni K., Takabatake T., APL Mater. 2016, 4, 104503;

Hebert S., Berthebaud D., Daou R., Breard Y., Pelloquin D., Guilmeau E., Gascoin F., Lebedev O., Maignan A., J. Phys. Condens. Matter 2016, 28, 013001. PubMed

Ang R., Khan A. U., Tsujii N., Takai K., Nakamura R., Mori T., Angew. Chem. Int. Ed. 2015, 54, 12909–12913; PubMed

Angew. Chem. 2015, 127, 13101–13105; PubMed

Balaz P., Dutkova E., Levinsky P., Daneu N., Kubickova L., Knizek K., Balaz M., Navratil J., Kasparova J., Ksenofontov V., Moller A., Hejtmanek J., Mater. Lett. 2020, 275, 128107.

Tsujii N., J. Electron. Mater. 2013, 42, 1974–1977;

Tsujii N., Mori T., Appl. Phys. Express 2013, 6; 043001;

Tsujii N., Mori T., Isoda Y., J. Electron. Mater. 2014, 43, 2371–2375;

Tsujii N., Meng F. Q., Tsuchiya K., Maruyama S., Mori T., J. Electron. Mater. 2016, 45, 1642–1647;

Berthebaud D., Lebedev O. I., Maignan A., J. Mater. 2015, 1, 68–74;

Lefevre R., Berthebaud D., Mychinko M. Y., Lebedev O. I., Mori T., Gascoin F., Maignan A., RSC Adv. 2016, 6, 55117–55124;

Xie H. Y., Su X. L., Yan Y. G., Liu W., Chen L. J., Fu J. F., Yang J. H., Uher C., Tang X. F., NPG Asia Mater. 2017, 9, e390;

Vaure L., Liu Y., Cadavid D., Agnese F., Aldakov D., Pouget S., Cabotu A., Reiss P., Chenevier P., ChemNanoMat 2018, 4, 982–991;

Navratil J., Kasparova J., Plechacek T., Benes L., Olmrova-Zmrhalova Z., Kucek V., Drasar C., J. Electron. Mater. 2019, 48, 1795–1804.

Hicks L. D., Dresselhaus M. S., Phys. Rev. B 1993, 47, 16631–16634; PubMed

Hicks L. D., Dresselhaus M. S., Phys. Rev. B 1993, 47, 12727–12731; PubMed

Dresselhaus M. S., Chen G., Tang M. Y., Yang R. G., Lee H., Wang D. Z., Ren Z. F., Fleurial J. P., Gogna P., Adv. Mater. 2007, 19, 1043–1053;

Biswas K., He J. Q., Blum I. D., Wu C. I., Hogan T. P., Seidman D. N., Dravid V. P., Kanatzidis M. G., Nature 2012, 489, 414–418; PubMed

Heremans J. P., Dresselhaus M. S., Bell L. E., Morelli D. T., Nat. Nanotechnol. 2013, 8, 471–473; PubMed

He J. Q., Kanatzidis M. G., Dravid V. P., Mater. Today 2013, 16, 166–176.

Poudeu P. F. P., D′Angelo J., Downey A. D., Short J. L., Hogan T. P., Kanatzidis M. G., Angew. Chem. Int. Ed. 2006, 45, 3835–3839; PubMed

Angew. Chem. 2006, 118, 3919–3923;

Johnsen S., He J. Q., Androulakis J., Dravid V. P., Todorov I., Chung D. Y., Kanatzidis M. G., J. Am. Chem. Soc. 2011, 133, 3460–3470. PubMed

Liang D. X., Ma R. S., Jiao S. H., Pang G. S., Feng S. H., Nanoscale 2012, 4, 6265–6268; PubMed

Park J., Xia Y., Ozolins V., J. Appl. Phys. 2019, 125, 125102.

Balaz P., Mechanochemistry in Nanoscience and Minerals Engineering, Springer, Berlin Heidelberg, 2008, p. 413;

Balaz P., Balaz M., Achimovicova M., Bujinakova Z., Dutkova E., J. Mater. Sci. 2017, 52, 11851–11890.

Lan Y. C., Minnich A. J., Chen G., Ren Z. F., Adv. Funct. Mater. 2010, 20, 357–376.

Dutkova E., Bujnakova Z., Kovac J., Skorvanek I., Sayagues M. J., Zorkovska A., Kovac J., Balaz P., Adv. Powder Technol. 2018, 29, 1820–1826.

Levinsky P., Hejtmanek J., Knizek K., Pashchenko M., Navratil J., Masschelein P., Dutkova E., Balaz P., Acta Phys. Pol. A 2020, 137, 904–907.

Balaz P., Achimovicova M., Balaz M., Chen K., Dobrozhan O., Guilmeau E., Hejtmanek J., Knizek K., Kubickova L., Levinsky P., Puchy V., Reece M. J., Varga P., Zhang R., ACS Sustainable Chem. Eng. 2021, 9, 5, 2003–2016.

Zhao S. X., Wang G. R., Yang H. Y., Chen G. B., Qiu X. M., Trans. Nonferrous Met. Soc. China 2021, 31, 1465–1474;

Cullity D. B., Elements of X-ray Diffraction, Second Edition, Addison-Wesley Publishing Company, Inc., London, 1978.

Juhasz A. Z., Opoczky L., Mechanical Activation of Minerals by Grinding: Pulverizing and Morphology of Particles, Ellis Horwood, Chichester, 1990, p. 213.

Tkacova K., Mechanical Activation of Minerals, Elsevier, Amsterdam: 1989, p. 155.

Boldyrev V. V., Tkacova K., J. Mater. Synth. Process. 2000, 8, 121–132.

Miyasaka K., Senna M., React. Solids 1986, 2, 135–149;

Inoue S. I., Senna M., React. Solids 1988, 5, 155–166.

Senna M., Part. Part. Syst. Charact. 1989, 6, 163–167.

Tkacova K., Balaz P., Hydrometallurgy 1988, 21, 103–112.

Zeier W. G., Zevalkink A., Gibbs Z. M., Hautier G., Kanatzidis M. G., Snyder G. J., Angew. Chem. Int. Ed. 2016, 55, 6826–6841; PubMed

Angew. Chem. 2016, 128, 6938–6954.

Tian Z. T., Esfarjani K., Shiomi J., Henry A. S., Chen G., Appl. Phys. Lett. 2011, 99, 053122.

Balaz P., Bastl Z., Tkacova K., J. Mater. Sci. Lett. 1993, 12, 511–512;

Li J. H., Tan Q., Li J. F., J. Alloys Compd. 2013, 551, 143–149;

Granata G., Takahashi K., Kato T., Tokoro C., Miner. Eng. 2019, 131, 280–285;

Huang Z. W., Zhao L. D., J. Mater. Chem. C 2020, 8, 12054–12061.

Balaz P., Tkacova K., Avvakumov E. G., J. Therm. Anal. 1989, 35, 1325–1330;

Gock E., Erzmetall 1978, 31, 282–288 (in German).

Tkacova K., Boldyrev V. V., Pavluchin Yu. T., Avvakumov E. G., Sadykov R. S., Balaz P., Izv. Sib. Otdel. AN SSSR 2 1984, 9–13 (in Russian).

Baláž P., Extractive Metallurgy of Activated Minerals, Elsevier, Amsterdam: 2000, p. 278.

Navratil J., Levinský P., Hejtmánek J., Pashchenko M., Knizek K., Kubickova L., Kmjec T., Drasar C., J. Phys. Chem. C 2020, 124, 20773–20783.

Ge Z. H., Zhang B. P., Chen Y. X., Yu Z. X., Liu Y., Li J. F., Chem. Commun. 2011, 47, 12697–12699; PubMed

Pearce C. I., Pattrick R. A. D., Vaughan D. J., Rev. Mineral. Geochem. 2006, 61, 127–180;

Qiu P., Zhang T., Qiu Y., Shi X., Chen L., Energy Environ. Sci. 2014, 7, 4000–4006.

Ohlberg S. M., Strickler D. W., J. Am. Ceram. Soc. 1962, 45, 170–171.

Li Y., Kawashima N., Li J., Chandra A. P., Gerson A. R., Adv. Colloid Interface Sci. 2013, 197–198, 1–32. PubMed