Dye-Sensitized (DSSC) and Perovskites Solar Cells (PSC): Materials and Devices (A. Abbotto)

Our group is involved with the design, synthesis, and characterization of organic and organometallic materials and devices for third generation photovoltaics, including liquid and solid-state n- and p-dye-sensitized solar cells (n-DSSC and p-DSSC), perovskite-based solar cells (PSC), and polymeric/small molecule organic solar cells (OPV). DSSCs, pioneered by Michael Grätzel and thus commonly referred to as Grätzel cells, feature a network of disordered and inexpensive TiO2 nanoparticles coated with light-harvesting dye molecules and typically surrounded by a liquid-phase electrolyte or hole conductor. Photons captured by the dye generate electron-hole pairs which separate at the surface of the nanoparticles. Electrons are injected and transported through the TiO2 layer while positive charges migrate via the electrolyte to the opposite side of the cell. Our work, in collaboration with national and international private and public partners, focuses on the synthesis of new materials photosensitizers, semiconductor oxides and electrolytes with tailored properties and optimized performances thanks to the use of a fruitful combination of electron-rich and electron-poor (hetero)aromatic building units, a variety of structural design, and different symmetries and geometries.

In the field of PSC (pervoskite-based solar cells) we investigate new organic molecular and polymeric components as organic precursors for the perovskite layer and as HTM.

 

 

In the frame of the Solar Research Center MIB-SOLAR and its facilities, the group also performs fabrication and characterization of DSSC, PSC and OPV small cells and modules, also in collaboration with private companies. The best power conversion efficiencies top out at ca. 11% (lab scale).

 

In addition to the main research topic, hybrid systems (DSSC-CIGS-Si and PSC-CIGS-Si) and solid state DSSC and PSC devices are under active investigation.

The activity of the group is part of leading european and national networks on optimization and industrial application of DSCs with grants from Fondazione Cariplo, MIUR-PRIN, FP7, and private companies.

In summary.

The DSC group of Prof. A. Abbotto at UNIMIB – Solar Energy Center MIB-Solar  has been  involved in the last years in research for materials and devices for DSSC and PSC.
Materials include:

  • organometallic and organic dyes
  • iodine-free electrolytes
  • quasi solid-state DSSC
  • nanostructured TiO2
  • perovskites and HTM

Devices include fabrication and characterization of liquid and solid-state cells and modules up to 8×8″. Facilities include:

  • 1000 ft2 ISO 7 clean room
  • screen printers
  • ozone cleaning
  • class ABA solar simulators for cells and modules
  • laser scribing
  • IPCE and APCE
  • glove boxes with spin coaters and evaporators

Recent Publications and Patents on DSSC.

    1. Abbotto, A.; Barolo, C.; Yum, J.-H.; Bellotto, L.; De Angelis, F.; Grätzel, M.; Marinzi, C.; Nazeeruddin, M. K.
      “Ruthenium sensitizers based on heteroaromatic conjugated bipyridines for dye-sensitized solar cells”,
      SPIE Proceed. 2008, 6999, 69990O-1 – 69990O-9.
    2. Abbotto, A.; Bellotto, L.; De Angelis, F.; Manfredi, N.; Marinzi, C.
      Heteroaromatic donor-acceptor p-conjugated 2,2′-bipyridines“,
      Eur. J. Org. Chem. 2008, 5047-5054.
    3. Abbotto, A.; Barolo, C.; Bellotto, L.; De Angelis,F.; Grätzel, M.; Manfredi, N.; Marinzi, C.; Fantacci, S.; Yum, J.-H.; Nazeeruddin, M. K.
      Heteroaromatic conjugated bipyridine based ruthenium sensitizer for efficient dye-sensitized solar cells“,
      Chem. Commun. 2008, 5318-5320.
    4. Abbotto, A.; Manfredi, N.; Marinzi, C.; Angelis, F. D.; Mosconi, E.; Yum, J.-H.; Xianxi, Z.; Nazeeruddin, M.K.; Gratzel, M.
      Di-branched di-anchoring organic dyes for dye-sensitized solar cells“,
      Energy Environ. Sci. 2009, 2, 1094-1101.
    5. Abbotto, A.; De Angelis, F.; Nazeeruddin, M. D.; Graetzel, M.; Marinzi, C.; Manfredi, N.
      Novel Ligands for Sensitizing Dyes of Dye-Sensitized Solar Cells
      Eur.Pat. Appl. EP 09171711.6, 2009; PCT Int. Appl. (2011), WO 2011039715 A1 20110407 (publication date 7 April 2011).
    6. Abbotto, A.; Manfredi, N.; Coluccini, C.; Roberto, D.; Ugo, R.; Dragonetti, C.; Valore, A.; Colombo, A.
      “Nuovi complessi ciclometallati per celle solari”
      Ital. pat. Appl. 2010.
    7. Mosquera Vázquez, S.; Abbotto, A.; De Angelis, F.; Foggi, P.; Lapini, A.; Lima, M.; Lobello, M.; Marcelli, A.; Tourón Touceda, P.
      “Transient absorption spectroscopy of a heteroaromatic donor–acceptor-π-conjugated 2,2’-bipyridine dye”
      J. Mol. Struct. 2011, 993, 464-469; dx.doi.org/10.1016/j.molstruc.2011.01.042.
    8. Abbotto, A.; Sauvage, F.; Barolo, C.; De Angelis, F.; Fantacci, S.; Graetzel, M.; Manfredi, N.; Marinzi, C.; Nazeeruddin, M. K.
      Panchromatic ruthenium sensitizer based on electron-rich heteroarylvinylene p-conjugated quaterpyridine for dye-sensitized solar cells
      Dalton Trans. 2011, 40, 234-242.
    9. Abbotto, A.; Simonutti, R.; Manfredi, N.; Bianchi, A.
      “Celle fotovoltaiche a colorante con elettroliti solidi a base di copolimeri a blocchi”
      italian patent application, 2011
    10. Abbotto, A.; Manfredi N.
      Electron-rich heteroaromatic conjugated polypyridine ruthenium sensitizers for dye-sensitized solar cells (review)“, Dalton Trans., 2011, dx.doi.org/10.1039/C1DT10832H.
    11. Abbotto, A.; Leandri, V.; Manfredi, N.; De Angelis, F.; Pastore, M.; Yum, J.-H.; Nazeeruddin, M. K.; Grätzel, M.
      Bis-Donor-Bis-Acceptor Tribranched Organic Sensitizers for Dye-Sensitized Solar Cells
      Eur. J. Org. Chem., 2011, 6195
    12. Coluccini, C.; Manfredi, N.; Herrera Calderon, E.; Salamone, M. M.; Ruffo, R.; Roberto, D.; Lobello, M. G.; De Angelis, F.; Abbotto, A.
      Photophysical and Electrochemical Properties of Thiophene-Based 2-Arylpyridines
      Eur. J. Org. Chem., 2011, 5587-5595
    13. Abbotto, A.; Manfredi, N.; Coluccini, C.; Roberto, D.; Ugo, R.; Dragonetti, C.; Valore, A.; Colombo, A.
      “New Cyclometalated Complexes for Solar Cells”
      PCT Int. Appl. 2012, PCT/EP2011/062936
    14. Dragonetti, C.; Valore, A.; Colombo, A.; Roberto, D.; Trifiletti, V.; Manfredi, N.; Salamone, M. M.; Ruffo, R.; Abbotto, A.
      A new thiocyanate-free cyclometallated ruthenium complex for dye-sensitized solar cells: beneficial effects of substitution on the cyclometallated ligand
      J. Organomet. Chem. 2012, 714, 88-93
    15. Dell’Orto, E.; Raimondo, L.; Sassella, A.; Abbotto, A.
      Dye-sensitized solar cells: spectroscopic evaluation of dye loading on TiO2
      J. Mater. Chem. 2012, 22, 11364 – 11369
    16. Abbotto, A.; Coluccini, C.; Dell’Orto, E.; Manfredi, N.; Trifiletti, V.; Salamone, M. M.; Ruffo, R.; Acciarri, M.; Colombo, A.; Dragonetti, C.; Ordanini, S.; Roberto, D.; Valore, A.
      Thiocyanate-free cyclometalated ruthenium sensitizers for solar cells based on heteroaromatic-substituted 2-arylpyridines
      Dalton Trans., 2012, 41, 11731-11738.
    17. Coluccini, C.; Manfredi, N.; Salamone, M. M.; Ruffo, R.; Lobello, M. G.; De Angelis, F.; Abbotto, A.
      Quaterpyridine ligands for panchromatic Ru(II) dye sensitizers
      J. Org. Chem. 2012; 77, 7945-7956.
    18. Abbotto, A.; Simonutti, R.; Manfredi, N.; Bianchi, A.
      “Block copolymer-based solid electrolytes for dye photovoltaic cells, and cells thus obtained”
      PCT Int. Appl. 2012
    19. Maiorana, S.; Licandro, E.; Longhi, E.; Cauteruccio, S.; Abbotto, A.; Baldoli, C.; De Angelis, F.
      “Metal-free photosensitizers”
      PCT Int. Appl. 2012; WO 2012/107488.
    20. Di Carlo, G.; Orbelli Biroli, A.; Pizzotti, M.; Tessore, F.; Trifiletti, V.; Ruffo, R.; Abbotto, A.; Amat, A.; De Angelis, F.; Mussini, P. R.
      Tetraaryl Zn(II) Porphyrinates Substituted at ?-Pyrrolic Positions as Sensitizers in Dye-Sensitized Solar Cells: A Comparison with meso-Disubstituted Push-Pull Zn(II) Porphyrinates“,
      Chem. Eur. J. 2013, 19, 10723-10740.
    21. Le Donne, A.; Scaccabarozzi, A.; Tombolato, S.; Binetti, S.; Acciarri, M.; Abbotto, A.
      Solar Photovoltaics: A Review
      Rev. Adv. Sci. Eng. 2013, 2, 170-178.
    22. Dragonetti, C.; Valore, A.; Colombo, A.; Magni, M.; Mussini, P.; Roberto, D.; Ugo, R.; Valsecchi, A.; Trifiletti, V.; Manfredi, N.; Abbotto, A.
      Ruthenium Oxyquinolate Complexes for Dye-Sensitized Solar Cells
      Inorganica Chimica Acta 2013, 405, 98-104.
    23. Trifiletti, V.; Ruffo, R.; Turrini, C.; Tassetti, D.; Brescia, R.; Di Fonzo, F.; Riccardi, C.; Abbotto, A.
      Dye-sensitized solar cells containing plasma jet deposited hierarchical nanostructured TiO2 thin photoanodes
      J. Mater. Chem. A 2013, 1, 11665-11673.
    24. Leandri, V.; Ruffo, R.; Trifiletti, V.; Abbotto, A.
      Asymmetric Tribranched Dyes: an Intramolecular Co-Sensitization Approach for Dye-Sensitized Solar Cells
      Eur. J. Org. Chem. 2013, 6793-6801 (cover article).
    25. Lobello, M. G.; Fantacci, S.; Manfredi, N.; Coluccini, C.; Abbotto, A.; Nazeeruddin, Md. K.; De Angelis, F.
      Design of Ru(II) sensitizers endowed by three anchoring units for adsorption mode and light harvesting optimization
      Thin Solid Films 2014, 560, 86-93; dx.doi.org/10.1016/j.tsf.2013.08.112.
    26. Manfredi, N.; Bianchi, A.; Causin, V.; Ruffo, R.; Simonutti, R.; Abbotto, A.
      Electrolytes for quasi solid-state dye-sensitized solar cells based on blockcopolymers
      J. Polym. Sci. A 2013, 52, 719-727; dx.doi.org/10.1002/pola.27055
    27. Di Carlo, G.; Orbelli Biroli, A.; Tessore, F. Pizzotti, M.; Mussini, P. R.; Amat, A.; De Angelis, F.; Abbotto, A.; Trifiletti, V.; Ruffo, R.
      A Physico-Chemical Investigation of the Panchromatic Effect on β-Substituted ZnII Porphyrinates for DSSCs: The Role of the π Bridge between a Dithienylethylene Unit and the Porphyrinic Ring
      J. Phys. Chem. C 2014, 118, 7307-7320.
    28. Colombo, A.; Dragonetti, C.; Valore, A.; Coluccini, C.; Manfredi, N.; Abbotto, A.
      Thiocyanate-free ruthenium(II) 2,2′-Bipyridyl complexes for dye-sensitized solar cells
      Polyhedron, 2014, 82, 50-56.
    29. Manfredi, N.; Cecconi, B.; Abbotto, A.
      Multi-branched multi-anchoring metal-free dyes for dye-sensitized solar cells
      Eur. J. Org. Chem. 2014, 7069-7086.
    30. Abbotto, A.; Acciarri, M.; Biagini, P.; Binetti, S. “Organic dye for a dye sensitized solar cell” PCT Int. Appl. 2014, WO 2014053626 A1 20140410 (Università di Milano Bicocca – eni SpA)
    31. Baldoli, C.; Bertuolo, S.; Licandro, E.; Viglianti, L.; Mussini, P.; Marotta, G.; Salvatori, P.; De Angelis, F.; Manca, P.; Manfredi, N.; Abbotto, A.,
      Benzodithiophene Based Organic Dyes for DSSC: Effect of Alkyl Chain Substitution on Dye Efficiency
      Dyes and Pigments, 2015121, 351-362.
    32. Karamshuk, S.; Caramori, S.; Manfredi, N.; Salamone, M.; Ruffo, R.; Carli, S.; Bignozzi, C. A.; Abbotto, A.
      Molecular level factors affecting the efficiency of organic chromophores for p-type dye sensitized solar cells
      Energies 2016, 9, 33-50.
    33. Boldrini, C. L.; Manfredi, N.; Perna, F. M.; Trifiletti, V.; Capriati, V.; Abbotto, A.
      Dye-sensitized solar cells using an aqueous choline chloride-based deep eutectic solvent as an effective electrolyte solution
      Energy Technol. 20175, 345-353.
    34. Gatti, T.; Manfredi, N.; Boldrini, C.; Lamberti, F.; Abbotto, A.; Menna, E.
      “A D-π-A organic dye – reduced graphene oxide covalent dyad as a new concept photosensitizer for light harvesting applications”
      Carbon 2017115, 746-753.
    35. Manfredi, N.; Trifiletti, V.; Melchiorre, F.; Giannotta, G.; Biagini, P.; Abbotto, A.
      Performance enhancement of dye-sensitized solar cell by peripheral aromatic and heteroaromatic functionalization in dibranched organic sensitizers
      New J. Chem. 2018, 42, 9281-9290.
    36. Boldrini, C. L.; Manfredi, N.; Perna, F. M.; Capriati, V.;* Abbotto, A.*
      Designing Eco-Sustainable Dye-Sensitized Solar Cells by the Use of a Menthol-based Hydrophobic Eutectic Solvent as an Effective Electrolyte Medium
      Chem. Eur. J. 2018, 24, 17656-17659.
    37. Dova, D.; Cauteruccio, S.; Manfredi, N.; Prager, S.; Dreuw, A.; Arnaboldi, S.; Mussini, P. R.; Licandro, E.; Abbotto, A.
      Helical push-pull systems for solar cells: Electrochemical, computational, photovoltaic and NMR data
      Data in Brief 2018, 21, 2339-2349.
    38. Dova, D.; Cauteruccio, S.; Manfredi, N.; Prager, S.; Dreuw, A.; Arnaboldi, S.; Mussini, P. R.; Licandro, E.; Abbotto, A.
      An unconventional helical push-pull system for solar cells
      Dyes&Pigments 2019, 161, 382-388,

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