TY - JOUR
T1 - Ultrafast Spectroelectrochemistry Reveals Photoinduced Carrier Dynamics in Positively Charged CdSe Nanocrystals
AU - Honarfar, Alireza
AU - Chabera, Pavel
AU - Lin, Weihua
AU - Meng, Jie
AU - Mourad, Hassan
AU - Pankratova, Galina
AU - Gorton, Lo
AU - Zheng, Kaibo
AU - Pullerits, Tõnu
PY - 2021
Y1 - 2021
N2 - Extra charges in semiconductor nanocrystals are of paramount importance for their electrically driven optoelectronic and photovoltaic applications. Optical excitations of such charged nanocrystals lead to rapid recombination via an Auger process, which can deteriorate the performance of the corresponding devices. While numerous articles report trion Auger processes in negatively charged nanocrystals, optical studies of well-controlled positive charging of nanocrystals and detailed studies of positive trions remain rare. In this work, we used electrochemistry to achieve positive charging of CdSe nanocrystals, so-called quantum dots (QDs), in a controlled way. Femtosecond transient absorption spectroscopy was applied for in situ investigation of the charge carrier dynamics after optical excitation of the electrochemically charged QD assembly on TiO2. We observe that without bias (i.e., neutral QDs), sub-picosecond hot carrier cooling is followed by multiple phases of the dynamics corresponding to electron injection and transfer to the TiO2. Positive charging first leads to activation of the hole traps close to the valence band maximum, which opens a rapid recombination channel of the optical excitation. A further increase in the positive bias interrupts the electron injection to TiO2, and if nanocrystals are positively charged, it leads to Auger relaxation in a few hundred picosecond timescale. This study represents a step toward the understanding of the effect of positive charging on the performance of semiconductor nanocrystals under conditions which closely mimic their potential applications.
AB - Extra charges in semiconductor nanocrystals are of paramount importance for their electrically driven optoelectronic and photovoltaic applications. Optical excitations of such charged nanocrystals lead to rapid recombination via an Auger process, which can deteriorate the performance of the corresponding devices. While numerous articles report trion Auger processes in negatively charged nanocrystals, optical studies of well-controlled positive charging of nanocrystals and detailed studies of positive trions remain rare. In this work, we used electrochemistry to achieve positive charging of CdSe nanocrystals, so-called quantum dots (QDs), in a controlled way. Femtosecond transient absorption spectroscopy was applied for in situ investigation of the charge carrier dynamics after optical excitation of the electrochemically charged QD assembly on TiO2. We observe that without bias (i.e., neutral QDs), sub-picosecond hot carrier cooling is followed by multiple phases of the dynamics corresponding to electron injection and transfer to the TiO2. Positive charging first leads to activation of the hole traps close to the valence band maximum, which opens a rapid recombination channel of the optical excitation. A further increase in the positive bias interrupts the electron injection to TiO2, and if nanocrystals are positively charged, it leads to Auger relaxation in a few hundred picosecond timescale. This study represents a step toward the understanding of the effect of positive charging on the performance of semiconductor nanocrystals under conditions which closely mimic their potential applications.
U2 - 10.1021/acs.jpcc.1c02729
DO - 10.1021/acs.jpcc.1c02729
M3 - Journal article
SN - 1932-7447
VL - 125
SP - 14332
EP - 14337
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 26
ER -