摘要：
Transientabsorption (TA) spectroscopy is uniquely suited for understandingkinetic processes initiated by light over vast ranges of time. Incombination with white light probes, the recorded differential absorptionspectra can contain spectroscopic signatures characteristic of specificcharge carrier population densities. However, disentangling the often-complexand convoluted spectra is made challenging without robust analysismethods relating the underlying physical mechanisms to the spectralcomponents. In this work, we address the origin of the transient spectraof a model system of emerging solar energy harvesting materials usinga monoclinic BiVO4 thin film. Using ground-state opticalproperties of the semiconductor, we find the main derivative-likespectral response to be related to shifting and broadening of oscillators,rather than specific carrier-related transitions. However, by usingthe Drude optical model of free carriers, we also identify the transientresponse related to free-hole density. Importantly, sample heatingfrom the optical pumping, which begins at 10 ps and plateausby 200 ps, dominates the overall spectral response at longertimes. On the basis of a physical model of the spectral response,a kinetic model is developed that describes the pump power dependenceof the free-hole density, as well as the temporal evolution of thespectral changes associated with shifting and broadening of oscillators.First-principles density functional theory calculations are used torationalize experimental measurements. This comprehensive approachto analyzing and modeling the TA spectra offers a generalizable basisfor understanding the complex pump–probe data, reveals thermalheating artifacts that are frequently erroneously assigned to long-livedphotocarriers, and offers a path to eliminating ambiguity in analysisof photocarrier dynamics in solid-state systems.
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