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This joint experimental-theoretical spectroscopy study of the fullerene derivative PC

In the quest towards more durable solution-processed solar cells, the stability of the active layer materials under operation conditions is important. While lifetimes of several years have been demonstrated for encapsulated organic solar cells, it is generally known that degradation events can be accounted for by air components (O2 and/or water vapour) leaking into the cell through a non-ideal sealing. Here we present a fundamental study of intentional photo-degradation of the electron-acceptor PC60BM ([6,6]-phenyl-C61-butyric acid methyl ester) in air, with the purpose of improving the understanding of the electronic effects of fullerene photo-oxidation. We have studied spincoated thin films of PC60BM by X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure spectroscopy, and Fourier Transform Infrared Spectroscopy, before and after exposing them to simulated sunlight in air. The changes observed in the spectra obtained by these complementary methods were compared with calculated spectra of a large set of possible oxidation products of PC60BM where oxygen atoms have been attached to the C60 cage. The best fit with experimental IR spectra of photodegraded PC60BM films was obtained for a linear combination of calculated spectra for two degradation products, a dicarbonyl and an anhydride, both with open cages with 58 carbon atoms, and the pristine PC60BM molecule. From this comparison, we conclude that the conjugation of the fullerene cage is disturbed by the formation of several carbonyl-based derivatives on the C60 cage, accompanied by a transition from sp2 to sp3-hybridized carbon. The π* resonance in the C1s NEXAFS spectrum was found to be a very sensitive probe for small changes to the fullerene cage, and FT-IR was needed in combination with O1s NEXAFS, to identify the oxidation products. Article part of Blazinic's (2019) doctoral thesis Probing the effects of photodegradation of acceptor materials in polymer solar cells: bulk, surface, and molecular level as manuscript.

Encapsulated organic solar cells often show a burn-in behaviour under illumination. This burn-in manifests itself as a rapid performance loss followed by a much slower progression of the degradation. Here we investigate the burn-in for PCDTBT:PC70BM solar cells under a wide range of illumination intensities. We find that increasing the sunlight concentration from 1 Sun to up to 100 Suns does not change the degradation behaviour, i.e. the dependence of all principal photovoltaic parameters on the dose of solar exposure (in Sun hours). This suggests that the degradation mechanisms under solar concentration (≤100 Suns) are the same as those observed under 1 Sun. This result makes it possible to use concentrated sunlight for accelerated stability assessment of these devices. We also find that devices with PEDOT:PSS as hole transport material show a rapid drop in open-circuit voltage of around 100 mV during the first Sun hour of light exposure. By replacing PEDOT:PSS with MoO3 this initial process can be prevented and only the much slower part of the photo-degradation takes place.

We here demonstrate the use of solution processed NiOx thin films as the hole transport layer (HTL) in a thiophene–quinoxaline copolymer:fullerene solar cell. The NiOx films, which are prepared by UV-ozone treating a nickel formate precursor, outperform the solar cells prepared in this study that use PEDOT:PSS as HTL. The power conversion efficiency improves from 5.3% to 6.1% when replacing PEDOT:PSS with NiOx. Unlike most conventional ways of fabricating solution processed NiOx HTLs, our method does not require high temperature (>300 °C). In fact, we were able to produce high performing NiOx HTLs without the use of any thermal annealing. X-ray photoelectron spectroscopy revealed that a mixture of oxides and hydroxides is formed as a result of the UV-ozone treatment, which differs in composition from those formed by high temperature annealing; UV-ozone treatment produces NiOOH, while only the high temperature annealing produces any significant amount of NiO. Contact potential difference (CPD) measurements reveal an increased work function for all UV-ozone treated NiOx films, consistent with the presence of NiOOH at the surface. The high work function of the UV-ozone treated NiOx films leads to an improved energy level matching between the donor and the HTL, resulting in higher fill factor and hole injection current.

Probing the distribution of donor and acceptor molecules in the active layer of polymer solar cells requires high-resolution methods that provide chemical contrast. A combination of the synchrotron-based soft X-ray technique near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning transmission X-ray microscopy (STXM) can map surface composition and local composition in lateral phase-separated domains, as well as identify molecular signatures of degradation. Here we illustrate, by way of selected results, the relevance of these complementary techniques to the field of organic photovoltaics. We demonstrate firstly that the determination of local composition from X-ray absorption spectra requires cautious use of fitting techniques. Furthermore, we show that drop-like clusters of PC70BM formed during the transfer of spin-coated polymer:PC70BM blend films onto Cu-grids lead to an underestimation of PC70BM/polymer concentration ratios. Finally, we show that the selective degradation of one of the components can impair the accurate determination of local blend composition.

Organic photovoltaic cells based on ternary blends of materials with complementary properties represent an approach to improve the photon-absorption and/or charge transport within the devices. However, the more complex nature of the ternary system, i.e. in diversity of materials' properties and morphological features, complicates the understanding of the processes behind such optimizations. Here, organic photovoltaic cells with wider absorption spectrum composed of two electron-donor polymers, F8T2, poly(9,9-dioctylfluorene -alt- bithiophene), and PTB7, poly([4,8-bis[(2′-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2′-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]), mixed with [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM) are investigated. We demonstrate an improvement of 25% in power conversion efficiency in comparison with the most efficient binary blend control devices. The active layers of these ternary cells exhibit gross phase separation, as determined by Atomic Force Microscopy (AFM) and Synchrotron-based Scanning Transmission X-ray Microscopy (STXM).

A short lifetime is the main factor hindering the wider implementation of low-cost organic photovoltaics in large-area and outdoor applications. Ingress of oxygen and water vapour through non-ideal encapsulation layers is a known cause of degradation for polymer/fullerene based solar cells. To better understand the origin of this performance degradation, we study the effect of intentional exposure of the photo-active layer to simulated sunlight (AM1.5) in air both on the solar cell performance and on the molecular semiconductor materials. Cathode-free thin films of a blend of the electron donor polymer poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and the electron acceptor fullerene derivative [6,6]-phenyl-C

A short lifetime is the main factor hindering the wider implementation of low-cost organic photovoltaics in large-area and outdoor applications. Ingress of oxygen and water vapour through non-ideal encapsulation layers is a known cause of degradation for polymer/fullerene based solar cells. To better understand the origin of this performance degradation, we study the effect of intentional exposure of the photo-active layer to simulated sunlight (AM1.5) in air both on the solar cell performance and on the molecular semiconductor materials. Cathode-free thin films of a blend of the electron donor polymer poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and the electron acceptor fullerene derivative [6,6]-phenyl-C70-butyric acid methyl ester (PC70BM) were exposed to simulated sunlight in air. Fourier-transform infrared spectra demonstrate the formation of carbonyl photo-oxidation products in the blend films, as well as in the pristine polymer and fullerene films. Solar cells prepared with photo-oxidized active layers show increasingly degraded electrical performance (lower short circuit current, open circuit voltage and fill factor) with increasing exposure time. The increased diode ideality factor indicates that trap-assisted recombination hinders device operation after exposure. The external quantum efficiency decreases drastically with increasing exposure time over the whole photon energy range, while the UV-vis absorption spectra of the blend films only show a mild photo-induced bleaching. This demonstrates that not only the photo-induced degradation of the solar cell performance is not predominantly caused by the loss in light absorption, but charge transport and collection are also hampered. This is explained by the fact that photo-oxidation of PC70BM causes bonds in its conjugated cage to break, as evidenced by the decreased π* intensity in C1s-NEXAFS spectra of PC70BM films. This degradation of unoccupied states of PC70BM will hinder the transport of photo-generated electrons to the electrode. Surface photovoltage spectroscopy gives direct evidence for gap states at the surface of a PC70BM film, formed after 2 hours of exposure and resulting in upward band bending at the PC70BM/air surface. These observations indicate that the photo-oxidation of PC70BM is likely to be the main cause of the performance degradation observed when the photoactive layer of a TQ1:PC70BM solar cell is intentionally exposed to light in air.

The polymer TQ1, (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl]) is a popular candidate as donor in organic solar cells. A suitable acceptor molecule together with TQ1 is [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM). We have studied films of TQ1 by fluorescence spectroscopy, with and without PC70BM, in solution and spin-casted from different solvents. The solvents used in this study were chloroform, chlorobenzene, and ortho-dichlorobenzene, while 1-chloronaphthalene was used as solvent additive. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as a fluorescence quencher. Lateral phase-separation occurs in the blend films and its magnitude depends on the solvent used. These morphological differences cause alterations in the fluorescence from TQ1. The degree of quenching is coupled to the morphology through the distance between TQ1 and PC70BM in the film.

The film morphology and device performance of planar heterojunction solar cells based on the molecular donor material α-sexithiophene (6T) are investigated. Planar heterojunctions of 6T with two different acceptor molecules, the C60 fullerene and diindenoperylene (DIP), have been prepared. The growth temperature of the 6T bottom layer has been varied between room temperature and 100 °C for each acceptor. By means of X-ray diffraction and X-ray absorption, we show that the crystallinity and the molecular orientation of 6T is influenced by the preparation conditions and that the 6T film templates the growth of the subsequent acceptor layer. These structural changes are accompanied by changes in the characteristic parameters of the corresponding photovoltaic cells. This is most prominently observed as a shift of the open circuit voltage (Voc): In the case of 6T/C60 heterojunctions, Voc decreases from 0.4 to 0.3 V, approximately, if the growth temperature of 6T is increased from room temperature to 100 °C. By...

We have studied the photo-degradation in air of a blend of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1), and how the photo-degradation affects the solar cell performance. Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, changes to the electronic structure of TQ1 and PCBM caused by illumination in ambient air are investigated and compared between the pristine materials and the blend. The NEXAFS spectra show that the unoccupied molecular orbitals of TQ1 are not significantly changed by the exposure of pristine TQ1 to light in air, whereas those of PCBM are severely affected as a result of photo-induced degradation of PCBM. Furthermore, the photo-degradation of PCBM is accelerated by blending it with TQ1. While the NEXAFS spectrum of TQ1 remains unchanged upon illumination in air, its valence band spectrum shows that the occupied molecular orbitals are weakly affected. Yet, UV-Vis absorption spectra demonstrate photo-bleaching of TQ1, which is attenuated in the presence of PCBM in blend films. Illumination of the active layer of TQ1: PCBM solar cells prior to cathode deposition causes severe losses in electrical performance.

The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C 71 - butyric acid methyl ester (PC 70 BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %. We have studied TQ1 films, with and without PC 70 BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene ( o -DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC 70 BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC 70 BM. Furthermore, if using a bad solvent for PC 70 BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC 70 BM. Clear differences were found, comparing the TQ1:PC 70 BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition. The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.

Fullerenes have been a main focus of scientific research since their discovery due to the interesting possible applications in various fields like organic photovoltaics (OPVs). In particular, the derivative [6,6]-phenyl-C60-butyric acid methyl ester (PCBM) is currently one of the most popular choices due to its higher solubility in organic solvents compared to unsubstituted C60. One of the central issues in the field of OPVs is device stability, since modules undergo deterioration (losses in efficiency, open circuit voltage, and short circuit current) during operation. In the case of fullerenes, several possibilities have been proposed, including dimerization, oxidation, and impurity related deterioration. We have studied by means of density functional theory the possibility of oxygen adsorption on the C60 molecular moiety of PCBM. The aim is to provide guidelines for near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) measurements which can probe the presence of atomic or molecular oxygen on the fullerene cage. By analysing several configurations of PCBM with one or more adsorbed oxygen atoms, we show that a joint core level XPS and O1s NEXAFS investigation could be effectively used not only to confirm oxygen adsorption but also to pinpoint the bonding configuration and the nature of the adsorbate.

The distribution of electron donor and acceptor in the active layer is known to strongly influence the electrical performance of polymer solar cells for most of the high performance polymer:fullerene systems. The formulation of the solution from which the active layer is spincoated plays an important role in the quest for morphology control. We have studied how the choice of solvent and the use of small amounts of a low vapour pressure additive in the coating solution influence the film morphology and the solar cell performance for blends of poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and [6,6]-phenyl C71-butyric acid methyl ester (PC70BM). We have investigated the lateral morphology using atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM), the vertical morphology using dynamic secondary ion mass spectrometry (d-SIMS) and variable-angle spectroscopic ellipsometry (VASE), and the surface composition using near-edge X-ray absorption fine structure (NEXAFS). The lateral phase-separated domains observed in films spincoated from single solvents, increase in size with increasing solvent vapour pressure and decreasing PC70BM solubility, but are not observed when 1-chloronaphthalene (CN) is added. A strongly TQ1-enriched surface layer is formed in all TQ1:PC70BM blend films and rationalized by surface energy differences. The photocurrent and power conversion efficiency strongly increased upon the addition of CN, while the leakage current decreased by one to two orders of magnitude. The higher photocurrent correlates with the finer lateral structure and stronger TQ1-enrichment at the interface with the electron-collecting electrode. This indicates that the charge transport and collection are not hindered by this polymer-enriched surface layer. Neither the open-circuit voltage nor the series resistance of the devices are sensitive to the differences in morphology. © 2015 The Royal Society of Chemistry., E.M. acknowledges funding from the Swedish Research Council (Project 2010-4155) and the G¨oran Gustafsson Foundation for Research in Natural Sciences and Medicine. M.C.-Q. thanks the Spanish Ministerio de Econom´ıa y Competitividad for nancial support through project PHOTOCOMB (MAT2012-37776). A.O. acknowledges the R¨ontgen–°Angstr¨om– Cluster for nancial support. E.W. acknowledges the Swedish Research Council for nancial support. We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI)