Using a novel spectroscopy technique, physicists in Japan have revealed how organic materials accumulate electrical charge through long-term illumination by sunlight – leading to material degradation. Ryota Kabe and colleagues at the Okinawa Institute of Science and Technology have shown how charge separation occurs gradually via a rare multi-photon ionization process, offering new insights into how plastics and organic semiconductors degrade in sunlight.

In a typical organic solar cell, an electron-donating material is interfaced with an electron acceptor. When the donor absorbs a photon, one of its electrons may jump across the interface, creating a bound electron-hole pair which may eventually dissociate – creating two free charges from which useful electrical work can be extracted.

Although such an interface vastly boosts the efficiency of this process, it is not necessary for charge separation to occur when an electron donor is illuminated. “Even single-component materials can generate tiny amounts of charge via multiphoton ionization,” Kabe explains. “However, experimental evidence has been scarce due to the extremely low probability of this process.”

To trigger charge separation in this way, an electron needs to absorb one or more additional photons while in its excited state. Since the vast majority of electrons fall back into their ground states before this can happen, the spectroscopic signature of this charge separation is very weak. This makes it incredibly difficult to detect using conventional spectroscopy techniques, which can generally only make observations over timescales of up to a few milliseconds.

The opposite approach

“While weak multiphoton pathways are easily buried under much stronger excited-state signals, we took the opposite approach in our work,” Kabe describes. “We excited samples for long durations and searched for traces of accumulated charges in the slow emission decay.”

Key to this approach was an electron donor called NPD. This organic material has a relatively long triplet lifetime, where an excited electron is prevented from transitioning back to its ground state. As a result, these molecules emit phosphorescence over relatively long timescales.

In addition, Kabe’s team dispersed their NPD samples into different host materials with carefully selected energy levels. In one medium, the energies of both the highest-occupied and lowest-unoccupied molecular orbitals lay below NPD’s corresponding levels, so that the host material acted as an electron acceptor. As a result, charge transfer occurred in the same way as it would across a typical donor-acceptor interface.

Yet in another medium, the host’s lowest-unoccupied orbital lay above NPD’s – blocking charge transfer, and allowing triplet states to accumulate instead. In this case, the only way for charge separation to occur was through multi-photon ionization.

Slow emission decay analysis

Since NPD’s long triplet lifetime allowed its electrons to be excited gradually over an extended period of illumination, its weak charge accumulation became detectable through slow emission decay analysis. In contrast, more conventional methods involve multiple, ultra-fast laser pulses, severely restricting the timescale over which measurements can be made. Altogether, this approach enabled the team to clearly distinguish between the two charge generation pathways.

“Using this method, we confirmed that charge generation occurred via resonance-enhanced multiphoton ionization mediated by long-lived triplet states, even in single-component organic materials,” Kabe describes.

This result offers insights into how plastics and organic semiconductors are degraded by sunlight over years or decades. The conventional explanation is that sunlight generates free radicals. These are molecules that lose an electron through ionization, leaving behind an unpaired electron which readily reacts with other molecules in the surrounding environment. Since photodegradation unfolds over such a long timescale, researchers could not observe this charge generation in single-component organic materials – until now.

“The method will be useful for analysing charge behaviour in organic semiconductor devices and for understanding long-term processes such as photodegradation that occur gradually under continuous light exposure,” Kabe says.

The research is described in Science Advances.

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