وثيقة

Dye-induced emission quenching of quantum dots : role of charge carrier lifetime, confinement and wavefunction engineering.

المصدر
Doctoral dissertation
عناوين أخرى
تبريد انبعاث الكوانتم دوت الناجم عن الصبغة : دور عمر حاملات الشحنة والحبس والهندسة الموجية
الدولة
Oman
مكان النشر
Muscat
الناشر
Sultan Qaboos University
ميلادي
2024
اللغة
الأنجليزية
نوع الرسالة الجامعية
Doctoral dissertation
الملخص الإنجليزي
Optical excitation of semiconductor quantum dots (QDs) generates electron-hole pairs, and their radiative recombination yields intrinsic photoluminescence (PL). However, this absorption-emission cycle is often interrupted due to the trapping of photoexcited charge carriers into localized electronic states, commonly known as traps. Generally, the trapping of charge carriers quenches the QD emission, hence lowering the PL quantum yield. This thesis work investigates the role of the excited state lifetime, charge carrier’s confinement, and wavefunction engineering of core/shell and core/shell/shell cadmium-free QDs in charge trapping due to the attachment of dye molecules on the QD surface. In the first part, PL quenching of nanoassemblies of CuInS2/ZnS (CIS) QDs and rhodamine 560 molecules (Rh560) is spectroscopically investigated by steadystate and femtosecond-to-nanosecond time-resolved techniques. Transient absorption measurements of the CIS-Rh560 assemblies resolved the fast component of electron trapping that occurs in tens to hundreds of picoseconds, while PL lifetime measurements resolved the slow components of trapping that occur in hundreds of nanoseconds. Unlike traditional CdSe/ZnS QDs, the PL lifetime of CIS QDs approaches the typical time scale of fluorescence intermittency. As a result, the excited state of CIS QDs is vulnerable to the blinking process and the weight of dynamic quenching increases, which leads to an upward curvature in the Stern-Volmer plot. In the second part, PL quenching of nanoassemblies of CIS and InP/ZnS (InP) QDs with Rh560 and rhodamine 575 (Rh575) dye molecules of different ionic characters (Rh560; cationic and Rh575; zwitterionic) is investigated. These QDs show different excited state lifetimes and electron confinement energies. CIS exhibits a lifetime ca. 290 ns and weak confinement energy of 664 meV whereas InP has a lifetime ca. 37 ns and strong confinement energy of 1194 meV, SternVolmer analysis shows that (i) dynamic quenching is dominating in all QD-dye assemblies with only a minor contribution from static quenching and (ii) quenching is generally more pronounced in CIS-dye assemblies as compared to InP-dye assemblies. These results are explained on the basis of differences in electron trapping rates in QD-dye assemblies due to the charge carriers' wavefunction extension onto the QDs' shell surface. In addition, Rh560 dye exhibits a stronger interaction in comparison to Rh575 dye. This is attributed to the variation in electrostatic interaction between the dyes and the partial negative charges of the QD shell surface. Finally, PL quenching of InP/ZnS core/shell (InP CS) and InP/ZnSe/ZnS core/shell/shell (InP CSS) QDs in the assembly with Rh560 and Rh575 dye molecules is investigated. The major observation is that the steady-state and bimolecular quenching rate constants of CSS QDs are 7.5 to 21.7 times larger than that of CS QDs. Interestingly, the direct excitation of dye molecules in the QD-dye assembly leads to the efficient excitation energy transfer from dye to the CS QDs, which yields QD’s PL recovery. Energy transfer is less efficient in CSS QDs and exhibits a net QD PL quenching. Moreover, in CSS QD-dye assemblies, the PL quenching rate is 6.1 to 39.5 times higher than the energy transfer rate.
الملخص العربي
تعتمد معظم تطبيقات حصاد الضوء الاصطناعي على امتصاص الضوء الفعال والطاقة المستحثة ضوئياً أو على عمليات نقل الشحنة بين الأجزاء المانحة والمستقبلة في التجمعات النانوية العضوية وغير العضوية. لقيت أشباه الموصلات الكوانتم دوت اهتماما كبيرمواد غير عضوية متعددة الاستخدامات بسبب خصائصها الضوئية والإلكترونية المتعددة على الحجم وسميتها الأقل وكذلك توافقها الحيوي.
قالب العنصر
الرسائل والأطروحات الجامعية

مواد أخرى لنفس الموضوع

الرسائل والأطروحات الجامعية
5
0
Al-Farsi, Basim Abdullah Darwish.
Sultan Qaboos University.
2024