Radiation Hardness of Perovskite Solar Cells Based on Aluminum‐Doped Zinc Oxide Electrode Under Proton Irradiation

Due to their high specific power and potential to save both weight and stow volume, perovskite solar cells have gained increasing interest to be used for space applications. However, before they can be deployed into space, their resistance to ionizing radiations such as high‐energy protons must be demonstrated. In this report, we investigate the effect of 150 keV protons on the performance of perovskite solar cells based on aluminium‐doped zinc oxide (AZO) transparent conducting oxide (TCO). Record power conversion efficiency of 15% and 13.6% were obtained for cells based on AZO under AM1.5G and AM0 illumination, respectively. We demonstrate that perovskite solar cells can withstand proton irradiation up to 1013 protons.cm−2 without significant loss in efficiency. At this irradiation dose, Si or GaAs solar cells would be completely or severely degraded when exposed to 150 keV protons. From 1014 protons.cm−2, a decrease in short‐circuit current of the perovskite cells is observed, which is consistent with interfacial degradation due to deterioration of the Spiro‐OMeTAD HTL during proton irradiation. Using a combination of non‐destructive characterization techniques, results suggest that the structural and optical properties of perovskite remain intact up to high fluence levels. Although shallow trap states are induced by proton irradiation in perovskite bulk at low fluence levels, they can release charges efficiently and are not detrimental to the cell's performance. This work highlights the potential of perovskite solar cells based on AZO TCO to be used for space applications and give a deeper understanding of interfacial degradation due to proton irradiation

Use of gas cluster ion source depth profiling to study the oxidation of fullerene thin films by XPS

The analysis of organic materials such as phenyl-C61-butyric acid methyl ester (PC61BM) by depth profiling is typically fraught with difficulty due to the fragile nature of the sample. In this work we utilise a gas cluster ion source for the controlled depth profiling of organic materials that would historically have been too fragile to analyse and obtain quantitative compositional data through the whole thickness of the film. In particular we examine the oxygen diffusion and photo-oxidation kinetics of one of the most commonly used electron acceptor materials for many organic optoelectronic applications, namely PC61BM, in both neat films and in blends with polystyrene. Exposure to AM1.5G light and air under ambient conditions, results in a higher level of surface oxidation of blended PC61BM:polystyrene than is observed for either pure control film. Gas cluster ion source depth profiling further confirms that this oxidation is strongest at the extreme surface, but that over time elevated oxygen levels associated with oxidised organic species are observed to penetrate through the whole blended film. The results presented herein provide further insights on the environmental stability of fullerene based organic optoelectronic devices

Twisted carotenoids do not support efficient intramolecular singlet fission in the orange carotenoid protein

Singlet exciton fission is the spin-allowed generation of two triplet electronic excited states from a singlet state. Intramolecular singlet fission has been suggested to occur on individual carotenoid molecules within protein complexes, provided the conjugated backbone is twisted out-of-plane. However, this hypothesis has only been forwarded in protein complexes containing multiple carotenoids and bacteriochlorophylls in close contact. To test the hypothesis on twisted carotenoids in a 'minimal' one-carotenoid system, we study the orange carotenoid protein (OCP). OCP exists in two forms: in its orange form (OCPo), the single bound carotenoid is twisted, whereas in its red form (OCPr), the carotenoid is planar. To enable room-temperature spectroscopy on canthaxanthin-binding OCPo and OCPr without laser-induced photoconversion, we trap them in trehalose glass. Using transient absorption spectroscopy, we show that there is no evidence of long-lived triplet generation through intramolecular singlet fission, despite the canthaxanthin twist in OCPo

Characterization of stability of benchmark organic photovoltaic films after proton and electron bombardments

Organic solar cells have attractive potential for space applications as they have very high specific power (power generated per weight) and ultra-high flexibility (to reduce stowed volume). However, one critical issue is whether they are stable under the harsh space environment, particularly their stability under high energy, high flux, electron and proton bombardment. In this paper, the stability of benchmark organic photovoltaic layers under proton bombardment (150 keV with a fluence of 1 × 1012/cm2) and electron bombardment (1 MeV with a fluence of 1 × 1013/cm2) under vacuum is investigated. Raman spectroscopy, photoluminescence spectroscopy, and optical reflectance spectroscopy are applied to study their chemical/structural, photo-chemical/morphological, and optical stability after the bombardments. The results show that all the benchmark organic photovoltaic films are stable under the radiation, implying that organic solar cells could be feasible for space applications

Proton Radiation Hardness of Perovskite Solar Cells Utilizing a Mesoporous Carbon Electrode

Funder: Airbus Endeavr WalesFunder: Alexander von Humboldt FoundationWhen designing spacefaring vehicles and orbital instrumentation, the onboard systems such as microelectronics and solar cells require shielding to protect them from degradation brought on by collisions with high‐energy particles. Perovskite solar cells (PSCs) have been shown to be much more radiation stable than Si and GaAs devices, while also providing the ability to be fabricated on flexible substrates. However, even PSCs have their limits, with higher fluences being a cause of degradation. Herein, a novel solution utilizing a screen‐printed, mesoporous carbon electrode to act bi‐functionally as an encapsulate and the electrode is presented. It is demonstrated that the carbon electrode PSCs can withstand proton irradiation up to 1 × 1015 protons cm−2 at 150 KeV with negligible losses (<0.07%) in power conversion efficiency. The 12 μm thick electrode acts as efficient shielding for the perovskite embedded in the mesoporous TiO2. Through Raman and photoluminescence spectroscopy, results suggest that the structural properties of the perovskite and carbon remain intact. Simulations of the device structure show that superior radiation protection comes in conjunction with good device performance. This work highlights the potential of using a carbon electrode for future space electronics which is not limited to only solar cells

Toward Improved Environmental Stability of Polymer:Fullerene and Polymer:Nonfullerene Organic Solar Cells: A Common Energetic Origin of Light- and Oxygen-Induced Degradation

With the emergence of nonfullerene electron acceptors resulting in further breakthroughs in the performance of organic solar cells, there is now an urgent need to understand their degradation mechanisms in order to improve their intrinsic stability through better material design. In this study, we present quantitative evidence for a common root cause of light-induced degradation of polymer:nonfullerene and polymer:fullerene organic solar cells in air, namely, a fast photo-oxidation process of the photoactive materials mediated by the formation of superoxide radical ions, whose yield is found to be strongly controlled by the lowest unoccupied molecular orbital (LUMO) levels of the electron acceptors used. Our results elucidate the general relevance of this degradation mechanism to both polymer:fullerene and polymer:nonfullerene blends and highlight the necessity of designing electron acceptor materials with sufficient electron affinities to overcome this challenge, thereby paving the way toward achieving long-term solar cell stability with minimal device encapsulation

The role of fullerenes in the environmental stability of polymer:fullerene solar cells

Environmental stability is a common challenge for the commercialisation of low cost, encapsulation-free organic opto-electronic devices. Understanding the role of materials degradation is the key to address this challenge, but most such studies have been limited to conjugated polymers. Here we quantitatively study the role of the common fullerene derivative PCBM in limiting the stability of benchmark organic solar cells, showing that a minor fraction (<1%) of photo-oxidised PCBM, induced by short exposure to either solar or ambient laboratory lighting conditions in air, consistent with typical processing and operating conditions, is sufficient to compromise device performance severely. We identify the effects of photo-oxidation of PCBM on its chemical structure, and connect this to specific changes in its electronic structure, which significantly alter the electron transport and recombination kinetics. The effect of photo-oxidation on device current–voltage characteristics, electron mobility and density of states could all be explained with the same model of photoinduced defects acting as trap states. Our results demonstrate that the photochemical instability of PCBM and chemically similar fullerenes remains a barrier for the commercialisation of organic opto-electronic devices

Triplets in extended nematic liquid crystals and polarons in their blends

Photoinduced absorption shows that triplets are the primary photoexcited species in a series of conjugated liquid crystals containing thiophene and fluorene groups. We find that the triplet generation rate can be varied substantially by molecular design. The introduction of extra thiophene groups into the elongated molecules changes the intersystem crossing rate by over two orders of magnitude, while modifying the singlet and triplet energies by only small amounts. This result is attributed to the high spin-orbit coupling constant of sulfur: An increase in the number of sulfur atoms increases the spin-orbit coupling between the singlet and triplet states. These results are relevant to the design of organic light emitting diodes, lasers, and other devices where triplet formation has a major impact on device performance. The molecules are shown to act as effective electron donors when blended with a perylene molecule which acts as an electron acceptor. The electron transfer rate is faster than the singlet lifetime so that the blend shows the efficient charge separation required for a photovoltaic device. © 2007 American Institute of Physics.Link_to_subscribed_fulltex