Yüksek Sıcaklıkta Uzun Bir Süre Çekirdekleştirilen Kolloidal CdSe Kuantum Noktalarının Sentezi ve Optik Karakterizasyonu

Abstract

Kolloidal CdSe kuantum noktaları, koordine olmayan oktadesen çözücü içerisinde sıcak-enjeksiyon tekniği kullanılarak yaklaşık 300oC’de 15 s çekirdekleştirildi ve 272oC’de 245 dakikaya kadar büyütüldü. CdSe kuantum noktalarının sentezinde stearik asit bir kaplama ajanı olarak kullanıldı. Bu çalışmada kullanılan çekirdekleşme zamanı literatürdekilere göre oldukça uzundu ve optik özelliklere olan etkisi incelendi. Birinci eksiton soğurma ve karşılık gelen rekombinasyon tepeleri, sırasıyla, optik soğurma ve fotolüminesans spektrumlarında gözlendi. Stokes kayma değeri 70 meV’ye kadar değişti. 20 dakika için büyütülen numunenin optik soğurma ve fotolüminesans spektrumlarında bir tepe ve omuz yapısı elde edildi. Yüksek sıcaklık altında yeterince uzun bir sürede çekirdekleştirilen bu kuantum noktalarının çift büyüklük dağılımına sahip olabileceği gösterildi. CdSe kuantum noktalarının görüntüleri geçirgenlik elektron mikroskopi vasıtasıyla elde edildi. Resimleri, ImageJ görüntü işleme programı ile işlendi. 12 dakika büyütülen CdSe kuantum noktalarının ortalama büyüklüğü 2.63 nm olarak bulundu. Büyüklük dağılımı tekil dağılımlı kuantum noktalarınkine nazaran 4.6 kat arttı. Cd ve Se elementlerine ait X-ışınları enerji geçiş tepeleri enerji dağılımlı X-ışınları spektrumlarında gözlendi. Bu kuantum noktalarını saran stearik asit moleküllerinin simetrik ve asimetrik tireşim modları Fourier dönüşümlü kızıl ötesi spektroskopi kullanılarak, sırasıyla, 2848 cm-1 ve 2914 cm-1 civarında belirlendi.

Keywords

• optik soğurma,fotolüminesans,Fourier dönüşümlü kızılötesi spektroskopi,geçirimli elektron mikroskopi,CdSe kuantum noktaları,geçirimli elektron mikroskopi

Synthesis and Optical Characterization of Colloidal CdSe Quantum Dots Nucleated for A Long Time at High Temperature

Abstract

Colloidal CdSe quantum dots were nucleated at about 300oC for 15 s and growth at 272oC up to 245 min in non-coordinating solvent octadecene by using hot-injection technique. Stearic acid was used as a capping agent in the synthesis of CdSe quantum dots. The nucleation time used in this study was considerably longer than those in the literature and its effect on the optical properties was examined. The first excitonic absorption and corresponding recombination peaks were observed in their optical absorption and photoluminescence spectra, respectively. The value of Stokes shift changed up to 70 meV. A peak and shoulder structure was obtained in the optical absorption and photoluminescence spectra of the sample growth for 20 min. It was indicated that CdSe quantum dots which are nucleated at high temperature for a sufficiently long period may have double size distribution. The images of CdSe quantum dots were obtained via transmission electron microscopy. Their images were processed with the image processing program ImageJ. The average size of CdSe quantum dots growth for 12 min was found as 2.63 nm. The size dispersion increased 4.6 times with respect to that of the monodisperse quantum dots. The X-ray energy transition peaks belong to Cd and Se elements were observed in their energy dispersive X-ray spectra. Symmetric and asymmetric vibrational modes of stearic acid molecules capping these quantum dots were determined at about 2848 cm-1 and 2914 cm-1 , respectively, by using Fourier transform infrared spectroscopy.

Keywords

• optical absorption,photoluminescence,Fourier transform infrared spectroscopy,transmission electron microscopy,: CdSe quantum dots,transmission electron microscopy

References

1. [13] C. de M. Donegá, P. Liljeroth and D. Vanmaekelbergh, “Physicochemical Evaluation of the Hot-Injection Method, a Synthesis Route for Monodisperse Nanocrystals”, Small, vol. 1, pp. 1152-1162, 2005.
2. [14] A.Veamatahau, B. Jiang, T. Seifert, S. Makuta, K. Latham, M. Kanehara, T. Teranishi and Y. Tachibana, “Origin of surface trap states in CdS quantum dots: Relationship between size dependent photoluminescence and sulfur vacancy trap states”, Phys. Chem. Chem. Phys., vol. 17, pp. 2850-2858, 2015.
3. [15] M. H. Yükselici, “Growth kinetics of CdSe nanoparticles in glass”, J. Phys.: Condens. Matter, vol. 14, pp. 1153–1162, 2002.
4. [16] L.-Y. Chen, H.-L. Chou, C.-H. Chen and C.-H. Tseng, “Surface Modification of CdSe and CdS Quantum Dots-Experimental and Density Function Theory Investigation” in Nanocrystals – Synthesis, Characterization and Applications, S. Neralla, Rijeka: InTechOpen, 2012, pp. 149-168.
5. [17] Z. E. Shoeb, S. M. Hammad and A. A. Yousef, “Oleochemicals I: Studies on the preparation and the structure of lithium soaps”, Grasas y Aceites, vol. 50, pp. 426-434, 1999.
6. [1] P. Guyot-Sionnest, “Colloidal quantum dots”, C. R. Physique, vol. 9, pp. 777–787, 2008.
7. [2] C. B. Murray, D. J. Norris and M. G. Bawendi, “Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites”, J. Am. Chem. Soc., vol. 115, pp. 8706–8715, 1993.
8. [3] V. Wood and V. Bulović, “Colloidal quantum dot light-emitting devices”, Nano Rev., vol. 1, pp. 1-7, 2010.

9. [4] A. Franceschetti, H. Fu, L. W. Wang and A. Zunger, “Many-body pseudopotential theory of excitons in InP and CdSe quantum dots”, Phys. Rev. B, vol. 60, pp. 1819-1829, 1999.
10. [5] T. Erdem and H. V. Demir, “Color science of nanocrystal quantum dots for lighting and displays”, Nanophotonics, vol. 2, pp. 57–81, 2013.
11. [6] K. T. Shimizu, M. Böhmer, D. Estrada, S. Gangwal, S. Grabowski, H. Bechtel, E. Kang, K. J. Vampola, D. Chamberlin, O. B. Shchekin and J. Bhardwaj, “Toward commercial realization of quantum dot based white light-emitting diodes for general illumination”, Photonics Research, vol. 5, pp. A1-A6, 2017.
12. [7] G. G. Yordanov, H. Yoshimura and C. D. Dushkin, “Fine control of the growth and optical properties of CdSe quantum dots by varying the amount of stearic acid in a liquid paraffin matrix”, Colloids and Surfaces A: Physicochem. Eng. Aspects, vol. 322, pp. 177–182, 2008.
13. [8] G. G. Yordanov, C. D. Dushkin, G. D. Gicheva, B. H. Bochev and E. Adachi, “Synthesis of high-quality semiconductor nanoparticles in a composite hot-matrix”, Colloid Polym. Sci., vol. 284, pp. 229–232, 2005.
14. [9] Q. Dai, D. Li, S. Jiang, H. Chen, Y. Wang, S. Kan, B. Liu, Q. Cui and G. Zou, “Synthesis of monodisperse CdSe nanocrystals directly open to air: Monomer reactivity tuned by the selenium ligand”, J. Cryst. Growth, vol. 292, pp. 14–18, 2006.
15. [10] S. M. Farkhani and A. Valizadeh, “Review: three synthesis methods of CdX (X = Se, S or Te) quantum dots”, IET Nanobiotechnology, vol. 8, pp. 59–76, 2014.
16. [11] M. Z. Hu and T. Zhu, “Semiconductor Nanocrystal Quantum Dot Synthesis Approaches Towards Large-Scale Industrial Production for Energy Applications”, Nanoscale Res. Lett., vol. 10, pp. 1-15, 2015.
17. [12] L. Qu, W. W. Yu and X. Peng, “In Situ Observation of the Nucleation and Growth of CdSe Nanocrystals”, Nano Lett., vol. 4, pp. 465-469, 2004.