Description of the Adsorption and Exciton Delocalizing Properties of p-Substituted Thiophenols on CdSe Quantum Dots

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• 作者：Kenneth O. Aruda ; Victor A. Amin ; Christopher M. Thompson ; Bryan Lau ; Alexander B. Nepomnyashchii ; Emily A. Weiss
• 刊名：Langmuir
• 出版年：2016
• 出版时间：April 12, 2016
• 年：2016
• 卷：32
• 期：14
• 页码：3354-3364
• 全文大小：530K
• 年卷期：0
• ISSN：1520-5827

文摘

This work describes the quantitative characterization of the interfacial chemical and electronic structure of CdSe quantum dots (QDs) coated in one of five p-substituted thiophenolates (X-TP, X = NHb>2b>, CHb>3b>O, CHb>3b>, Cl, or NOb>2b>), and the dependence of this structure on the p-substituent X. ¹H NMR spectra of mixtures of CdSe QDs and X-TPs yield the number of X-TPs bound to the surface of each QD. The binding data, in combination with the shift in the energy of the first excitonic peak of the QDs as a function of the surface coverage of X-TP and Raman and NMR analysis of the mixtures, indicate that X-TP binds to CdSe QDs in at least three modes, two modes that are responsible for exciton delocalization and a third mode that does not affect the excitonic energy. The first two modes involve displacement of OPA from the QD core, whereas the third mode forms cadmium–thiophenolate complexes that are not electronically coupled to the QD core. Fits to the data using the dual-mode binding model also yield the values of Δrb>1b>, the average radius of exciton delocalization due to binding of the X-TP in modes 1 and 2. A 3D parametrized particle-in-a-sphere model enables the conversion of the measured value of Δrb>1b> for each X-TP to the height of the potential barrier that the ligand presents for tunneling of excitonic hole into the interfacial region. The height of this barrier increases from 0.3 to 0.9 eV as the substituent, X, becomes more electron-withdrawing.