Dissecting charge relaxation pathways in CdSe/CdS nanocrystals using femtosecond two-dimensional electronic spectroscopy.
Exciton relaxation dynamics of CdSe and quasi-type-II CdSe/CdS core/shell nanocrystals were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The use of 2DES allowed for determination of structure-specific and state-resolved carrier dynamics for CdSe nanocrystals formed with five, or fewer, CdS passivation monolayers (ML). For CdSe and CdSe/CdS nanocrystals formed with one through three MLs of CdS, excitation using broad bandwidth femtosecond visible laser pulses generated electron-hole pairs among the |X1〉 = 2.14 eV and |X2〉 = 2.27 eV exciton states. For both excitations, the electron is promoted to the lowest energy excited (1Se) conduction-band state and the hole is in the 1S3/2(X1) or 2S3/2(X2) valence-band state. Therefore, the relaxation dynamics of the hot hole were isolated by monitoring the-time-dependent amplitude of 2DES cross peaks. The time constant for hot hole relaxation within the CdSe valence band was 150 ± 45 fs. Upon passivation by CdS, this hole relaxation time constant increased to 170 ± 30 fs (CdSe/CdS-3ML). This small increase was attributed to the formation of a graded, or alloyed, interfacial region that precedes the growth of a uniform CdS capping layer. The small increase in hole relaxation time reflects the larger nanocrystal volume of the CdSe/CdS system with respect to the CdSe nanocrystal core. In contrast, the dynamics of larger core/shell nanocrystals (≥4ML CdS) exhibited a picosecond buildup in 2DES cross-peak amplitude. This time-dependent response was attributed to interfacial hole transfer from CdS to CdSe valence-band states. Importantly, the 2DES data distinguish CdSe exciton relaxation from interfacial carrier transfer dynamics. In combination, isolation of structurally well-defined nanocrystals and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices.
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. kknappenberger@fsu.edu.
J W
http://orcid.org/0000-0003-1308-1519
JW
Jarrett
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. kknappenberger@fsu.edu.
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C
Yi
IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy.
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T
Stoll
IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy and Paul Scherrer Institute, CH-4232 Villigen PSI, Switzerland.
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J
Rehault
IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy and Laboratoire de Spectroscopie Ultrarapide, EPFL, CH-1015 Lausanne, Switzerland.
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A
Oriana
IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy.
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F
Branchi
IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy.
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Cerullo
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. kknappenberger@fsu.edu and IFN-CNR, Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano, Italy and National High Magnetic Field Laboratory, 1800 E. Paul Dirac Drive, Tallahassee, Florida 32310-4005, USA.
K L
http://orcid.org/0000-0003-4123-3663
KL
Knappenberger