Ultrafast laser spectroscopy uncovers mechanisms of light energy conversion in photosynthesis and sustainable energy materials

The invention of the laser in 1960 gave us the ruby laser, which generally produced chaotic pulses of light. Six years later, in 1966, a concept called passive mode-locking applied to neodymium-glass lasers produced reasonably well-behaving picosecond pulses. This triggered an intense activity, with respect to developing improved laser pulse sources, measurement techniques, and application to chemistry, physics, and biology. Initially, only ∼10 –ps-long pulses at a few wavelengths were available. Nevertheless, insight into the function of complex biological systems, like photosynthetic proteins, and molecules of chemical interest was gained in very early studies. Today, both duration and color of ultrashort pulses can be tuned to almost any value. This has of course opened up possibilities to study almost any atomic, molecular, or solid-state system and any dynamic process. This review focuses on the use of laser spectroscopy to investigate light energy conversion mechanisms in both natural photosynthesis and a topical selection of novel materials for solar energy conversion. More specifically, in photosynthesis we will review light harvesting and primary electron transfer; materials for solar energy conversion that we discuss include sensitized semiconductors (dye sensitized solar cells), polymer:fullerene and polymer:polymer bulk heterojunctions (organic solar cells), organometal halide perovskites, as well as molecular and hybrid systems for production of solar fuel and valuable chemicals. All these scientific areas, and in particular photosynthesis and the solar cell materials, have been extensively studied with ultrafast spectroscopy, resulting in a vast literature; a comprehensive review of the individual materials is, therefore, not feasible, and we will limit our discussion to work that we think has been of particular importance for understanding the function of the respective systems.