Structural and optical properties of ZnSe and ZnSe/ZnS quantum dots prepared by using green method
Source abstract
Abstract
We report the green synthesis, structural characterization, optical measurements, and theoretical modeling of ZnSe and ZnSe/ZnS quantum dots (QDs) synthesized via a rapid aqueous method using thioglycolic acid (TGA) as a stabilizer. The synthesis was carried out at 90 °C and pH 8.5, employing zinc acetate, NaHSe as a selenium source, and thiourea for ZnS shell growth. X-ray diffraction (XRD) analysis confirmed cubic-phase ZnSe with a dominant (111) peak, while ZnSe/ZnS core–shell samples exhibited additional peaks attributed to hexagonal ZnS, indicating successful passivation. Williamson–Hall analysis yields a core crystallite size of ~ 2.3 nm and reveals a compressive interfacial strain of − 2.2% in the core–shell heterostructure. Optical characterization via UV-Vis and photoluminescence (PL) spectroscopy techniques showed redshift in both absorption and emission with increasing reaction time and temperature, consistent with quantum size effects and shell-induced modifications. Theoretical modeling by using modified Brus equation based on Kane’s effective mass approximation, and a recently developed thermoelastic strain theory quantitatively explained the bandgap evolution by accounting for size-dependent confinement and elastic strain at the core–shell interface. Calculated bandgap values showed strong agreement with experimental data: 3.67–3.71 eV from absorption and 3.39–3.41 eV from PL. The integration of green chemistry and strain-sensitive bandgap engineering underscores the potential of the QDs for low-toxicity optoelectronic and biosensing applications.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Quantum Dots Synthesis And Properties · Semiconductor Quantum Structures and Devices · Silicon Nanostructures and Photoluminescence
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (44)
Show source-provided references
1. H. Ünlü, N.J.M. Horing, Eds., Progress in Nanoscale and Low-Dimensional Materials and Devices: Properties, Synthesis, Characterization, Modelling and Applications, Vol. 144. In Topics in Applied Physics, Vol. 144 (Springer International Publishing, Cham, 2022). https://doi.org/10.1007/978-3-030-93460-610.1007/978-3-030-93460-6 ↗
2. A.L. Efros, L.E. Brus, Nanocrystal quantum dots: from discovery to modern development. ACS Nano 15(4), 6192–6210 (2021). https://doi.org/10.1021/acsnano.1c0139910.1021/acsnano.1c01399 ↗
3. F.P. García De Arquer, D.V. Talapin, V.I. Klimov, Y. Arakawa, M. Bayer, E.H. Sargent, Semiconductor quantum dots: technological progress and future challenges. Science 373(6555), eaaz8541 (2021). https://doi.org/10.1126/science.aaz854110.1126/science.aaz8541 ↗
4. J. Fan et al., Recent progress of quantum dots light-emitting diodes: materials, device structures, and display applications. Adv. Mater. 36(37), 2312948 (2024). https://doi.org/10.1002/adma.20231294810.1002/adma.202312948 ↗
5. S. Kargozar, S.J. Hoseini, P.B. Milan, S. Hooshmand, H. Kim, M. Mozafari, Quantum dots: a review from concept to clinic. Biotechnol. J. 15(12), 2000117 (2020). https://doi.org/10.1002/biot.20200011710.1002/biot.202000117 ↗
6. C.B. Murray, D.J. Norris, M.G. Bawendi, Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites. J. Am. Chem. Soc. 115(19), 8706–8715 (1993). https://doi.org/10.1021/ja00072a02510.1021/ja00072a025 ↗
7. F. Zhang, D. Yi, H. Sun, H. Zhang, Cadmium-based quantum dots: preparation, surface modification, and applications. J. Nanosci. Nanotechnol. 14(2), 1409–1424 (2014). https://doi.org/10.1166/jnn.2014.875110.1166/jnn.2014.8751 ↗
8. N. Chen et al., The cytotoxicity of cadmium-based quantum dots. Biomaterials 33(5), 1238–1244 (2012). https://doi.org/10.1016/j.biomaterials.2011.10.07010.1016/j.biomaterials.2011.10.070 ↗
9. S. Chahal et al., A comparison of carbon dot and CdTe quantum dot toxicity in Drosophila melanogaster. Environ. Sci. Adv. 3(6), 912–924 (2024). https://doi.org/10.1039/D4VA00017J10.1039/D4VA00017J ↗
10. M. Alaraby, E. Demir, A. Hernández, R. Marcos, Assessing potential harmful effects of CdSe quantum dots by using Drosophila melanogaster as in vivo model. Sci. Total Environ. 530, 66–75 (2015). https://doi.org/10.1016/j.scitotenv.2015.05.06910.1016/j.scitotenv.2015.05.069 ↗
11. M. Zonouzi-Marand, M. Naderi, R.W.M. Kwong, Toxicological assessment of cadmium-containing quantum dots in developing zebrafish: physiological performance and neurobehavioral responses. Aquat. Toxicol. 247, 106157 (2022). https://doi.org/10.1016/j.aquatox.2022.10615710.1016/j.aquatox.2022.106157 ↗
12. L. Hu et al., Bioaccumulation and toxicity of CdSe/ZnS quantum dots in Phanerochaete chrysosporium. Colloids Surf. B Biointerfaces 159, 303–311 (2017). https://doi.org/10.1016/j.colsurfb.2017.08.00610.1016/j.colsurfb.2017.08.006 ↗
13. European Commission, Commission Regulation (EU) No 494/2011 of 20 May 2011 amending Regulation (EC) No 1907/2006 of the European Parliament and of the Council on Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), L134/2, 2011. https://eur-lex.europa.eu/eli/reg/2011/494/oj/eng
14. Directive 2011/65/EU of the European Parliament and of the council on the restriction of the use of certain hazardous substances in electrical and electronic equipment, L174/88. https://eur-lex.europa.eu/eli/dir/2011/65/oj
15. G. Dickson, Display industry ready for new EU cadmium regulations. Inf. Disp. 40(4), 37–39 (2024). https://doi.org/10.1002/msid.150410.1002/msid.1504 ↗
16. N. Pradhan, D. Goorskey, J. Thessing, X. Peng, An alternative of CdSe nanocrystal emitters: pure and tunable impurity emissions in ZnSe nanocrystals. J. Am. Chem. Soc. 127(50), 17586–17587 (2005). https://doi.org/10.1021/ja055557z10.1021/ja055557z ↗
17. S. Jana et al., Prevention of photooxidation in blue–green emitting cu doped ZnSe nanocrystals. Chem. Commun. 46(16), 2853 (2010). https://doi.org/10.1039/b925980e10.1039/b925980e ↗
18. C. Wang, S. Xu, Y. Wang, Z. Wang, Y. Cui, Aqueous synthesis of multilayer Mn:ZnSe/cu:ZnS quantum dots with white light emission. J. Mater. Chem. C. 2(4), 660–666 (2014). https://doi.org/10.1039/C3TC31602E10.1039/C3TC31602E ↗
19. Y. Wang et al., One-pot synthesis of multicolor MnSe:ZnSe nanocrystals for optical coding. J. Colloid Interface Sci. 415, 7–12 (2014). https://doi.org/10.1016/j.jcis.2013.10.00910.1016/j.jcis.2013.10.009 ↗
20. C. Li et al., Colloidal Zn-based semiconductor nanocrystals: recent advances and challenges. Adv. Opt. Mater. 13(6), 2402510 (2025). https://doi.org/10.1002/adom.20240251010.1002/adom.202402510 ↗
21. G. Liu et al., Recent advances of eco-friendly quantum dots light-emitting diodes for display. Prog. Quantum Electron. 86, 100415 (2022). https://doi.org/10.1016/j.pquantelec.2022.10041510.1016/j.pquantelec.2022.100415 ↗
22. X. Deng, F. Zhang, Y. Zhang, H. Shen, Heavy-metal-free blue-emitting ZnSe(Te) quantum dots: synthesis and light-emitting applications. J. Mater. Chem. C. 11(42), 14495–14514 (2023). https://doi.org/10.1039/D3TC02699J10.1039/D3TC02699J ↗
23. P. Reiss, M. Protière, L. Li, Core/shell semiconductor nanocrystals. Small 5(2), 154–168 (2009). https://doi.org/10.1002/smll.20080084110.1002/smll.200800841 ↗
24. M. Lomascolo, A. Cretı̀, G. Leo, L. Vasanelli, L. Manna, Exciton relaxation processes in colloidal core/shell ZnSe/ZnS nanocrystals. Appl. Phys. Lett. 82(3), 418–420 (2003). https://doi.org/10.1063/1.153705010.1063/1.1537050 ↗
25. M.A. Hines, P. Guyot-Sionnest, Synthesis and characterization of strongly luminescing ZnS-capped CdSe nanocrystals. J. Phys. Chem. 100(2), 468–471 (1996). https://doi.org/10.1021/jp953056210.1021/jp9530562 ↗
26. Z. Lin, M. Wang, L. Wei, X. Song, Y. Xue, X. Yao, Synthesis and characterization of ZnSe/ZnS core/shell nanocrystals by aqueous reflux route. J. Alloys Compd. 509(33), 8356–8359 (2011). https://doi.org/10.1016/j.jallcom.2011.03.07010.1016/j.jallcom.2011.03.070 ↗
27. H.-S. Chen et al., Colloidal ZnSe, ZnSe/ZnS, and ZnSe/ZnSeS quantum dots synthesized from ZnO. J. Phys. Chem. B. 108(44), 17119–17123 (2004). https://doi.org/10.1021/jp047035w10.1021/jp047035w ↗
28. Y. Wang, C. Wang, S. Xu, Z. Wang, Y. Cui, Cation-inverting-injection: a novel method for synthesis of aqueous ZnSe quantum dots with bright excitionic emission and suppressed trap emission. Nanotechnology 25(29), 295602 (2014). https://doi.org/10.1088/0957-4484/25/29/29560210.1088/0957-4484/25/29/295602 ↗
29. G.-Y. Lan, Y.-W. Lin, Y.-F. Huang, H.-T. Chang, Photo-assisted synthesis of highly fluorescent ZnSe(S) quantum dots in aqueous solution. J. Mater. Chem. 17(25), 2661 (2007). https://doi.org/10.1039/b702469j10.1039/b702469j ↗
30. Z. Fang, Y. Li, H. Zhang, X. Zhong, L. Zhu, Facile synthesis of highly luminescent UV-blue-emitting ZnSe/ZnS core/shell nanocrystals in aqueous media. J. Phys. Chem. 113(32), 14145–14150 (2009). https://doi.org/10.1021/jp903806b10.1021/jp903806b ↗
31. L.C. He, Y.A. Zhang, S.L. Zhang, X.T. Zhou, Z.X. Lin, T.L. Guo, Preparation and characterization of ZnSe quantum dots by the cation-inverting-injection method in aqueous solution. Mater. Technol. 33(3), 205–213 (2018). https://doi.org/10.1080/10667857.2017.139677610.1080/10667857.2017.1396776 ↗
32. S.L. Zhang et al., Facile and green synthesis of core–shell ZnSe/ZnS quantum dots in aqueous solution. J. Mater. Sci. Mater. Electron. 29(19), 16805–16814 (2018). https://doi.org/10.1007/s10854-018-9775-810.1007/s10854-018-9775-8 ↗
33. D.L. Klayman, T.S. Griffin, Reaction of selenium with sodium borohydride in protic solvents. A facile method for the introduction of selenium into organic molecules. J. Am. Chem. Soc. 95(1), 197–199 (1973). https://doi.org/10.1021/ja00782a03410.1021/ja00782a034 ↗
34. A.M. Smith, S. Nie, Semiconductor nanocrystals: structure, properties, and band gap engineering. Acc. Chem. Res. 43(2), 190–200 (2010). https://doi.org/10.1021/ar900106910.1021/ar9001069 ↗
35. H. Ünlü, A thermoelastic model for strain effects on bandgaps and band offsets in heterostructure core/shell quantum dots. Eur. Phys. J. Appl. Phys. 86(3), 30401 (2019). https://doi.org/10.1051/epjap/201918035010.1051/epjap/2019180350 ↗
36. L.E. Brus, Electron–electron and electron-hole interactions in small semiconductor crystallites: the size dependence of the lowest excited electronic state. J. Chem. Phys. 80(9), 4403–4409 (1984). https://doi.org/10.1063/1.44721810.1063/1.447218 ↗
37. Y. Kayanuma, Quantum-size effects of interacting electrons and holes in semiconductor microcrystals with spherical shape. Phys. Rev. B 38(14), 9797–9805 (1988). https://doi.org/10.1103/PhysRevB.38.979710.1103/PhysRevB.38.9797 ↗
38. G.H.E. Al-Shabeeb, A.K. Arof, On the electronic structure and band gap of ZnSxSe1−x. Eur. Phys. J. Plus 128(12), 153 (2013). https://doi.org/10.1140/epjp/i2013-13153-610.1140/epjp/i2013-13153-6 ↗
39. H. Ünlü, in Progress in Nanoscale and Low-Dimensional Materials and Devices. Topics in Applied Physics, vol 144., ed. by H. Ünlü, N. J. M. Horing. Strain in Microscale and Nanoscale Semiconductor Heterostructures (Springer International Publishing, Cham, 2022). https://doi.org/10.1007/978-3-030-93460-6_210.1007/978-3-030-93460-6_2 ↗
40. O. Madelung, in Landolt-Börnstein. Numerical Data and Functional Relationships in Science and Technology, Vol. 17, Part A and Part D (Springer, 1982)
41. H. Ünlü, A thermodynamic model for determining pressure and temperature effects on the bandgap energies and other properties of some semiconductors. Solid. State. Electron 35(9), 1343–1352 (1992). https://doi.org/10.1016/0038-1101(92)90170-H10.1016/0038-1101(92)90170-H ↗
42. D. Malkoç, H. Ünlü, The temperature-dependent tight binding theory modelling of strain and composition effects on the electronic structure of CdSe- and ZnSe-based core/shell quantum dots. Materials 18(2), 283 (2025). https://doi.org/10.3390/ma1802028310.3390/ma18020283 ↗
43. Y.P. Varshni, Temperature dependence of the energy gap in semiconductors. Physica 34(1), 149–154 (1967). https://doi.org/10.1016/0031-8914(67)90062-610.1016/0031-8914(67)90062-6 ↗
44. A. Buba, Optoelectronic properties of zinc selenide (ZnSe) thin films deposited using chemical bath deposition (CBD) technique. BJAST 14(3), 1–7 (2016). https://doi.org/10.9734/bjast/2016/2362210.9734/bjast/2016/23622 ↗