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A major limitation of transient optical spectroscopy is that relatively high laser fluences are required to enable broadband, multichannel detection with acceptable signal-to-noise levels. Under typical experimental conditions, many condensed phase and nanoscale materials exhibit fluence-dependent dynamics, including higher order effects such as carrier–carrier annihilation. With the proliferation of commercial laser systems, offering both high repetition rates and high pulse energies, have come new opportunities for high sensitivity pump-probe measurements at low pump fluences. However, experimental considerations needed to fully leverage the statistical advantage of these laser systems have not been fully described. Here, we demonstrate a high repetition rate, broadband transient spectrometer capable of multichannel shot-to-shot detection at 90 kHz. Importantly, we find that several high-speed cameras exhibit a time-domain fixed pattern noise resulting from interleaved analog-to-digital converters, which is particularly detrimental to the conventional “ON/OFF” modulation scheme used in pump-probe spectroscopy. Using a modified modulation and data processing scheme, we achieve a noise level of 10−5 in 4 s for differential transmission, an order of magnitude lower than for commercial 1 kHz transient spectrometers for the same acquisition time. We leverage the high sensitivity of this system to measure the differential transmission of monolayer graphene at low pump fluence. We show that signals on the order of 10−6 OD can be measured, enabling a new data acquisition regime for low-dimensional materials.
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Transient Absorption Microscopy Using Widefield Lock-in Camera Imaging
Over the past decade, the proliferation of pulsed laser sources with high repetition rates has facilitated a merger of ultrafast time-resolved spectroscopy with imaging microscopy. In transient absorption microscopy (TAM), the excited-state dynamics of a system are tracked by measuring changes in the transmission of a focused probe pulse following photoexcitation of a sample. Typically, these experiments are done using a photodiode detector and lock-in amplifier synchronized with the laser and images highlighting spatial heterogeneity in the TAM signal are constructed by scanning the probe across a sample. Performing TAM by instead imaging a spatially defocused widefield probe with a multipixel camera could dramatically accelerate the acquisition of spatially resolved dynamics, yet approaches for such widefield imaging generally suffer from reduced signal-to-noise due to an incompatibility of multipixel cameras with high-frequency lock-in detection. Herein, we describe implementation of a camera capable of high-frequency lock-in detection, thereby enabling widefield TAM imaging at rates matching those of high repetition rate lasers. Transient images using a widefield probe and two separate pump pulse configurations are highlighted. In the first, a widefield probe was used to image changes in the spatial distribution of photoexcited molecules prepared by a tightly focused pump pulse, while in the second, a widefield probe detected spatial variations in photoexcited dynamics within a heterogeneous organic crystal excited by a defocused pump pulse. These results highlight the ability of high-sensitivity lock-in detection to enable widefield TAM imaging, which can be leveraged to further our understanding of excited-state dynamics and excitation transport within spatially heterogeneous systems.
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- PAR ID:
- 10532653
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry C
- Volume:
- 128
- Issue:
- 28
- ISSN:
- 1932-7447
- Page Range / eLocation ID:
- 11723 to 11731
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acs.jpcc.4c02984
