Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots

Jia, Yanyan; Chen, Jinquan; Wu, Kaifeng; Kaledin, Alex; Musaev, Djamaladdin G.; Xie, Zhaoxiong; Lian, Tianquan

doi:10.1039/c6sc00192k

Enhancing photo-reduction quantum efficiency using quasi-type II core/shell quantum dots

Journal Article · Tue Mar 01 23:00:00 EST 2016 · Chemical Science

DOI:https://doi.org/10.1039/c6sc00192k· OSTI ID:1624935

Jia, Yanyan ^[1]; Chen, Jinquan ^[2]; Wu, Kaifeng ^[2]; Kaledin, Alex ^[2]; Musaev, Djamaladdin G. ^[2]; Xie, Zhaoxiong ^[3]; Lian, Tianquan ^[2]

Emory Univ., Atlanta, GA (United States). Dept. of Chemistry; Xiamen Univ. (China). State Key Lab. of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Dept. of Chemistry; DOE/OSTI
Emory Univ., Atlanta, GA (United States). Dept. of Chemistry
Xiamen Univ. (China). State Key Lab. of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Dept. of Chemistry

Quantum confined semiconductor nanocrystals have emerged as a new class of materials for light harvesting and charge separation applications due to the ability to control their properties through rational design of their size, shape and composition. We report here a study of enhancing the quantum yield of methyl viologen (MV²⁺) photoreduction using colloidal quasi-type II CdSe/CdS core/shell quantum dots (QDs). The steady-state quantum yield of MV^+c radical generation, in the presence of thiols as sacrificial donors, increased monotonically with the CdS shell thickness within the studied thickness regime (0–4.7 CdS monolayers). Using ultrafast transient absorption and time-resolved photoluminescence decay spectroscopy, we found that both the rates of electron transfer from the QD to MV²⁺ and the subsequent charge recombination in QD⁺–MV^+c complexes decreased exponentially with the shell thickness, consistent with calculated 1S electron and hole densities at the QD surfaces, respectively. Interestingly, the hole transfer rate remained relatively independent of shell thickness, likely due to a cancellation of the reduction of hole transfer coupling strength with the increased number of hole acceptor ligands on the QD surface at larger shell thickness. As a result, with increasing CdS shell thickness, the charge recombination loss decreases, enhancing the photoreduction quantum efficiency. This novel approach for improving photoreduction quantum efficiency should be applicable to many type II and quasi-type II core/shell quantum dots.

View Accepted Manuscript (DOE)

Research Organization:: Emory Univ., Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF)

Grant/Contract Number:: FG02-07ER15906

OSTI ID:: 1624935

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 7 Vol. 7; ISSN 2041-6520; ISSN CSHCBM

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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