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Supporting Information

Poisson Distributed Electron Transfer Dynamics from

Single Quantum Dots to C60 Molecules

Nianhui Song,1Haiming Zhu,1Shengye Jin,1Wei Zhan,2Tianquan Lian1 *

1Department of Chemistry, Emory University, Atlanta, Georgia 30322 USA

2Department of Chemistry and Biochemistry, Auburn University, Auburn, AL 36849 USA

* Corresponding author, Email: tlian@emory.edu

RECEIVED DATE (to be automatically inserted)

S1. Transient absorption spectrometer

Femtosecond Transient Visible Absorption Measurements.The femtosecond (0.1 ps to 1 ns)

transient absorption (TA) spectrometer used in this study is based on a regeneratively amplified

Ti: sapphire laser system (coherent Legend, 800 nm, 150 fs, 3 mJ / pulse and 1 KHz repetition rate) and

Helios spectrometer (Ultrafast Systems LLC). Pump pulses at 400 nm were generated by frequency

doubling of the 800 nm pulse at a --barium borate (BBO) crystal. The energy of the 400 nm pump pulse

was controlled to be ~ 20 nJ by a variable neutral-density filter wheel to avoid multiexciton generation

S1
in the QD samples. The pump beam at the sample had a diameter of 300 -m. A white light continuum

probe (from 410-700nm) was generated by attenuating and focusing ~ 10 -J of the 800 nm pulse into a

Sapphire window. The probe beam was collimated and focused with Al parabolic reflectors onto

samples with a beam size of 150 -m. After the sample, the probe beam was collimated and focused into

a fiber optics coupled multichannel spectrometer with CMOS sensor and detected at a frequency of 1

KHz. The pump pulses were chopped by a synchronized chopper to 500 Hz. For all spectroscopy

measurements, the samples were put in a 1 mm cuvette and were constantly stirred by a magnetic stirrer

to avoid photodegradation.

Nanosecond Transient Absorption Measurement.Nanosecond (0.5 ns to 1 -s) transient

absorption was performed with the EOS spectrometer (Ultrafast Systems LLC). The pump pulses at 400

nm were generated in the regeneratively amplified Ti: sapphire laser system as described above. The

white light continuum probe pulse (380 -1700 nm, 0.5 ns pulse width, 20 KHz repetition rate) was

generated by focusing a Nd: YAG laser into a photonic crystal fiber. The probe pulse was synchronized

with the femtosecond amplifier and the delay time was controlled by a digital delay generator (CNT-90,

Pendulum Instruments). The probe light was detected by the same multichannel spectrometers used in

the femtosecond setup. To connect the femtosecond and nanosecond results, the nanosecond spectra

have been scaled (to account for slight differences in excitation power densities) such that the spectra at

delay time 0.6 - 1 ns agree with those measured by the femtosecond setup.

S2. Ensemble-averaged transient absorption spectra of QD-C60 complexes

S2
 free QD QD-C60
0.002 0.002

0.000
0.000

- 0.002
1-2 ps

-Abs (OD)
-Abs (OD)

- 0.002 5-10 ps
1-2 ps - 0.004 20-50 ps
5-10 ps 100-200 ps
- 0.004 20-50 ps
- 0.006 400-600 ps
100-200 ps 800-1400 ps
400-600 ps
- 0.006 a) 0-1 ns 800-1400 ps - 0.008 c) 0-1 ns

- 0.008 - 0.010

0.000
0.000

-Abs (OD)
-Abs (OD)

- 0.002
0.5-1.5 ns 0.5-1.5 ns
- 0.002
5-10 ns 5-10 ns
20-30 ns 20-30 ns
- 0.004
50-80 ns 50-80 ns
100-150 ns - 0.004 100-150 ns
d) 0.5 -1000 ns
300-500 ns 300-500 ns
- 0.006 b) 0.5 -1000 ns
800-1000ns 800-1000ns

450 500 550 600 650 700 450 500 550 600 650 700
wavelength (nm) wavelength (nm)

Figure S1. Transient absorption spectra of QDs (a, b) and QD-C60 complexes (c, d) at indicated delay times
after 400 nm excitation. The femtosecond (a, c, 0-1.5 ns) and nanosecond (b, d, 0.5 -1000 ns) TA spectra
have been scaled such that they overlap at 0.5-1.5 ns.

S3. Ensemble-averaged transient absorption kinetics of QD-C60 complexes

0.0
free QD
- 0.2 QD-C60
-bs (Normalized)

- 0.4

- 0.6

- 0.8

- 1.0

0.00 0.05 0.10 1 10 100

delay time (ns)

Figure S2. 1S exciton band bleach recovery kinetics of QD and QD-C60 complexes In the presence of C60
the QD exciton bleach recovers faster, indicating electron transfer from the QD to adsorbed C60 molecules.

S4. Relative standard deviation of ET rates in single QD-C60 complexes

S3
 0.4
0.3
2
0.2
0.1
0.0
0.3 3

Probability
0.2
0.1
0.0
0.3 4
0.2
0.1
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Relative SD

Figure S3.Histograms of relative standard deviations of ET rates for QD-C60 complexes from samples
2 (red), 3 (blue), and 4 (green).

S4