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Opportunities and challenges in probing local composition of organic material blends for photovoltaics

Published online by Cambridge University Press:  14 February 2017

Rickard Hansson
Affiliation:
Department of Engineering and Physics, Karlstad University, Karlstad 651 88, Sweden
Leif K.E. Ericsson*
Affiliation:
Department of Engineering and Physics, Karlstad University, Karlstad 651 88, Sweden
Natalie P. Holmes
Affiliation:
Centre for Organic Electronics, University of Newcastle, Callaghan, NSW 2308, Australia
Vanja Blazinic
Affiliation:
Department of Engineering and Physics, Karlstad University, Karlstad 651 88, Sweden
Paul Dastoor
Affiliation:
Centre for Organic Electronics, University of Newcastle, Callaghan, NSW 2308, Australia
Ellen Moons
Affiliation:
Department of Engineering and Physics, Karlstad University, Karlstad 651 88, Sweden
*
a) Address all correspondence to this author. e-mail: [email protected]
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Abstract

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.

Type
Invited Article
Copyright
Copyright © Materials Research Society 2017 

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Footnotes

Contributing Editor: Dean DeLongchamp

References

REFERENCES

Peet, J., Heeger, A.J., and Bazan, G.C.: “Plastic” solar cells: Self-assembly of bulk heterojunction nanomaterials by spontaneous phase separation. Acc. Chem. Res. 42, 17001708 (2009).CrossRefGoogle ScholarPubMed
Kippelen, B. and Brédas, J-L.: Organic photovoltaics. Energy Environ. Sci. 2, 251261 (2009).CrossRefGoogle Scholar
Salleo, A., Kline, R.J., DeLongchamp, D.M., and Chabinyc, M.L.: Microstructural characterization and charge transport in thin films of conjugated polymers. Adv. Mater. 22, 38123838 (2010).CrossRefGoogle ScholarPubMed
Brady, M.A., Su, G.M., and Chabinyc, M.L.: Recent progress in the morphology of bulk heterojunction photovoltaics. Soft Matter 7, 1106511077 (2011).CrossRefGoogle Scholar
Liu, F., Gu, Y., Jung, J.W., Jo, W.H., and Russell, T.P.: On the morphology of polymer-based photovoltaics. J. Polym. Sci., Part B: Polym. Phys. 50, 10181044 (2012).CrossRefGoogle Scholar
Hansson, R., Ericsson, L.K.E., Holmes, N.P., Rysz, J., Opitz, A., Campoy-Quiles, M., Wang, E., Barr, M.G., Kilcoyne, A.L.D., Zhou, X., Dastoor, P., and Moons, E.: Vertical and lateral morphology effects on solar cell performance for a thiophene–quinoxaline copolymer:PC70BM blend. J. Mater. Chem. A 3, 69706979 (2015).CrossRefGoogle Scholar
Xue, B., Vaughan, B., Poh, C-H., Burke, K.B., Thomsen, L., Stapleton, A., Zhou, X., Bryant, G.W., Belcher, W., and Dastoor, P.C.: Vertical stratification and interfacial structure in P3HT:PCBM organic solar cells. J. Phys. Chem. C 114, 1579715805 (2010).CrossRefGoogle Scholar
Anselmo, A.S., Dzwilewski, A., Svensson, K., and Moons, E.: Molecular orientation and composition at the surface of spin-coated polyfluorene:fullerene blend films. J. Polym. Sci., Part B: Polym. Phys. 51, 176182 (2013).CrossRefGoogle Scholar
Backe, O., Lindqvist, C., Mendaza, A.D.D., Gustafsson, S., Wang, E.G., Andersson, M.R., Muller, C., and Olsson, E.: Mapping fullerene crystallization in a photovoltaic blend: An electron tomography study. Nanoscale 7, 84518456 (2015).CrossRefGoogle Scholar
Holmes, N.P., Burke, K.B., Sista, P., Barr, M., Magurudeniya, H.D., Stefan, M.C., Kilcoyne, A.L.D., Zhou, X.J., Dastoor, P.C., and Belcher, W.J.: Nano-domain behaviour in P3HT:PCBM nanoparticles, relating material properties to morphological changes. Sol. Energy Mater. Sol. Cells 117, 437445 (2013).CrossRefGoogle Scholar
Lindqvist, C., Sanz-Velasco, A., Wang, E.G., Backe, O., Gustafsson, S., Olsson, E., Andersson, M.R., and Muller, C.: Nucleation-limited fullerene crystallisation in a polymer-fullerene bulk-heterojunction blend. J. Mater. Chem. A 1, 71747180 (2013).CrossRefGoogle Scholar
van Duren, J.K.J., Yang, X., Loos, J., Bulle-Lieuwma, C.W.T., Sieval, A.B., Hummelen, J.C., and Janssen, R.A.J.: Relating the morphology of poly(p-phenylenevinylene)/methanofullerene blends to solar-cell performance. Adv. Funct. Mater. 14, 425434 (2004).CrossRefGoogle Scholar
Yang, X., van Duren, J.K.J., Janssen, R.A.J., Michels, M.A.J., and Loos, J.: Morphology and thermal stability of the active layer in poly(p-phenylenevinylene)/methanofullerene plastic photovoltaic devices. Macromolecules 37, 21512158 (2004).CrossRefGoogle Scholar
Barrau, S., Andersson, V., Zhang, F.L., Masich, S., Bijleveld, J., Andersson, M.R., and Inganas, O.: Nanomorphology of bulk heterojunction organic solar cells in 2D and 3D correlated to photovoltaic performance. Macromolecules 42, 46464650 (2009).CrossRefGoogle Scholar
Loos, J., Sourty, E., Lu, K., Freitag, B., Tang, D., and Wall, D.: Electron tomography on micrometer-thick specimens with nanometer resolution. Nano Lett. 9, 17041708 (2009).CrossRefGoogle ScholarPubMed
Andersson, B.V., Herland, A., Masich, S., and Inganäs, O.: Imaging of the 3D nanostructure of a polymer solar cell by electron tomography. Nano Lett. 9, 853855 (2009).CrossRefGoogle ScholarPubMed
van Bavel, S., Sourty, E., de With, G., Veenstra, S., and Loos, J.: Three-dimensional nanoscale organization of polymer solar cells. J. Mater. Chem. 19, 53885393 (2009).CrossRefGoogle Scholar
Collins, B.A. and Ade, H.: Quantitative compositional analysis of organic thin films using transmission NEXAFS spectroscopy in an X-ray microscope. J. Electron Spectrosc. Relat. Phenom. 185, 119128 (2012).CrossRefGoogle Scholar
Collins, B.A., Li, Z., Tumbleston, J.R., Gann, E., McNeill, C.R., and Ade, H.: Absolute measurement of domain composition and nanoscale size distribution explains performance in PTB7:PC71BM solar cells. Adv. Energy Mater. 3, 6574 (2013).CrossRefGoogle Scholar
He, X.X., Collins, B.A., Watts, B., Ade, H., and McNeill, C.R.: Studying polymer/fullerene intermixing and miscibility in laterally patterned films with X-ray spectromicroscopy. Small 8, 19201927 (2012).CrossRefGoogle ScholarPubMed
McNeill, C.R., Watts, B., Thomsen, L., Belcher, W.J., Greenham, N.C., and Dastoor, P.C.: Nanoscale quantitative chemical mapping of conjugated polymer blends. Nano Lett. 6, 12021206 (2006).CrossRefGoogle ScholarPubMed
McNeill, C.R., Watts, B., Thomsen, L., Belcher, W.J., Greenham, N.C., Dastoor, P.C., and Ade, H.: Evolution of laterally phase-separated polyfluorene blend morphology studied by X-ray spectromicroscopy. Macromolecules 42, 33473352 (2009).CrossRefGoogle Scholar
McNeill, C.R. and Ade, H.: Soft X-ray characterisation of organic semiconductor films. J. Mater. Chem. C 1, 187201 (2013).CrossRefGoogle Scholar
Obst, M., Wang, J., and Hitchcock, A.P.: 3-d chemical imaging with STXM tomography. J. Phys.: Conf. Ser. 186, 012045 (2009).Google Scholar
Thompson, A., Attwood, D., Gullikson, E., Howells, M., Kim, K-J., Kirz, J., Kortright, J., Lindau, I., Liu, Y., Pianetta, P., Robinson, A., Scofield, J., Underwood, J., Williams, G., and Winick, H.: X-Ray Data Booklet (Lawrence Berkeley National Laboratory, University of California, Berkeley, 2009).Google Scholar
Stöhr, J.: NEXAFS Spectroscopy (Springer-Verlag, Berlin Heidelberg, 1992).CrossRefGoogle Scholar
Nahid, M.M., Gann, E., Thomsen, L., and McNeill, C.R.: NEXAFS spectroscopy of conjugated polymers. Eur. Polym. J. 81, 532554 (2016).CrossRefGoogle Scholar
Hub, C., Wenzel, S., Raabe, J., Ade, H., and Fink, R.H.: Surface sensitivity in scanning transmission X-ray microspectroscopy using secondary electron detection. Rev. Sci. Instrum. 81, 033704 (2010).CrossRefGoogle ScholarPubMed
Dhez, O., Ade, H., and Urquhart, S.G.: Calibrated NEXAFS spectra of some common polymers. J. Electron Spectrosc. Relat. Phenom. 128, 8596 (2003).CrossRefGoogle Scholar
Watts, B., Swaraj, S., Nordlund, D., Luning, J., and Ade, H.: Calibrated NEXAFS spectra of common conjugated polymers. J. Chem. Phys. 134, 024702 (2011).CrossRefGoogle ScholarPubMed
Attwood, D.: Soft X-rays and Extreme Ultraviolet Radiation (Cambridge University Press, Cambridge, 1999).CrossRefGoogle Scholar
Kilcoyne, A.L.D., Tyliszczak, T., Steele, W.F., Fakra, S., Hitchcock, P., Franck, K., Anderson, E., Harteneck, B., Rightor, E.G., Mitchell, G.E., Hitchcock, A.P., Yang, L., Warwick, T., and Ade, H.: Interferometer-controlled scanning transmission X-ray microscopes at the advanced light source. J. Synchrotron Radiat. 10, 125136 (2003).CrossRefGoogle ScholarPubMed
Flechsig, U., Quitmann, C., Raabe, J., Böge, M., Fink, R., and Ade, H.: The PolLux microspectroscopy beamline at the Swiss light source. AIP Conf. Proc. 879, 505508 (2006).CrossRefGoogle Scholar
Raabe, J., Tzvetkov, G., Flechsig, U., Boge, M., Jaggi, A., Sarafimov, B., Vernooij, M.G., Huthwelker, T., Ade, H., Kilcoyne, D., Tyliszczak, T., Fink, R.H., and Quitmann, C.: PolLux: A new facility for soft X-ray spectromicroscopy at the Swiss light source. Rev. Sci. Instrum. 79, 113704 (2008).CrossRefGoogle ScholarPubMed
Kiel, J.W., Kirby, B.J., Majkrzak, C.F., Maranville, B.B., and Mackay, M.E.: Nanoparticle concentration profile in polymer-based solar cells. Soft Matter 6, 641646 (2010).CrossRefGoogle Scholar
Parnell, A.J., Dunbar, A.D.F., Pearson, A.J., Staniec, P.A., Dennison, A.J.C., Hamamatsu, H., Skoda, M.W.A., Lidzey, D.G., and Jones, R.A.L.: Depletion of PCBM at the cathode interface in P3HT/PCBM thin films as quantified via neutron reflectivity measurements. Adv. Mater. 22, 24442447 (2010).CrossRefGoogle ScholarPubMed
Ro, H.W., Akgun, B., O’Connor, B.T., Hammond, M., Kline, R.J., Snyder, C.R., Satija, S.K., Ayzner, A.L., Toney, M.F., Soles, C.L., and DeLongchamp, D.M.: Poly(3-hexylthiophene) and [6,6]-phenyl-C61-butyric acid methyl ester mixing in organic solar cells. Macromolecules 45, 65876599 (2012).CrossRefGoogle Scholar
Anselmo, A.S., Lindgren, L., Rysz, J., Bernasik, A., Budkowski, A., Andersson, M.R., Svensson, K., van Stam, J., and Moons, E.: Tuning the vertical phase separation in polyfluorene:fullerene blend films by polymer functionalization. Chem. Mater. 23, 22952302 (2011).CrossRefGoogle Scholar
Björström, C.M., Bernasik, A., Rysz, J., Budkowski, A., Nilsson, S., Svensson, M., Andersson, M.R., Magnusson, K.O., and Moons, E.: Multilayer formation in spin-coated thin films of low-bandgap polyfluorene:PCBM blends. J. Phys.: Condens. Matter 17, L529L534 (2005).Google Scholar
Chen, D., Liu, F., Wang, C., Nakahara, A., and Russell, T.P.: Bulk heterojunction photovoltaic active layers via bilayer interdiffusion. Nano Lett. 11, 20712078 (2011).CrossRefGoogle ScholarPubMed
Collins, B.A., Gann, E., Guignard, L., He, X., McNeill, C.R., and Ade, H.: Molecular miscibility of polymer−fullerene blends. J. Phys. Chem. Lett. 1, 31603166 (2010).CrossRefGoogle Scholar
Treat, N.D., Brady, M.A., Smith, G., Toney, M.F., Kramer, E.J., Hawker, C.J., and Chabinyc, M.L.: Interdiffusion of PCBM and P3HT reveals miscibility in a photovoltaically active blend. Adv. Energy Mater. 1, 8289 (2011).CrossRefGoogle Scholar
Anselmo, A.S., Dzwilewski, A., Svensson, K., and Moons, E.: Photodegradation of the electronic structure of PCBM and C60 films in air. Chem. Phys. Lett. 652, 220224 (2016).CrossRefGoogle Scholar
Pedersen, E.B.L., Tromholt, T., Madsen, M.V., Bottiger, A.P.L., Weigand, M., Krebs, F.C., and Andreasen, J.W.: Spatial degradation mapping and component-wise degradation tracking in polymer–fullerene blends. J. Mater. Chem. C 2, 51765182 (2014).CrossRefGoogle Scholar
Hansson, R., Lindqvist, C., Ericsson, L.K., Opitz, A., Wang, E., and Moons, E.: Photo-degradation in air of the active layer components in a thiophene–quinoxaline copolymer:fullerene solar cell. Phys. Chem. Chem. Phys. 18, 1113211138 (2016).CrossRefGoogle Scholar
Brumboiu, I.E., Ericsson, L., Hansson, R., Moons, E., Eriksson, O., and Brena, B.: The influence of oxygen adsorption on the NEXAFS and core-level XPS spectra of the C60 derivative PCBM. J. Chem. Phys. 142, 054306 (2015).CrossRefGoogle ScholarPubMed
Brumboiu, I.E., Anselmo, A.S., Brena, B., Dzwilewski, A., Svensson, K., and Moons, E.: Near-edge X-ray absorption fine structure study of the C60-derivative PCBM. Chem. Phys. Lett. 568–569, 130134 (2013).CrossRefGoogle Scholar
Patel, S.N., Su, G.M., Luo, C., Wang, M., Perez, L.A., Fischer, D.A., Prendergast, D., Bazan, G.C., Heeger, A.J., Chabinyc, M.L., and Kramer, E.J.: NEXAFS spectroscopy reveals the molecular orientation in blade-coated pyridal[2,1,3]thiadiazole-containing conjugated polymer thin films. Macromolecules 48, 66066616 (2015).CrossRefGoogle Scholar
Ade, H., Watts, B., Swaraj, S., McNeill, C., Thomsen, L., Belcher, W., and Dastoor, P.C.: NEXAFS microscopy of polymeric materials: Successes and challenges encountered when characterizing organic devices. J. Phys.: Conf. Ser. 186, 012102 (2009).Google Scholar
Wang, E., Hou, L., Wang, Z., Hellstrom, S., Zhang, F., Inganäs, O., and Andersson, M.R.: An easily synthesized blue polymer for high-performance polymer solar cells. Adv. Mater. 22, 52405244 (2010).CrossRefGoogle ScholarPubMed
Kim, Y., Yeom, H.R., Kim, J.Y., and Yang, C.: High-efficiency polymer solar cells with a cost-effective quinoxaline polymer through nanoscale morphology control induced by practical processing additives. Energy Environ. Sci. 6, 19091916 (2013).CrossRefGoogle Scholar
Zhang, W.: Morphology control of polymer:fullerene solar cells by nanoparticle self-assembly. PhD thesis, Dept. of Materials Science and Engineering, University of Delaware, Newark, 2016.Google Scholar
Rispens, M.T., Meetsma, A., Rittberger, R., Brabec, C.J., Sariciftci, N.S., and Hummelen, J.C.: Influence of the solvent on the crystal structure of PCBM and the efficiency of MDMO-PPV:PCBM ‘plastic’ solar cells. Chem. Commun. 39, 21162118 (2003).CrossRefGoogle Scholar
Kern, W.: The evolution of silicon wafer cleaning technology. J. Electrochem. Soc. 137, 18871892 (1990).CrossRefGoogle Scholar
Kern, W. and Puotinen, D.A.: Cleaning solutions based on hydrogen peroxide for use in silicon semiconductor technology. RCA Rev. 31, 187206 (1970).Google Scholar
Kissinger, G. and Kissinger, W.: Hydrophilicity of silicon wafers for direct bonding. Phys. Status Solidi A 123, 185192 (1991).CrossRefGoogle Scholar
Watts, B., Thomsen, L., and Dastoor, P.C.: Methods in carbon K-edge NEXAFS: Experiment and analysis. J. Electron Spectrosc. Relat. Phenom. 151, 105120 (2006).CrossRefGoogle Scholar
Watts, B. and Ade, H.: A simple method for determining linear polarization and energy calibration of focused soft X-ray beams. J. Electron Spectrosc. Relat. Phenom. 162, 4955 (2008).CrossRefGoogle Scholar
Henke, B.L., Gullikson, E.M., and Davis, J.C.: X-ray interactions: Photoabsorption, scattering, transmission, and reflection at E = 50–30,000 eV, Z = 1–92. At. Data Nucl. Data Tables 54, 181342 (1993).CrossRefGoogle Scholar
Watts, B., Warnicke, P., Pilet, N., and Raabe, J.: Nanoscale measurement of the absolute mass density of polymers. Phys. Status Solidi A 212, 518522 (2015).CrossRefGoogle Scholar
Zheng, Y., Li, S., Zheng, D., and Yu, J.: Effects of different polar solvents for solvent vapor annealing treatment on the performance of polymer solar cells. Org. Electron. 15, 26472653 (2014).CrossRefGoogle Scholar
Han, B., Gopalan, S-A., Lee, K-D., Kang, B-H., Lee, S-W., Lee, J-S., Kwon, D-H., Lee, S-H., and Kang, S-W.: Preheated solvent exposure on P3HT:PCBM thin film: A facile strategy to enhance performance in bulk heterojunction photovoltaic cells. Curr. Appl. Phys. 14, 14431450 (2014).CrossRefGoogle Scholar
Liu, Y-X., , L-F., Ning, Y., Lu, Y-Z., Lu, Q-P., Zhang, C-M., Fang, Y., Tang, A-W., Hu, Y-F., Lou, Z-D., Teng, F., and Hou, Y-B.: Effects of acetone-soaking treatment on the performance of polymer solar cells based on P3HT/PCBM bulk heterojunction. Chin. Phys. B 23, 118802 (2014).CrossRefGoogle Scholar
Henriksson, P., Lindqvist, C., Abdisa, B., Wang, E., George, Z., Kroon, R., Müller, C., Yohannes, T., Inganäs, O., and Andersson, M.R.: Stability study of quinoxaline and pyrido pyrazine based co-polymers for solar cell applications. Sol. Energy Mater. Sol. Cells 130, 138143 (2014).CrossRefGoogle Scholar
Hintz, H., Egelhaaf, H.J., Peisert, H., and Chassé, T.: Photo-oxidation and ozonization of poly(3-hexylthiophene) thin films as studied by UV/VIS and photoelectron spectroscopy. Polym. Degrad. Stab. 95, 818825 (2010).CrossRefGoogle Scholar
Manceau, M., Bundgaard, E., Carle, J.E., Hagemann, O., Helgesen, M., Sondergaard, R., Jorgensen, M., and Krebs, F.C.: Photochemical stability of [small pi]-conjugated polymers for polymer solar cells: A rule of thumb. J. Mater. Chem. 21, 41324141 (2011).CrossRefGoogle Scholar
Chambon, S., Rivaton, A., Gardette, J-L., Firon, M., and Lutsen, L.: Aging of a donor conjugated polymer: Photochemical studies of the degradation of poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene]. J. Polym. Sci., Part A: Polym. Chem. 45, 317331 (2007).CrossRefGoogle Scholar
Jørgensen, M., Norrman, K., and Krebs, F.C.: Stability/degradation of polymer solar cells. Sol. Energy Mater. Sol. Cells 92, 686714 (2008).CrossRefGoogle Scholar
Rivaton, A., Tournebize, A., Gaume, J., Bussière, P., Gardette, J., and Therias, S.: Photostability of organic materials used in polymer solar cells. Polym. Int. 63, 13351345 (2014).CrossRefGoogle Scholar
Reese, M.O., Nardes, A.M., Rupert, B.L., Larsen, R.E., Olson, D.C., Lloyd, M.T., Shaheen, S.E., Ginley, D.S., Rumbles, G., and Kopidakis, N.: Photoinduced degradation of polymer and polymer–fullerene active layers: Experiment and theory. Adv. Funct. Mater. 20, 34763483 (2010).CrossRefGoogle Scholar
Chambon, S., Rivaton, A., Gardette, J., and Firon, M.: Photo- and thermal degradation of MDMO-PPV:PCBM blends. Sol. Energy Mater. Sol. Cells 91, 394398 (2007).CrossRefGoogle Scholar