Long-Term Stable Organic Solar Cells through Amphiphilic Additives

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1. 1

   Berger, P. R.; Kim, M. Polymer Solar Cells: P3ht:Pcbm and Beyond. J. Renewable Sustainable Energy 2018, 10 (1), 013508,  DOI: 10.1063/1.5012992

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   Polymer solar cells: P3HT:PCBM and beyond

   Berger, P. R.; Kim, M.

   Journal of Renewable and Sustainable Energy (2018), 10 (1), 013508/1-013508/26CODEN: JRSEBH; ISSN:1941-7012. (American Institute of Physics)

   A review. For the last two decades, polymer solar cells (PSCs) have been a cynosure of the photovoltaic community, as evidenced by the growing no. of patent applications and scientific publications. Efforts to achieve high power conversion efficiency in PSC, propelled by advances in device architecture, material combination, and nanomorphol. control, evolved into poly(3-hexylthiophene-2,5-diyl) (P3HT):phenyl-C61-Butyric-Acid-Me Ester (PCBM) bulk heterojunction PSCs, which had been the best seller in PSC research for a decade. Subsequently, PSC research was redirected towards the synthesis of low bandgap materials and optimization of tandem cells, which led to a power conversion efficiency of ∼13%. Even though this efficiency may not be sufficient enough to compete with that of inorg. solar cells, unique properties of PSCs, such as mass roll-to-roll prodn. capability, as well as flexibility and lightness, suggest their niche market opportunities. In this review, an overview of developments in PSCs is presented during the last three decades encompassing pre- and post-P3HT:PCBM era. Emphasis is given on evolution in device architecture, coupled with material selection for pre-P3HT:PCBM era, and synthesis of low-bandgap materials, coupled with a tandem structure for post-P3HT:PCBM era. Last but not least, efforts toward the longer operational lifetime of PSCs by encapsulation are reviewed. (c) 2018 American Institute of Physics.
2. 2

   Cheng, P.; Yang, Y. Narrowing the Band Gap: The Key to High-Performance Organic Photovoltaics. Acc. Chem. Res. 2020, 53 (6), 1218– 1228,  DOI: 10.1021/acs.accounts.0c00157

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   Narrowing the Band Gap: The Key to High-Performance Organic Photovoltaics

   Cheng, Pei; Yang, Yang

   Accounts of Chemical Research (2020), 53 (6), 1218-1228CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)

   A review. Conspectus: Org. photovoltaics (OPVs) have attracted considerable attention in the last two decades to overcome the terawatt energy challenge and serious environmental problems. During their early development, only wide-band-gap org. semiconductors were synthesized and employed as the active layer, mainly utilizing photons in the UV-visible region and yielding power conversion efficiencies (PCEs) lower than 5%. Afterward, considerable efforts were made to narrow the polymer donor band gap in order to utilize the IR photons, which led to the enhancement of the PCE from 5% to 12% in about a decade. Since 2017, the study of narrow-band-gap non-fullerene acceptors helped usher in a new era in OPV research and boosted the achievable the PCE to 17% in only 3 years. In essence, the history of OPV development in the last 15 years can be summarized as an attempt to narrow the band gap of org. semiconductors and better position the energy levels. There are multiple benefits of a narrower band gap: (1) considerable IR photons can be utilized, and as a result, the short-circuit c.d. can increase significantly; (2) the energy offset of the LUMO energy levels or HOMO energy levels between the donor and acceptor can be reduced, which will reduce the open-circuit voltage loss by minimizing the loss caused by the donor/acceptor charge transfer state; (3) because of the unique MOs of org. semiconductors, the red-shifted absorption will induce high transmittance in the visible region, which is ideal for the rear subcells in tandem-junction OPVs and transparent OPVs. In this Account, we first summarize our work beginning in 2008 on the design and synthesis of narrow-band-gap polymer donors/non-fullerene acceptors. Several strategies for constructing these materials, including enhancing the intramol. charge transfer effect and steric hindrance/energy level engineering are discussed. In this part, in addn. to systematic analyses of the design of narrow-band-gap polymer donors based on BDT/TT or BDT/DPP, donors/acceptors based on the new donor moieties DTP or BZPT are discussed as well. Esp., we highlight our work on the first report on the narrow-band-gap acceptor Y1 (based on the new donor moiety BZPT), which pioneered the future development and usage of acceptors belonging to the Y1 family (or series). Subsequently, we analyze several reported certified world record single-junction or tandem-junction OPVs that use these narrow-band-gap donors or acceptors. We share our experiences and insights from a device perspective in terms of donor/acceptor selection, energy level alignment management, film morphol. control, current matching of subcells, interconnecting layer construction, interface engineering, and device geometry selection. In this part, the construction of high-performance ternary-blend OPVs and transparent OPVs based on these narrow-band-gap donors/acceptors is also discussed. Finally, in order to push the field into the 20-25% high-efficiency era in the next few years, some suggestions to further develop narrow-band-gap donors/acceptors and related device technologies are proposed.
3. 3

   Bishnoi, S.; Datt, R.; Arya, S.; Gupta, S.; Gupta, R.; Tsoi, W. C.; Sharma, S. N.; Patole, S. P.; Gupta, V. Engineered Cathode Buffer Layers for Highly Efficient Organic Solar Cells: A Review. Adv. Mater. Interfaces 2022, 9 (19), 2101693,  DOI: 10.1002/admi.202101693

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   Cheng, P.; Zhan, X. Stability of Organic Solar Cells: Challenges and Strategies. Chem. Soc. Rev. 2016, 45 (9), 2544– 2582,  DOI: 10.1039/C5CS00593K

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   Stability of organic solar cells: challenges and strategies

   Cheng, Pei; Zhan, Xiaowei

   Chemical Society Reviews (2016), 45 (9), 2544-2582CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)

   Org. solar cells (OSCs) present some advantages, such as simple prepn., light wt., low cost and large-area flexible fabrication, and have attracted much attention in recent years. Although the power conversion efficiencies have exceeded 10%, the inferior device stability still remains a great challenge. In this review, we summarize the factors limiting the stability of OSCs, such as metastable morphol., diffusion of electrodes and buffer layers, oxygen and water, irradn., heating and mech. stress, and survey recent progress in strategies to increase the stability of OSCs, such as material design, device engineering of active layers, employing inverted geometry, optimizing buffer layers, using stable electrodes and encapsulation. Some research areas of device stability that may deserve further attention are also discussed to help readers understand the challenges and opportunities in achieving high efficiency and high stability of OSCs towards future industrial manuf.
6. 6

   Hoppe, H.; Niggemann, M.; Winder, C.; Kraut, J.; Hiesgen, R.; Hinsch, A.; Meissner, D.; Sariciftci, N. S. Nanoscale Morphology of Conjugated Polymer/Fullerene-Based Bulk-Heterojunction Solar Cells. Adv. Funct. Mater. 2004, 14 (10), 1005– 1011,  DOI: 10.1002/adfm.200305026

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   Nanoscale morphology of conjugated polymer/fullerene-based bulk-heterojunction solar cells

   Hoppe, Harald; Niggemann, Michael; Winder, Christoph; Kraut, Juergen; Hiesgen, Renate; Hinsch, Andreas; Meissner, Dieter; Sariciftci, Niyazi Serdar

   Advanced Functional Materials (2004), 14 (10), 1005-1011CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)

   The relation between the nanoscale morphol. and device properties for conjugated polymer/fullerene bulk-heterojunction plastic solar cells, was studied. Complementary measurements on solid-state blends of poly[2-methoxy-5-(3,7-dimethyloctyloxy)]-1,4-phenylenevinylene (MDMO-PPV) and the sol. fullerene C60 deriv. 1-(3-methoxycarbonyl) propyl-1-Ph [6,6]C61 (PCBM), spin-cast from toluene or chlorobenzene solns., were made. The characterization of the nanomorphol. was carried out by SEM and AFM, while solar-cell devices were characterized by I-V and spectral photocurrent measurements. The morphol. was manipulated by annealing to increase the extent of phase sepn. in the thin-film blends and to identify the distribution of materials. Photoluminescence measurements confirm the demixing of the materials by the thermal treatment. The photoluminescence of PCBM clusters with sizes of up to a few hundred nanometers indicates a photocurrent loss in films of the coarser phase-sepd. blends cast from toluene. For toluene-cast films the scale of phase sepn. depends strongly on the ratio of MDMO-PPV to PCBM, as well as on the total concn. of the casting soln. Small beads of 20-30 nm diam. were obsd. in blend films cast from both toluene and chlorobenzene and these are attributed to MDMO-PPV.
7. 7

   Bronstein, H.; Nielsen, C. B.; Schroeder, B. C.; McCulloch, I. The Role of Chemical Design in the Performance of Organic Semiconductors. Nat. Rev. Chem 2020, 4 (2), 66– 77,  DOI: 10.1038/s41570-019-0152-9

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   The role of chemical design in the performance of organic semiconductors

   Bronstein, Hugo; Nielsen, Christian B.; Schroeder, Bob C.; McCulloch, Iain

   Nature Reviews Chemistry (2020), 4 (2), 66-77CODEN: NRCAF7; ISSN:2397-3358. (Nature Research)

   A review. Org. semiconductors are soln.-processable, lightwt. and flexible and are increasingly being used as the active layer in a wide range of new technologies. The versatility of synthetic org. chem. enables the materials to be tuned such that they can be incorporated into biol. sensors, wearable electronics, photovoltaics and flexible displays. These devices can be improved by improving their material components, not only by developing the synthetic chem. but also by improving the anal. and computational techniques that enable us to understand the factors that govern material properties. Judicious mol. design provides control of the semiconductor frontier MO energy distribution and guides the hierarchical assembly of org. semiconductors into functional films where we can manipulate the properties and motion of charges and excited states. This Review describes how mol. design plays an integral role in developing org. semiconductors for electronic devices in present and emerging technologies.
8. 8

   Cui, C.; Li, Y. Morphology Optimization of Photoactive Layers in Organic Solar Cells. Aggregate 2021, 2 (2), e31  DOI: 10.1002/agt2.31

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   Huang, Y.-C.; Liu, W.-S.; Tsao, C.-S.; Wang, L. Mechanistic Insights into the Effect of Polymer Regioregularity on the Thermal Stability of Polymer Solar Cells. ACS Appl. Mater. Interfaces 2019, 11 (43), 40310– 40319,  DOI: 10.1021/acsami.9b12482

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   Mechanistic Insights into the Effect of Polymer Regioregularity on the Thermal Stability of Polymer Solar Cells

   Huang, Yu-Ching; Liu, Wei-Shin; Tsao, Cheng-Si; Wang, Leeyih

   ACS Applied Materials & Interfaces (2019), 11 (43), 40310-40319CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)

   Thermal stability is a bottleneck toward commercialization of polymer solar cells (PSCs). The effect of PCBM aggregation on a multilength scale on the bulk-heterojunction (BHJ) structure, performance, and thermal stability of PSCs is studied here by grazing-incidence small- and wide-angle x-ray scattering. The evolution of hierarchical BHJ structures of a blend film tuned by regioregularity of polymers from the as-cast state to the thermally unstable state is systematically studied. The thermal stability of PSCs with high polymer regioregularity values can be improved because of the good mutual interaction between polymer crystallites and fullerene aggregates. The insights obtained from this study provide an approach to manipulate the film structure on a multilength scale and to enhance the thermal stability of P3HT-based PSCs.
10. 10

    Urquhart, S. G.; Martinson, M.; Eger, S.; Murcia, V.; Ade, H.; Collins, B. A. Connecting Molecular Conformation to Aggregation in P3ht Using near Edge X-Ray Absorption Fine Structure Spectroscopy. J. Phys. Chem. C 2017, 121 (39), 21720– 21728,  DOI: 10.1021/acs.jpcc.7b07143

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    Connecting Molecular Conformation to Aggregation in P3HT Using Near Edge X-ray Absorption Fine Structure Spectroscopy

    Urquhart, Stephen G.; Martinson, Mercedes; Eger, Shaylin; Murcia, Victor; Ade, Harald; Collins, Brian A.

    Journal of Physical Chemistry C (2017), 121 (39), 21720-21728CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)

    C 1s near edge x-ray absorption fine structure (NEXAFS) and UV-visible spectroscopy are used to examine differences between highly aggregated and poorly aggregated forms of the polymer poly(3-hexylthiophene) (P3HT), based on as-cast and annealed regiorandom and regioregular P3HT samples. UV-visible spectra show characteristic signatures of unaggregated P3HT in regiorandom P3HT, and of H-aggregation in regioregular P3HT samples. Distinct spectroscopic differences, including energy shifts, are obsd. in the NEXAFS spectra of aggregated P3HT relative to the unaggregated forms. These differences are reproduced with transition-potential d. functional theory (TP-DFT) calcns. which explore aggregation and mol. conformation. Differences in the NEXAFS spectra of P3HT are assigned to thiophene backbone twisting in the unaggregated forms of P3HT, and to various degrees of chain planarization in aggregated forms of P3HT that also correlate to the exciton bandwidth. These results open up the prospect of characterizing conformation and related difficult to assess structural details through NEXAFS spectroscopy and correlative theory and electronic structure anal.
11. 11

    Steyrleuthner, R.; Di Pietro, R.; Collins, B. A.; Polzer, F.; Himmelberger, S.; Schubert, M.; Chen, Z. H.; Zhang, S. M.; Salleo, A.; Ade, H.; Facchetti, A.; Neher, D. The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility N-Type Copolymer. J. Am. Chem. Soc. 2014, 136 (11), 4245– 4256,  DOI: 10.1021/ja4118736

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    The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility n-Type Copolymer

    Steyrleuthner, Robert; Di Pietro, Riccardo; Collins, Brian A.; Polzer, Frank; Himmelberger, Scott; Schubert, Marcel; Chen, Zhihua; Zhang, Shiming; Salleo, Alberto; Ade, Harald; Facchetti, Antonio; Neher, Dieter

    Journal of the American Chemical Society (2014), 136 (11), 4245-4256CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphol. To understand the influence of the chem. structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, x-ray, and TEM data, we quant. characterized the aggregation, crystn., and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the prepn. conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar cryst. structure along the three crystallog. axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectable π-stacking. Vertical electron mobilities were extd. from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallog. directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chem. and structural disorder with respect to classic semicryst. polymers such as poly(3-hexylthiophene).
12. 12

    Wang, S.; Fabiano, S.; Himmelberger, S.; Puzinas, S.; Crispin, X.; Salleo, A.; Berggren, M. Experimental Evidence That Short-Range Intermolecular Aggregation Is Sufficient for Efficient Charge Transport in Conjugated Polymers. Proc. Natl. Acad. Sci. U.S.A. 2015, 112 (34), 10599– 10604,  DOI: 10.1073/pnas.1501381112

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    Experimental evidence that short-range intermolecular aggregation is sufficient for efficient charge transport in conjugated polymers

    Wang, Suhao; Fabiano, Simone; Himmelberger, Scott; Puzinas, Skomantas; Crispin, Xavier; Salleo, Alberto; Berggren, Magnus

    Proceedings of the National Academy of Sciences of the United States of America (2015), 112 (34), 10599-10604CODEN: PNASA6; ISSN:0027-8424. (National Academy of Sciences)

    Efficiency, current throughput, and speed of electronic devices are to a great extent dictated by charge carrier mobility. The classic approach to impart high carrier mobility to polymeric semiconductors has often relied on the assumption that extensive order and crystallinity are needed. Recently, however, this assumption has been challenged, because high mobility has been reported for semiconducting polymers that exhibit a surprisingly low degree of order. Here, we show that semiconducting polymers can be confined into weakly ordered fibers within an inert polymer matrix without affecting their charge transport properties. In these conditions, the semiconducting polymer chains are inhibited from attaining long-range order in the π-stacking or alkyl-stacking directions, as demonstrated from the absence of significant X-ray diffraction intensity corresponding to these crystallog. directions, yet still remain extended along the backbone direction and aggregate on a local length scale. As a result, the polymer films maintain high mobility even at very low concns. Our findings provide a simple picture that clarifies the role of local order and connectivity of domains.
13. 13

    Wang, Y.; Guo, M.; Yang, L.; Li, L.; Qin, W.; Yin, S. Toward Morphological Stabilization in Polymer Bulk Heterojunction Solar Cells by Crosslinking Using an Additive. IEEE J. Photovoltaics 2016, 6 (3), 710– 718,  DOI: 10.1109/JPHOTOV.2016.2545342

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    Herrmann, F.; Muhsin, B.; Singh, C. R.; Shokhovets, S.; Gobsch, G.; Hoppe, H.; Presselt, M. Influence of Interface Doping on Charge-Carrier Mobilities and Sub-Bandgap Absorption in Organic Solar Cells. J. Phys. Chem. C 2015, 119 (17), 9036– 9040,  DOI: 10.1021/acs.jpcc.5b00124

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    Moustafa, E.; Torimtubun, A. A. A.; Pallares, J.; Marsal, L. F. Effect of Additives and Annealing on the Performance of Nonfullerene-Based Binary and Ternary Organic Photovoltaics. Sol. RRL 2022, 6 (5), 2100480,  DOI: 10.1002/solr.202100480

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    Nam, M.; Yoo, J.; Park, Y.; Noh, H. Y.; Park, Y.; Cho, J.; Kim, J.-A.; Kim, J.; Lee, H. H.; Chang, R. Ternary Blend Organic Solar Cells with Improved Morphological Stability. J. Mater. Chem. A 2019, 7 (16), 9698– 9707,  DOI: 10.1039/c9ta00382g

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    Xu, X.; Li, Y.; Peng, Q. Ternary Blend Organic Solar Cells: Understanding the Morphology from Recent Progress. Adv. Mater. 2022, 34 (46), 2107476,  DOI: 10.1002/adma.202107476

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    Ternary Blend Organic Solar Cells: Understanding the Morphology from Recent Progress

    Xu, Xiaopeng; Li, Ying; Peng, Qiang

    Advanced Materials (Weinheim, Germany) (2022), 34 (46), 2107476CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)

    A review. Ternary blend org. solar cells (TB-OSCs) incorporating multiple donor and/or acceptor materials into the active layer have emerged as a promising strategy to simultaneously improve the overall device parameters for realizing higher performances than binary devices. Whereas introducing multiple materials also results in a more complicated morphol. than their binary blend counterparts. Understanding the morphol. is crucially important for further improving the device performance of TB-OSC. This review introduces the soly. and miscibility parameters that affect the morphol. of ternary blends. Then, this review summarizes the recent processes of morphol. study on ternary blends from the aspects of mol. crystallinity, mol. packing orientation, domain size and purity, directly observation of morphol., vertical phase sepn. as well as morphol. stability. Finally, summary and prospects of TB-OSCs are concluded.
21. 21

    Liao, H.-C.; Chen, P.-H.; Chang, R. P.; Su, W.-F. Morphological Control Agent in Ternary Blend Bulk Heterojunction Solar Cells. Polymers 2014, 6 (11), 2784– 2802,  DOI: 10.3390/polym6112784

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    Park, S. A.; Kim, D. H.; Chung, D.; Kim, J.; Park, T.; Cho, S.; Kim, M. Asymmetric Polymer Additive for Morphological Regulation and Thermally Stable Organic Solar Cells. ACS Appl. Mater. Interfaces 2023, 15 (22), 27026– 27033,  DOI: 10.1021/acsami.3c04804

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    Habenicht, S. H.; Schramm, S.; Fischer, S.; Sachse, T.; Herrmann-Westendorf, F.; Bellmann, A.; Dietzek, B.; Presselt, M.; Weiß, D.; Beckert, R.; Gorls, H. Tuning the Polarity and Surface Activity of Hydroxythiazoles - Extending the Applicability of Highly Fluorescent Self-Assembling Chromophores to Supra-Molecular Photonic Structures. J. Mater. Chem. C 2016, 4 (5), 958– 971,  DOI: 10.1039/C5TC03632A

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    Tuning the polarity and surface activity of hydroxythiazoles - extending the applicability of highly fluorescent self-assembling chromophores to supra-molecular photonic structures

    Habenicht, S. H.; Schramm, S.; Fischer, S.; Sachse, T.; Herrmann-Westendorf, F.; Bellmann, A.; Dietzek, B.; Presselt, M.; Weiss, D.; Beckert, R.; Goerls, H.

    Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2016), 4 (5), 958-971CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)

    A small library of N,N-diethyl- and -diethanolsulfonamides of differently substituted 2-(2-pyridyl)- and 2-pyrazinyl-4-alkoxythiazoles was synthesized and studied in terms of their photophys. properties, electronic structure (quantum chem. calcns. at the CAM-B3LYP/6-31+G(d,p) level of theory) and thin film morphol. (Langmuir-Blodgett- and spin-cast films). By using the Langmuir-Blodgett technique to exert direct control over the degree of aggregation in thin films made from different thiazole type dyes. In combination with spectroscopic studies, the authors gained an in-depth understanding of the influence of aggregation on the electrooptical properties of thin films made of the here-studied substances.
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    Hupfer, M. L.; Kaufmann, M.; Herrmann-Westendorf, F.; Sachse, T.; Roussille, L.; Feller, K. H.; Weiß, D.; Deckert, V.; Beckert, R.; Dietzek, B.; Presselt, M. On the Control of Chromophore Orientation, Supramolecular Structure, and Thermodynamic Stability of an Amphiphilic Pyridyl-Thiazol Upon Lateral Compression and Spacer Length Variation. ACS Appl. Mater. Interfaces 2017, 9 (50), 44181– 44191,  DOI: 10.1021/acsami.7b13042

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    Hupfer, M. L.; Kaufmann, M.; May, S.; Preiß, J.; Weiß, D.; Dietzek, B.; Beckert, R.; Presselt, M. Enhancing the Supramolecular Stability of Monolayers by Combining Dipolar with Amphiphilic Motifs: A Case of Amphiphilic Push-Pull-Thiazole. Phys. Chem. Chem. Phys. 2019, 21 (24), 13241– 13247,  DOI: 10.1039/C9CP02013F

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    Hupfer, M. L.; Kaufmann, M.; Roussille, L.; Preiß, J.; Weiß, D.; Hinrichs, K.; Deckert, V.; Dietzek, B.; Beckert, R.; Presselt, M. Arylic Versus Alkylic-Hydrophobic Linkers Determine the Supramolecular Structure and Optoelectronic Properties of Tripodal Amphiphilic Push-Pull Thiazoles. Langmuir 2019, 35 (7), 2561– 2570,  DOI: 10.1021/acs.langmuir.8b03893

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    Hupfer, M. L.; Meyer, R.; Deckert-Gaudig, T.; Ghosh, S.; Skabeev, A.; Peneva, K.; Deckert, V.; Dietzek, B.; Presselt, M. Supramolecular Reorientation During Deposition onto Metal Surfaces of Quasi-Two-Dimensional Langmuir Monolayers Composed of Bifunctional Amphiphilic, Twisted Perylenes. Langmuir 2021, 37 (37), 11018– 11026,  DOI: 10.1021/acs.langmuir.1c01525

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    Lin, Y.; Nugraha, M. I.; Firdaus, Y.; Scaccabarozzi, A. D.; Aniés, F.; Emwas, A.-H.; Yengel, E.; Zheng, X.; Liu, J.; Wahyudi, W. A Simple N-Dopant Derived from Diquat Boosts the Efficiency of Organic Solar Cells to 18.3%. ACS Energy Lett. 2020, 5 (12), 3663– 3671,  DOI: 10.1021/acsenergylett.0c01949

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    28

    A Simple n-Dopant Derived from Diquat Boosts the Efficiency of Organic Solar Cells to 18.3%

    Lin, Yuanbao; Nugraha, Mohamad Insan; Firdaus, Yuliar; Scaccabarozzi, Alberto D.; Anies, Filip; Emwas, Abdul-Hamid; Yengel, Emre; Zheng, Xiaopeng; Liu, Jiakai; Wahyudi, Wandi; Yarali, Emre; Faber, Hendrik; Bakr, Osman M.; Tsetseris, Leonidas; Heeney, Martin; Anthopoulos, Thomas D.

    ACS Energy Letters (2020), 5 (12), 3663-3671CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)

    Mol. doping has recently been shown to improve the operating characteristics of org. photovoltaics (OPVs). Here, we prep. neutral Diquat (DQ) and use it as n-dopant to improve the performance of state-of-the-art OPVs. Adding DQ in ternary bulk-heterojunction (BHJ) cells based of PM6:Y6:PC71BM is found to consistently increase their power conversion efficiency (PCE) from 16.7 to 17.4%. Analyses of materials and devices reveal that DQ acts as n-type dopant and morphol. modifier for the BHJ leading to observable changes in its surface topog. The resulting n-doped BHJs exhibit higher optical absorption coeffs., balanced ambipolar transport, longer carrier lifetimes and suppressed bimol. recombination, which are ultimately responsible for the increased PCE. The use of DQ was successfully extended to OPVs based on PM6:BTP-eC9:PC71BM for which a max. PCE of 18.3% (uncertified) was achieved. Our study highlights DQ as a promising dopant for application in next generation org. solar cells.
29. 29

    Jeong, S.; Woo, S.-H.; Lyu, H.-K.; Kim, C.; Kim, H.; Han, Y. S. Improvement of Photovoltaic Properties by Addition of a Perylene Compound in P3ht: Pcbm Bhj System. J. Nanosci. Nanotechnol. 2012, 12 (5), 4147– 4153,  DOI: 10.1166/jnn.2012.5898

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30. 30

    Vivo, P.; Dubey, R.; Lehtonen, E.; Kivistö, H.; Vuorinen, T.; Lemmetyinen, H. Dipyrrolidinyl-Substituted Perylene Diimide as Additive for Poly (3-Hexylthiophene):[6, 6]-Phenyl C61 Butyric Acid Methylester Bulk-Heterojunction Blends. Thin Solid Films 2013, 548, 398– 405,  DOI: 10.1016/j.tsf.2013.08.106

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    Li, F.; Werner, A.; Pfeiffer, M.; Leo, K.; Liu, X. Leuco Crystal Violet as a Dopant for N-Doping of Organic Thin Films of Fullerene C60. J. Phys. Chem. B 2004, 108 (44), 17076– 17082,  DOI: 10.1021/jp0478615

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    31

    Leuco Crystal Violet as a Dopant for n-Doping of Organic Thin Films of Fullerene C60

    Li, Fenghong; Werner, Ansgar; Pfeiffer, Martin; Leo, Karl; Liu, Xianjie

    Journal of Physical Chemistry B (2004), 108 (44), 17076-17082CODEN: JPCBFK; ISSN:1520-6106. (American Chemical Society)

    The triphenylmethane dye crystal violet (CV) and its leuco base, leucocrystal violet (LCV), are investigated as dopants for n-type doping of fullerene C60. Conductivities up to 8 × 10-3 S/cm at 30° are achieved when C60 is doped with CV. Mass spectroscopy and optical spectroscopy (UV/VIS/NIR absorption and Fourier transform IR transmission) confirm that the leuco base LCV is formed during sublimation of the cationic CV dye. When the com. available LCV was directly used as a dopant in C60, a max. cond. of 1.3 × 10-2 S/cm was obtained at 30°. We found that in both cases, the leuco base became reoxidized to the cationic form by electron transfer to electron-accepting matrixes, leading to the doping effect. The donor properties of LCV in a charge-transfer complex with 7,7,8,8-tetracyanoquinodimethane (TCNQ) were confirmed by UV/VIS/NIR absorption and Fourier transform IR (FTIR) spectroscopy. C60 anions were obsd. in the FTIR or NIR absorption spectra of the mixed films of C60 and LCV. Photoinduced charge transfer between LCV and C60 provides free electrons, which increase the n-type cond. The electron transfer becomes irreversible by hydride abstraction.
32. 32

    Vivo, P.; Kaunisto, K.; Alekseev, A. S.; Pekkola, O.; Tolkki, A.; Chukharev, V.; Lemmetyinen, H. Vectorial Photoinduced Electron Transfer in Multicomponent Film Systems of Poly (3-Hexylthiophene), Porphyrin-Fullerene Dyad, and Perylenetetracarboxidiimide. Photochem. Photobiol. Sci. 2010, 9 (9), 1212– 1217,  DOI: 10.1039/c0pp00180e

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    Vivo, P.; Vuorinen, T.; Chukharev, V.; Tolkki, A.; Kaunisto, K.; Ihalainen, P.; Peltonen, J.; Lemmetyinen, H. Multicomponent Molecularly Controlled Langmuir- Blodgett Systems for Organic Photovoltaic Applications. J. Phys. Chem. C 2010, 114 (18), 8559– 8567,  DOI: 10.1021/jp1009862

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    Multicomponent Molecularly Controlled Langmuir-Blodgett Systems for Organic Photovoltaic Applications

    Vivo, Paola; Vuorinen, Tommi; Chukharev, Vladimir; Tolkki, Antti; Kaunisto, Kimmo; Ihalainen, Petri; Peltonen, Jouko; Lemmetyinen, Helge

    Journal of Physical Chemistry C (2010), 114 (18), 8559-8567CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)

    The capability of Violanthrone-79 (V-79) and N,N'-bis(2,5-di-tert-butylphenyl)-3,4:9,10-perylenebis(dicarboximide) (PDI) to act as electron acceptors, with respect to poly(3-hexylthiophene) (PHT) and to the photoinduced fullerene anion of porphyrin-fullerene (P-F) dyad, was demonstrated in Langmuir-Blodgett films by the time-resolved Maxwell displacement charge method. The introduction of V-79 and PDI in oriented multilayered films led to improved light harvesting and increased lifetime of the charge sepn., enhancing the photocurrent generation measured using a three-electrode photoelectrochem. cell. The best solar cell performance was achieved for the multifunctional film structure where efficient PHT-phthalocyanine heterojunction (PHT|ZnPH4) was combined with the P-F|V-79 system.
34. 34

    Kaloyanova, S.; Zagranyarski, Y.; Ritz, S.; Hanulová, M.; Koynov, K.; Vonderheit, A.; Müllen, K.; Peneva, K. Water-Soluble Nir-Absorbing Rylene Chromophores for Selective Staining of Cellular Organelles. J. Am. Chem. Soc. 2016, 138 (9), 2881– 2884,  DOI: 10.1021/jacs.5b10425

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    Water-Soluble NIR-Absorbing Rylene Chromophores for Selective Staining of Cellular Organelles

    Kaloyanova, Stefka; Zagranyarski, Yulian; Ritz, Sandra; Hanulova, Maria; Koynov, Kaloian; Vonderheit, Andreas; Muellen, Klaus; Peneva, Kalina

    Journal of the American Chemical Society (2016), 138 (9), 2881-2884CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)

    Biocompatible org. dyes emitting in the near-IR are highly desirable in fluorescence imaging techniques. Herein we report a synthetic approach for building novel small peri-guanidine-fused naphthalene monoimide and perylene monoimide chromophores. The presented structures possess near-IR absorption and emission, high photostability, and good water soly. After a fast cellular uptake, they selectively stain mitochondria with a low background in live and fixed cells. They can be addnl. modified in a one-step reaction with functional groups for covalent labeling of proteins. The low cytotoxicity allows a long time exposure of live cells to the dyes without the necessity of washing. Successful application in localization super-resoln. microscopy was demonstrated in phosphate-buffered saline without any reducing or oxidizing additives.
35. 35

    Fujimoto, K.; Takahashi, M.; Izawa, S.; Hiramoto, M. Development of Perylene-Based Non-Fullerene Acceptors through Bay-Functionalization Strategy. Materials 2020, 13 (9), 2148,  DOI: 10.3390/ma13092148

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36. 36

    Hupfer, M. L.; Ghosh, S.; Wang, Y.; Opsomer, T.; Mayerhöfer, T. G.; Dehaen, W.; Presselt, M. Dichroic Dipole Antenna Membranes from Aligned Linear Bophy Dyes. Adv. Mater. Interfaces 2021, 9 (1), 2101490,  DOI: 10.1002/admi.202101490

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37. 37

    Hupfer, M. L.; Koszarna, B.; Ghosh, S.; Gryko, D. T.; Presselt, M. Langmuir-Blodgett Films of Diketopyrrolopyrroles with Tunable Amphiphilicity. Langmuir 2021, 37 (34), 10272– 10278,  DOI: 10.1021/acs.langmuir.1c01113

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38. 38

    Presselt, M.; Dehaen, W.; Maes, W.; Klamt, A.; Martínez, T.; Beenken, W. J. D.; Kruk, M. Quantum Chemical Insights into the Dependence of Porphyrin Basicity on the Meso-Aryl Substituents: Thermodynamics, Buckling, Reaction Sites and Molecular Flexibility. Phys. Chem. Chem. Phys. 2015, 17 (21), 14096– 14106,  DOI: 10.1039/C5CP01808K

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    Mumyatov, A.; Prudnov, F.; Inasaridze, L.; Mukhacheva, O.; Troshin, P. High Lumo Energy Pyrrolidinofullerenes as Promising Electron-Acceptor Materials for Organic Solar Cells. J. Mater. Chem. C 2015, 3 (44), 11612– 11617,  DOI: 10.1039/C5TC02509E

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40. 40

    Hupfer, M. L.; Kaufmann, M.; Preiß, J.; Weiß, D.; Beckert, R.; Dietzek, B.; Presselt, M. Assembly of T-Shaped Amphiphilic Thiazoles on the Air-Water Interface: Impact of Polar Chromophore Moieties, as Well as Dipolarity and Pi-Extension of the Chromophore on the Supramolecular Structure. Langmuir 2019, 35 (7), 2587– 2600,  DOI: 10.1021/acs.langmuir.8b04063

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41. 41

    Hupfer, M. L.; Blaschke, D.; Schmidt, H.; Presselt, M. Embedding an Amphiphilic 4-Hydroxy Thiazole Dye in Langmuir Matrices: Studying Miscibilities with Arylic and Alkylic Matrix Amphiphiles Via Langmuir Isotherms and Photo-Induced Force Microscopy. Langmuir 2021, 37 (45), 13255– 13264,  DOI: 10.1021/acs.langmuir.1c01772

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42. 42

    Finkelmeyer, S. J.; Askins, E. J.; Eichhorn, J.; Ghosh, S.; Siegmund, C.; Tauscher, E.; Dellith, A.; Hupfer, M. L.; Dellith, J.; Ritter, U.; Strzalka, J.; Glusac, K.; Schacher, F. H.; Presselt, M. Tailoring the Weight of Surface and Intralayer Edge States to Control Lumo Energies. Adv. Mater. 2023, 35 (40), e2305006  DOI: 10.1002/adma.202305006

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43. 43

    Hupfer, M. L.; Dellith, J.; Seyring, M.; Diegel, M.; Dellith, A.; Ghosh, S.; Rettenmayr, M.; Dietzek-Ivanšić, B.; Presselt, M. Bifacial Dye Membranes: Ultrathin and Free-Standing Although Not Being Covalently Bound. Adv. Mater. 2023, 35 (1), 2204874,  DOI: 10.1002/adma.202204874

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44. 44

    Bertho, S.; Janssen, G.; Cleij, T. J.; Conings, B.; Moons, W.; Gadisa, A.; D’Haen, J.; Goovaerts, E.; Lutsen, L.; Manca, J. Effect of Temperature on the Morphological and Photovoltaic Stability of Bulk Heterojunction Polymer: Fullerene Solar Cells. Sol. Energy Mater. Sol. Cells 2008, 92 (7), 753– 760,  DOI: 10.1016/j.solmat.2008.01.006

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    44

    Effect of temperature on the morphological and photovoltaic stability of bulk heterojunction polymer:fullerene solar cells

    Bertho, Sabine; Janssen, Griet; Cleij, Thomas J.; Conings, Bert; Moons, Wouter; Gadisa, Abay; D'Haen, Jan; Goovaerts, Etienne; Lutsen, Laurence; Manca, Jean; Vanderzande, Dirk

    Solar Energy Materials & Solar Cells (2008), 92 (7), 753-760CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier B.V.)

    In high performance polymer:fullerene bulk heterojunction solar cells the nanoscale morphol. of interpenetrating acceptor:donor materials is optimized through appropriate prepn. conditions such as annealing and choice of solvent, but this initial state-of-the-art morphol. will not remain stable during long-term operation. We report the effects of prolonged storage at elevated temps. on both the morphol. and the photovoltaic performance for the model systems MDMO-PPV:PCBM and poly(3-hexylthiophene):PCBM as compared to high Tg PPV:PCBM based solar cells, where the high Tg PPV is characterized by its high glass transition temp. (138°). In situ monitoring of the photocurrent-voltage characteristics at elevated temps., in combination with a systematic transmission electron microscopy study and complementary optical spectroscopy, reveals distinct degrdn. kinetics and morphol. changes that indicate the occurrence of different underlying physicochem. mechanisms.
45. 45

    Chao, Y.-C.; Chuang, C.-H.; Hsu, H.-L.; Wang, H.-J.; Hsu, Y.-C.; Chen, C.-P.; Jeng, R.-J. Enhanced Thermal Stability of Organic Photovoltaics Via Incorporating Triphenylamine Derivatives as Additives. Sol. Energy Mater. Sol. Cells 2016, 157, 666– 675,  DOI: 10.1016/j.solmat.2016.07.041

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    45

    Enhanced thermal stability of organic photovoltaics via incorporating triphenylamine derivatives as additives

    Chao, Ying-Chieh; Chuang, Chia-Hsin; Hsu, Hsiang-Lin; Wang, Hsing-Ju; Hsu, Yu-Chi; Chen, Chih-Ping; Jeng, Ru-Jong

    Solar Energy Materials & Solar Cells (2016), 157 (), 666-675CODEN: SEMCEQ; ISSN:0927-0248. (Elsevier B.V.)

    In this work, we prepd. four star-shaped conjugated small mols., the triphenylamine dithiophene (TBT) derivs., namely TBT-H, TBT-Br, TBT-OH, and TBT-N3 presenting hydride, bromide, hydroxyl, and azide terminal functional groups, resp. These TBT derivs. were used as additives in the active layers of org. photovoltaics to investigate the effect of intermol. interactions (TBT-H, TBT-OH) or crosslinking (TBT-N3, TBT-Br) on the long-term thermal stability of the devices. From analyses of blend film morphologies, and optoelectronic and device performance, we obsd. significant enhancements in thermal stability during accelerated heating tests at 150 °C for the devices incorporated with the additives TBT-N3 and TBT-Br. These two additives functioned as crosslinkers, and constructed local borders that effectively impeded heat-promoted fullerene aggregation, thereby leading to highly stable morphologies. When compared with corresponding normal devices, the TBT-N3-derived devices based on poly(3-hexylthiophene) exhibited greater stability, with the power conversion efficiency (PCE) remaining as high as 2.5% after 144h at 150 °C. Because of this enhancement, a device based on an amorphous low-bandgap polymer, namely poly(thieno[3,4-b]thiophene-alt-benzodithiophene), with the addn. of TBT-N3 was fabricated. We obsd. a significant improvement in device stability, retaining approx. 60% (from 5.0 to 3.3%) of its initial PCE under accelerated heating (150 °C). In contrast, the PCE of the corresponding normal device decayed to 0.01% of its initial value.
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    Reinspach, J. A.; Diao, Y.; Giri, G.; Sachse, T.; England, K.; Zhou, Y.; Tassone, C.; Worfolk, B. J.; Presselt, M.; Toney, M. F.; Mannsfeld, S.; Bao, Z. Tuning the Morphology of Solution-Sheared P3ht:Pcbm Films. ACS Appl. Mater. Interfaces 2016, 8 (3), 1742– 1751,  DOI: 10.1021/acsami.5b09349

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47. 47

    Presselt, M.; Herrmann, F.; Shokhovets, S.; Hoppe, H.; Runge, E.; Gobsch, G. Sub-Bandgap Absorption in Polymer-Fullerene Solar Cells Studied by Temperature-Dependent External Quantum Efficiency and Absorption Spectroscopy. Chem. Phys. Lett. 2012, 542, 70– 73,  DOI: 10.1016/j.cplett.2012.05.063

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    47

    Sub-bandgap absorption in polymer-fullerene solar cells studied by temperature-dependent external quantum efficiency and absorption spectroscopy

    Presselt, Martin; Herrmann, Felix; Shokhovets, Sviatoslav; Hoppe, Harald; Runge, Erich; Gobsch, Gerhard

    Chemical Physics Letters (2012), 542 (), 70-73CODEN: CHPLBC; ISSN:0009-2614. (Elsevier B.V.)

    We study the sub-bandgap absorption in solar cells made of poly(3-hexylthiophene-2,5-diyl) and [6,6]-Ph C61 butyric acid Me ester (PCBM) by photothermal deflection absorption spectroscopy and measurement of temp.-dependent external quantum efficiency spectra. Several models for sub-bandgap absorption are critically reviewed in view of the external quantum efficiency results. The latter suggest polaron-related transitions as origin of the Gaussian sub-bandgap peak near 1.6 eV. Intermol. charge transfer excitations as an explanation cannot completely be ruled out. However, the assumption of charge transfer excitons with large binding energies is difficult to reconcile with the rapid loss of wt. of the Gaussian sub-bandgap peak seen in external quantum efficiency above room temp.
48. 48

    Presselt, M.; Bärenklau, M.; Rösch, R.; Beenken, W. J. D.; Runge, E.; Shokhovets, S.; Hoppe, H.; Gobsch, G. Sub-Bandgap Absorption in Polymer-Fullerene Solar Cells. Appl. Phys. Lett. 2010, 97 (25), 253302,  DOI: 10.1063/1.3527077

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    Presselt, M.; Herrmann, F.; Hoppe, H.; Shokhovets, S.; Runge, E.; Gobsch, G. Influence of Phonon Scattering on Exciton and Charge Diffusion in Polymer-Fullerene Solar Cells. Adv. Energy Mater. 2012, 2 (8), 999– 1003,  DOI: 10.1002/aenm.201100793

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    49

    Influence of phonon scattering on exciton and charge diffusion in polymer-fullerene solar cells

    Presselt, Martin; Herrmann, Felix; Hoppe, Harald; Shokhovets, Sviatoslav; Runge, Erich; Gobsch, Gerhard

    Advanced Energy Materials (2012), 2 (8), 999-1003CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)

    Thermally activated transport and phonon scattering in P3HT:PCBM (poly(3-hexylthiophene-2,5-diyl):[6,6]-phenylC61-butyric acid Me ester) bulk heterojunction (BHJ) org. solar cells is studied via temp.-dependent external-quantum-efficiency (EQE) spectroscopy. The hopping barriers for combined exciton and charge transport are balanced for the individual blended materials in a sample, which possesses a blending ratio and a morphol. that give rise to a maximal power-conversion efficiency. Increasing the PCBM wt. fraction leads to a redn. of exciton hopping barriers in PCBM, while for P3HT exciton hopping barriers remain const. This redn. of PCBM exciton hopping barriers is attributed to a higher PCBM crystallinity in the PCBM-rich solar cell as compared to the BHJ with the optimized blending ratio. The morphol.-dependent difference in exciton hopping activation energies between P3HT and PCBM is attributed to a higher impact of phonon scattering in P3HT than in PCBM, as concluded from the much stronger decrease of P3HT-related temp.-dependent external quantum efficiencies above room temp. in the PCBM-rich BHJ solar cell. All EQE data of P3HT:PCBM-based BHJ solar cells is modeled consistently over a broad temp. range by a simple anal. expression involving temp. activation and phonon scattering, without the need to distinguish two sep. hopping regimes.
50. 50

    Hupfer, M. L.; Herrmann-Westendorf, F.; Kaufmann, M.; Weiß, D.; Beckert, R.; Dietzek, B.; Presselt, M. Autonomous Supramolecular Interface Self-Healing Monitored by Restoration of Uv/Vis Absorption Spectra of Self-Assembled Thiazole Layers. Chem.─Eur. J. 2019, 25 (36), 8630– 8634,  DOI: 10.1002/chem.201901549

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    Hupfer, M.; Herrmann-Westendorf, F.; Dietzek, B.; Presselt, M. In Situ Photothermal Deflection Spectroscopy Revealing Intermolecular Interactions Upon Self-Assembly of Dye Monolayers. Analyst 2021, 146 (16), 5033– 5036,  DOI: 10.1039/D1AN00582K

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52. 52

    Das, S.; Presselt, M. Progress and Development in Structural and Optoelectronic Tunability of Supramolecular Nonbonded Fullerene Assemblies. J. Mater. Chem. C 2019, 7 (21), 6194– 6216,  DOI: 10.1039/C9TC00889F

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    52

    Progress and development in structural and optoelectronic tunability of supramolecular nonbonded fullerene assemblies

    Das, Saunak; Presselt, Martin

    Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2019), 7 (21), 6194-6216CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)

    A review. Assembly of fullerenes utilizing self-organization at solvent/non-solvent interfaces or by introducing hydrophobic(philic) end-groups have yielded diverse molecularly-ordered structures. Taking advantage of the multiple π-π interaction between adjacent C60-moieties, structurally elegant and functionally promising fullerene assemblies were synthesized by several groups over the last 20 yr. Considerable improvement of device parameters is witnessed if non-covalent fullerene layers assembled using interfacial self assembly are used as electron extn. layer, for example in hybrid solar cells. Thus a pre-detd. choice of C60-nanostructures for photovoltaic application stems from an understanding of fullerene-fullerene interaction, a priori from the mol. level. Could we eventually define the outcomes of the last 3 decades of fullerene aggregation chem.. This review summarizes the course of understanding of optoelectronic properties of fullerene-morphologies, bridging the gap between single mol. and device scale which shall be significant for their judicious implementation in mol. electronics.
53. 53

    Das, S.; Herrmann-Westendorf, F.; Schacher, F. H.; Tauscher, E.; Ritter, U.; Dietzek, B.; Presselt, M. Controlling Electronic Transitions in Fullerene Van Der Waals Aggregates Via Supramolecular Assembly. ACS Appl. Mater. Interfaces 2016, 8 (33), 21512– 21521,  DOI: 10.1021/acsami.6b06800

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54. 54

    Ghosh, R.; Spano, F. C. Excitons and Polarons in Organic Materials. Acc. Chem. Res. 2020, 53 (10), 2201– 2211,  DOI: 10.1021/acs.accounts.0c00349

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    54

    Excitons and Polarons in Organic Materials

    Ghosh, Raja; Spano, Frank C.

    Accounts of Chemical Research (2020), 53 (10), 2201-2211CODEN: ACHRE4; ISSN:0001-4842. (American Chemical Society)

    Conspectus: Excitons and polarons play a central role in the electronic and optical properties of org. semiconducting polymers and mol. aggregates, and are of fundamental importance in understanding the operation of org. optoelectronic devices such as solar cells and light-emitting diodes. For many conjugated org. mols. and polymers, the creation of neutral electronic excitations or ionic radicals is assocd. with significant nuclear relaxation, the bulk of which occurs along the vinyl-stretching mode or the arom.-quinoidal stretching mode when conjugated rings are present. Within a polymer chain or mol. aggregate, nuclear relaxation competes with energy- and charge-transfer, mediated by electronic interactions between the constituent units (repeat units for polymers and individual chromophores for a mol. aggregate); for neutral electronic excitations, such inter-unit interactions lead to extended excited states or excitons, while for pos. (or neg.) charges, interactions lead to delocalized hole (or electron) polarons. The electronic coupling as well as the local coupling between electronic and nuclear degrees of freedom in both excitons and polarons can be described with a Holstein Hamiltonian. However, although excitons and polarons derive from similarly structured Hamiltonians, their optical signatures are quite distinct, largely due to differing ground states and optical selection rules. In this Account, we explore the similarities and differences in the spectral response of excitons and polarons in org. polymers and mol. aggregates. We limit our anal. to the subspace of excitons and hole polarons contg. at most one excitation; hence, we omit the influence of bipolarons, biexcitons, and higher multiparticle excitations. Using a generic linear array of coupled units as a model host for both excitons and polarons, we compare and contrast the optical responses of both quasiparticles, with a particular emphasis on the spatial coherence length, the length over which an exciton or polaron possesses wave-like properties important for more efficient transport. For excitons, the UV-vis absorption spectrum is generally represented by a distorted vibronic progression with H-like or J-like signatures depending on the sign of the electronic coupling, Jex. The spectrum broadens with increasing site disorder, with the spectral area preserved due to an oscillator strength sum rule. For (hole) polarons, the generally stronger electronic coupling results in a mid-IR spectrum consisting of a narrow, low-energy peak (A) with energy near a vibrational quantum of the vinyl stretching mode, and a broader, higher-energy feature (B). In contrast to the UV-vis spectrum, the mid-IR spectrum is invariant to the sign of the electronic coupling, th, and completely resistant to long-range disorder, where it remains entirely homogeneously broadened. Even in the presence of short-range disorder, the width of peak A remains surprisingly narrow as long as |th| remains sufficiently large, a property that can be understood in terms of Herzberg-Teller coupling. Unlike for excitons, for polarons, the absorption spectral area decreases with increasing short-range disorder σ (i.e., there is no oscillator sum rule) reflective of a decreasing polaron coherence length. The intensity of the low-energy peak A in relation to B is an important signature of polaron coherence. By contrast, for excitons, the absorption spectrum contains no unambiguous signs of exciton coherence. One must instead resort to the shape of the steady-state photoluminescence spectrum. The Holstein-based model has been highly successful in accounting for the spectral properties of mol. aggregates as well as conjugated polymers like poly(3-hexylthiophene) (P3HT) in the mid-IR and UV-vis spectral regions.
55. 55

    Clark, J.; Silva, C.; Friend, R. H.; Spano, F. C. Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene. Phys. Rev. Lett. 2007, 98 (20), 206406,  DOI: 10.1103/PhysRevLett.98.206406

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    Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene

    Clark, Jenny; Silva, Carlos; Friend, Richard H.; Spano, Frank C.

    Physical Review Letters (2007), 98 (20), 206406/1-206406/4CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)

    The authors address the role of excitonic coupling on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By temp.-dependent absorption and photoluminescence spectroscopy, optical emission is overwhelmingly dominated by weakly coupled H aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to ext. the magnitude of the intermol. coupling energy, of ∼5 and 30 meV for films spun from isodurene and CHCl3 solns., resp.
56. 56

    Alam, S.; Anand, A.; Islam, M. M.; Meitzner, R.; Djoumessi, A. S.; Slowik, J.; Teklu, Z.; Fischer, P.; Kästner, C.; Khan, J. I. P3ht: Pcbm Polymer Solar Cells from a Didactic Perspective. J. Photonics Energy 2022, 12 (3), 035501,  DOI: 10.1117/1.jpe.12.035501

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    Cardona, C. M.; Li, W.; Kaifer, A. E.; Stockdale, D.; Bazan, G. C. Electrochemical Considerations for Determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications. Adv. Mater. 2011, 23 (20), 2367– 2371,  DOI: 10.1002/adma.201004554

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    Electrochemical Considerations for Determining Absolute Frontier Orbital Energy Levels of Conjugated Polymers for Solar Cell Applications

    Cardona, Claudia M.; Li, Wei; Kaifer, Angel E.; Stockdale, David; Bazan, Guillermo C.

    Advanced Materials (Weinheim, Germany) (2011), 23 (20), 2367-2371CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)

    Narrow bandgap conjugated polymers in combination with fullerene acceptors are under intense investigation in the field of org. photovoltaics (OPVs). The open circuit voltage, and thereby the power conversion efficiency, of the devices is related to the offset of the frontier orbital energy levels of the donor and acceptor components which are widely detd. by cyclic voltammetry. Inconsistencies have appeared in the use of the ferrocenium/ferrocene (Fc+/Fc) redox couple, as well as the values used for the abs. potentials of std. electrodes, which can complicate the comparison of materials properties and detn. of structure/property relationships.
58. 58

    Titov, A. V.; Ufimtsev, I. S.; Luehr, N.; Martinez, T. J. Generating Efficient Quantum Chemistry Codes for Novel Architectures. J. Chem. Theory Comput. 2013, 9 (1), 213– 221,  DOI: 10.1021/ct300321a

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    58

    Generating Efficient Quantum Chemistry Codes for Novel Architectures

    Titov, Alexey V.; Ufimtsev, Ivan S.; Luehr, Nathan; Martinez, Todd J.

    Journal of Chemical Theory and Computation (2013), 9 (1), 213-221CODEN: JCTCCE; ISSN:1549-9618. (American Chemical Society)

    We describe an extension of our graphics processing unit (GPU) electronic structure program TeraChem to include atom-centered Gaussian basis sets with d angular momentum functions. This was made possible by a "meta-programming" strategy that leverages computer algebra systems for the derivation of equations and their transformation to correct code. We generate a multitude of code fragments that are formally math. equiv., but differ in their memory and floating-point operation footprints. We then select between different code fragments using empirical testing to find the highest performing code variant. This leads to an optimal balance of floating-point operations and memory bandwidth for a given target architecture without laborious manual tuning. We show that this approach is capable of similar performance compared to our hand-tuned GPU kernels for basis sets with s and p angular momenta. We also demonstrate that mixed precision schemes (using both single and double precision) remain stable and accurate for mols. with d functions. We provide benchmarks of the execution time of entire SCF calcns. using our GPU code and compare to mature CPU based codes, showing the benefits of the GPU architecture for electronic structure theory with appropriately redesigned algorithms. We suggest that the meta-programming and empirical performance optimization approach may be important in future computational chem. applications, esp. in the face of quickly evolving computer architectures.
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    Beenken, W. J. D.; Sun, M.; Zhao, G.; Pullerits, T. Excited State Properties of Neutral and Charged Ter-Fluorene with and without a Keto-Defect. Phys. Status Solidi B 2008, 245 (5), 849– 853,  DOI: 10.1002/pssb.200743442

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    Song, C.; Wang, L.-P.; Sachse, T.; Preiß, J.; Presselt, M.; Martínez, T. J. Efficient Implementation of Effective Core Potential Integrals and Gradients on Graphical Processing Units. J. Chem. Phys. 2015, 143 (1), 014114,  DOI: 10.1063/1.4922844

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    Presselt, M.; Dietzek, B.; Schmitt, M.; Rau, S.; Winter, A.; Jäger, M.; Schubert, U. S.; Popp, J. A Concept to Tailor Electron Delocalization: Applying Qtaim Analysis to Phenyl-Terpyridine Compounds. J. Phys. Chem. A 2010, 114 (50), 13163– 13174,  DOI: 10.1021/jp107007a

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    A Concept to Tailor Electron Delocalization: Applying QTAIM Analysis to Phenyl-Terpyridine Compounds

    Presselt, Martin; Dietzek, Benjamin; Schmitt, Michael; Rau, Sven; Winter, Andreas; Jager, Michael; Schubert, Ulrich S.; Popp, Jurgen

    Journal of Physical Chemistry A (2010), 114 (50), 13163-13174CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    To gain a deeper understanding of how structural modifications may influence photochem. properties of 4'-phenyl-2,2':6',2''-terpyridines, the investigations presented here focus on electron delocalization in 4'-phenyl-2,2':6',2''-terpyridine derivs. and their Ru(II) and Zn(II) complexes. In those systems of neighboring arom. rings the considerable torsion between the rings is commonly regarded to be the limiting factor for a well pronounced π-conjugation between the rings. A common approach to improve the π-conjugation is to lower the steric hindrance, thus achieving a more planar geometry. Here, we present a fundamentally different approach towards enhanced π-conjugation by manipulation of the electronic properties of the pyridine-Ph (py-ph) bond. This is accomplished by introducing various substituents at the phenylene moiety or coordinating the terpyridine moiety to transition metal ions. The electron delocalization was quantified via the DFT-calcd. ellipticity in the bond-crit. point (BCP) of the py-ph bond. This ellipticity can be modified due to substituents in the para position of phenylene and via the transition metals coordinated to the terpyridine moiety. Changes in electron d. distribution induced by the substituents and the metal ions are further studied by means of intermol. electron d. difference plots. It was shown that a NH2 group in the para position of the Ph ring as well as the coordination to Ru(II) or Zn(II) ions significantly enhances the π-character of the py-ph bond. Surprisingly, an even higher π-character of the py-ph bond is achieved by introducing addnl. NH2 groups in ortho position to the py-ph bond, despite the increased torsion between pyridine and phenylene. The introduction of other substituents (-NO2, -Br, -CN, -vinyl, -ethynyl) studied within the presented work enables an actuation of the electron delocalization between terpyridine and phenylene. In doing so, the ellipticity is a concise quantity to characterize electron delocalization in the studied systems. Furthermore, the ellipticity in the BCP of the py-ph bond is related to the corresponding geometrical properties (e.g., bond length and dihedral angle) and to the DFT-calcd. HOMO and LUMO energies.
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    Presselt, M.; Schnedermann, C.; Muller, M.; Schmitt, M.; Popp, J. Derivation of Correlation Functions to Predict Bond Properties of Phenyl–CH Bonds Based on Vibrational and ¹H NMR Spectroscopic Quantities. J. Phys. Chem. A 2010, 114 (37), 10287– 10296,  DOI: 10.1021/jp105348d

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    62

    Derivation of Correlation Functions to Predict Bond Properties of Phenyl-CH Bonds Based on Vibrational and 1H NMR Spectroscopic Quantities

    Presselt, Martin; Schnedermann, Christoph; Mueller, Michael; Schmitt, Michael; Popp, Juergen

    Journal of Physical Chemistry A (2010), 114 (37), 10287-10296CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    The study of electron d. properties significantly contributes to the detn. of important chem. relations. The exptl. detn. of the electron d. distribution is limited to single crystals. However, equiv. information is often desired for mols., which do not crystallize in a sufficient manner. Furthermore, it is of high impact to study changes in the electron d. distribution (i.e., related reactivities) upon environmental variations. Consequently, here we investigate methods to derive electron d. properties from spectroscopic data. In particular correlation functions are introduced, which are able to predict electron d. properties in all five CH-bonds of monosubstituted benzene derivs. at once. The prediction performance for electron densities and the corresponding Laplacians is lower as compared to previously introduced local functions, but far less spectroscopic input data are needed. However, for ellipticities a higher prediction performance than this obtained for the previously derived local functions could be obtained despite the fact that less spectroscopic data were used. Thus, ellipticities are best predicted using 1H NMR data for the para position of monosubstituted benzene derivs.
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    Beenken, W.; Presselt, M.; Ngo, T. H.; Dehaen, W.; Maes, W.; Kruk, M. Molecular Structures and Absorption Spectra Assignment of Corrole Nh Tautomers. J. Phys. Chem. A 2014, 118 (5), 862– 871,  DOI: 10.1021/jp411033h

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    63

    Molecular Structures and Absorption Spectra Assignment of Corrole NH Tautomers

    Beenken, Wichard; Presselt, Martin; Ngo, Thien H.; Dehaen, Wim; Maes, Wouter; Kruk, Mikalai

    Journal of Physical Chemistry A (2014), 118 (5), 862-871CODEN: JPCAFH; ISSN:1089-5639. (American Chemical Society)

    The individual absorption spectra of the two NH tautomers of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole are assigned on the basis of the Gouterman four-orbital model and a quantum chem. TD-DFT study. The assignment indicates that the red-shifted T1 tautomer is the one with protonated pyrrole nitrogen atoms N(21), N(22) and N(23), whereas the blue-shifted T2 tautomer has pyrrole nitrogen atoms N(21), N(22) and N(24) protonated. A wave-like nonplanar distortion of the macrocycle in the ground state is found for both NH tautomers, with the wave axis going through the pyrroles contg. N(22) and N(24). The 7C plane detd. by the least-squares distances to the carbon atoms C1, C4, C5, C6, C9, C16, and C19 is suggested as a mean corrole macrocycle plane for the anal. of out-of-plane distortions. The magnitude of these distortions is distinctly different for the two NH tautomers, leading to substantial perturbations of their acid-base properties, which are rationalized by the interplay of the degree of out-of-plane distortion of the macrocycle as a whole and the tendency of the pyrrole nitrogen atoms toward pyramidalization, with the former leading to a basicity increase whereas the latter enhances the acidity.
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    Presselt, M.; Wojdyr, M.; Beenken, W. J. D.; Kruk, M.; Martinez, T. J. Steric and Electronic Contributions to the Core Reactivity of Monoprotonated 5-Phenylporphyrin: A Dft Study. Chem. Phys. Lett. 2014, 603 (0), 21– 27,  DOI: 10.1016/j.cplett.2014.04.011

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    Preiß, J.; Jäger, M.; Rau, S.; Dietzek, B.; Popp, J.; Martínez, T.; Presselt, M. How Does Peripheral Functionalization of Ruthenium(Ii)-Terpyridine Complexes Affect Spatial Charge Redistribution after Photoexcitation at the Franck-Condon Point?. ChemPhysChem 2015, 16 (7), 1395– 1404,  DOI: 10.1002/cphc.201500223

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    Fischer, S.; Vestfrid, J.; Mahammed, A.; Herrmann-Westendorf, F.; Schulz, M.; Muller, J.; Kiesewetter, O.; Dietzek, B.; Gross, Z.; Presselt, M. Photometric Detection of Nitric Oxide Using a Dissolved Iron(Iii) Corrole as a Sensitizer. ChemPlusChem 2016, 81 (7), 594– 603,  DOI: 10.1002/cplu.201500553

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    Preiß, J.; Herrmann-Westendorf, F.; Ngo, T. H.; Martínez, T.; Dietzek, B.; Hill, J. P.; Ariga, K.; Kruk, M. M.; Maes, W.; Presselt, M. Absorption and Fluorescence Features of an Amphiphilic Meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations. J. Phys. Chem. A 2017, 121 (45), 8614– 8624,  DOI: 10.1021/acs.jpca.7b08910

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    Sachse, T.; Martinez, T. J.; Presselt, M. On Combining the Conductor-Like Screening Model and Optimally Tuned Range-Separated Hybrid Density Functionals. J. Chem. Phys. 2019, 150 (17), 174117,  DOI: 10.1063/1.5064730

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    On combining the conductor-like screening model and optimally tuned range-separated hybrid density functionals

    Sachse, Torsten; Martinez, Todd J.; Presselt, Martin

    Journal of Chemical Physics (2019), 150 (17), 174117/1-174117/8CODEN: JCPSA6; ISSN:0021-9606. (American Institute of Physics)

    Range-sepd. hybrid functionals whose range-sepn. parameter γ has been nonempirically tuned to a particular mol. have been shown to yield frontier orbital energies and other properties in very good agreement with expts. However, many cases, such as org. optoelectronic devices, require the description of mols. embedded in an environment. This can be done by combining the γ-tuning procedure with polarizable continuum models in general and the very versatile conductor-like screening model in particular. There are at least two different ways of performing this combination. The partially vertical γ-tuning employs equil. solvation throughout. The strictly vertical γ-tuning, on the other hand, employs nonequil. solvation to obtain ionization energies. In this article, we compare ground-state and excited-state properties of several different mols. relevant to org. optoelectronics that were obtained using both of the two different tuning procedures. While there are significant differences in the ground-state properties, we see virtually no difference in the excited-state properties. Given these results, we conclude that both tuning procedures have to be used in conjunction for the correct description of both ground-state and excited-state properties. (c) 2019 American Institute of Physics.
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    Kozlíková, B.; Krone, M.; Falk, M.; Lindow, N.; Baaden, M.; Baum, D.; Viola, I.; Parulek, J.; Hege, H.-C. Visualization of Biomolecular Structures: State of the Art Revisited. Computer Graphics Forum 2017, 36 (8), 178– 204,  DOI: 10.1111/cgf.13072

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