Donaldson Paul M, Greetham Greg M, Middleton Chris T, Luther Bradley M, Zanni Martin T, Hamm Peter, Krummel Amber T
Central Laser Facility, Research Complex at Harwell, STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot OX11 0QX, United Kingdom.
PhaseTech Spectroscopy, Inc., 4916 East Broadway, Suite 125, Madison, Wisconsin 53716, United States.
Acc Chem Res. 2023 Aug 1;56(15):2062-2071. doi: 10.1021/acs.accounts.3c00152. Epub 2023 Jul 10.
ConspectusUltrafast spectroscopy and imaging have become tools utilized by a broad range of scientists involved in materials, energy, biological, and chemical sciences. Commercialization of ultrafast spectrometers including transient absorption spectrometers, vibrational sum frequency generation spectrometers, and even multidimensional spectrometers have put these advanced spectroscopy measurements into the hands of practitioners originally outside the field of ultrafast spectroscopy. There is now a technology shift occurring in ultrafast spectroscopy, made possible by new Yb-based lasers, that is opening exciting new experiments in the chemical and physical sciences. Amplified Yb-based lasers are not only more compact and efficient than their predecessors but also, most importantly, operate at many times the repetition rate with improved noise characteristics in comparison to the previous generation of Ti:sapphire amplifier technologies. Taken together, these attributes are enabling new experiments, generating improvements to long-standing techniques, and affording the transformation of spectroscopies to microscopies. This Account aims to show that the shift to 100 kHz lasers is a transformative step in nonlinear spectroscopy and imaging, much like the dramatic expansion that occurred with the commercialization of Ti:sapphire laser systems in the 1990s. The impact of this technology will be felt across a great swath of scientific communities. We first describe the technology landscape of amplified Yb-based laser systems used in conjunction with 100 kHz spectrometers operating with shot-to-shot pulse shaping and detection. We also identify the range of different parametric conversion and supercontinuum techniques which now provide a path to making pulses of light optimal for ultrafast spectroscopy. Second, we describe specific instances from our laboratories of how the amplified Yb-based light sources and spectrometers are transformative. For multiple probe time-resolved infrared and transient 2D IR spectroscopy, the gain in temporal span and signal-to-noise enables dynamical spectroscopy measurements from femtoseconds to seconds. These gains widen the applicability of time-resolved infrared techniques across a range of topics in photochemistry, photocatalysis, and photobiology as well as lower the technical barriers to implementation in a laboratory. For 2D visible spectroscopy and microscopy with white light, as well as 2D IR imaging, the high repetition rates of these new Yb-based light sources allow one to spatially map 2D spectra while maintaining high signal-to-noise in the data. To illustrate the gains, we provide examples of imaging applications in the study of photovoltaic materials and spectroelectrochemistry.
综述
超快光谱学和成像技术已成为材料、能源、生物和化学等广泛科学领域的科学家所使用的工具。超快光谱仪的商业化,包括瞬态吸收光谱仪、振动和频产生光谱仪,甚至多维光谱仪,使这些先进的光谱测量方法落入了超快光谱学领域之外的从业者手中。如今,超快光谱学正在发生技术变革,新型镱基激光器使这一变革成为可能,为化学和物理科学领域开启了令人兴奋的新实验。基于镱的放大激光器不仅比其前身更紧凑、更高效,而且最重要的是,与上一代钛宝石放大器技术相比,其重复频率提高了许多倍,噪声特性也得到了改善。综合起来,这些特性使得新实验成为可能,改进了长期存在的技术,并使光谱学向显微镜学转变。本综述旨在表明,向100 kHz激光器的转变是非线性光谱学和成像领域的一个变革性步骤,类似于20世纪90年代钛宝石激光系统商业化所带来的巨大发展。这项技术的影响将在广大科学领域中显现出来。我们首先描述与采用逐脉冲整形和检测的100 kHz光谱仪结合使用的基于镱的放大激光系统的技术概况。我们还确定了不同的参量转换和超连续谱技术的范围,这些技术现在为产生最适合超快光谱学的光脉冲提供了一条途径。其次,我们描述了我们实验室中基于镱的放大光源和光谱仪具有变革性的具体实例。对于多探针时间分辨红外光谱和瞬态二维红外光谱,时间跨度和信噪比的提高使得能够进行从飞秒到秒的动态光谱测量。这些进展拓宽了时间分辨红外技术在光化学、光催化和光生物学等一系列主题中的应用范围,并降低了实验室实施的技术门槛。对于二维可见光谱和白光显微镜以及二维红外成像,这些新型基于镱的光源的高重复频率允许在保持数据高信噪比的同时对二维光谱进行空间映射。为了说明这些进展,我们提供了在光伏材料研究和光谱电化学中的成像应用实例。