New fluorenone-containing organic photosensitizers for dye-sensitized solar cells

Abstract Four new organic dyes ( F1 – F4 ) comprising the triarylamine or fluorene unit as an electron-donating group, a less commonly used fluorenone spacer and a cyanoacrylic acid as the anchoring group in the molecular framework were synthesized, characterized and utilized in dye-sensitized solar cells (DSSCs). Their absorption, photoluminescence, electrochemical and photovoltaic properties were fully investigated in detail. Electrochemical data indicate that the tuning of the HOMO and LUMO energy levels can be conveniently accomplished by alternating the donor moiety. The photovoltaic performance can be increased by adding an electron-donating triarylamine or fluorene unit next to the fluorenone ring or increasing the number of thienyl ring next to the cyanoacrylic acid group, which is consistent with the results from electrochemical impedance spectroscopy. The maximal monochromatic incident photon-to-current conversion efficiency (IPCE) can reach up to 80% for DSSC devices based on F4 with the overall light to electricity conversion efficiency up to 4.71% ( V oc  = 565 mV, J sc  = 11.71 mA cm −2 and FF  = 0.71) under AM 1.5 irradiation (100 mW cm −2 ).

[1]  Liyuan Han,et al.  Incorporating a stable fluorenone unit into D–A–π–A organic dyes for dye-sensitized solar cells , 2012 .

[2]  Shane Ardo,et al.  Photodriven heterogeneous charge transfer with transition-metal compounds anchored to TiO2 semiconductor surfaces. , 2009, Chemical Society reviews.

[3]  H. Pettersson,et al.  Dye-sensitized solar cells. , 2010, Chemical Reviews.

[4]  John K. Stille,et al.  The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)] , 1986 .

[5]  Ullrich Scherf,et al.  Semiconducting Polyfluorenes—Towards Reliable Structure–Property Relationships , 2002 .

[6]  B. Grévin,et al.  Fluorenone core donor–acceptor–donor π-conjugated molecules end-capped with dendritic oligo(thiophene)s: synthesis, liquid crystalline behaviour, and photovoltaic applications , 2011 .

[7]  U. Giovanella,et al.  Synthesis and characterisation of fluorenone–thiophene-based donor–acceptor oligomers: role of moiety sequence upon packing and electronic properties , 2010 .

[8]  H. Tian,et al.  Unsymmetric platinum(II) bis(aryleneethynylene) complexes as photosensitizers for dye-sensitized solar cells. , 2012, Chemistry, an Asian journal.

[9]  H. Tian,et al.  Heteroleptic ruthenium complexes containing uncommon 5,5'-disubstituted-2,2'-bipyridine chromophores for dye-sensitized solar cells. , 2011, Dalton transactions.

[10]  Mohammad Khaja Nazeeruddin,et al.  Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes , 1993 .

[11]  Anders Hagfeldt,et al.  Molecular engineering of organic sensitizers for dye-sensitized solar cell applications. , 2008, Journal of the American Chemical Society.

[12]  Kuo-Chuan Ho,et al.  2,3-Disubstituted Thiophene-Based Organic Dyes for Solar Cells , 2008 .

[13]  H. Tian,et al.  Stable dyes containing double acceptors without COOH as anchors for highly efficient dye-sensitized solar cells. , 2012, Angewandte Chemie.

[14]  M. Orchin,et al.  Molecular Complexes with 2,4,7-Trinitrofluorenone. II1 , 1946 .

[15]  Hongjun Zhu,et al.  The synthesis, crystal structures and photophysical properties of a series of novel 4,6-diphenyl-1,9-anthrazolines , 2011 .

[16]  Michael Grätzel,et al.  Porphyrin-Sensitized Solar Cells with Cobalt (II/III)–Based Redox Electrolyte Exceed 12 Percent Efficiency , 2011, Science.

[17]  Hironori Arakawa,et al.  Photosensitization of a porous TiO2 electrode with merocyanine dyes containing a carboxyl group and a long alkyl chain , 2000 .

[18]  X. Lu,et al.  Dithiafulvenyl unit as a new donor for high-efficiency dye-sensitized solar cells: synthesis and demonstration of a family of metal-free organic sensitizers. , 2012, Organic letters.

[19]  Michael Grätzel,et al.  Efficient panchromatic sensitization of nanocrystalline TiO2 films by a black dye based on a trithiocyanato-ruthenium complex , 1997 .

[20]  Huilong Wang,et al.  Simple and Efficient Method for Obtaining Fluorene and Spirobifluorene Bromide Derivatives , 2008 .

[21]  H. Jianli,et al.  New D-π-A dyes for efficient dye-sensitized solar cells , 2012 .

[22]  M. Turner,et al.  Synthesis and properties of conjugated oligomers containing fluorene, fluorenone, thiophene and cyclopentadithiophenone units , 2006 .

[23]  He Tian,et al.  Photoelectrochemical studies of nanocrystalline TiO2 co-sensitized by novel cyanine dyes , 2005 .

[24]  L. Giribabu,et al.  Metal-free organic dyes for dye-sensitized solar cells: recent advances , 2012 .

[25]  J. Moser,et al.  Merocyanine Aggregation in Mesoporous Networks , 1996 .

[26]  Jun Chen,et al.  Arylamine organic dyes for dye-sensitized solar cells. , 2013, Chemical Society reviews.

[27]  Naoki Koide,et al.  Methods of Measuring Energy Conversion Efficiency in Dye-sensitized Solar Cells , 2005 .

[28]  M. Newman,et al.  2,4,5,7-Tetranitrofluorenone † , 2003 .

[29]  H. Tian,et al.  Narrowing band gap of platinum acetylide dye-sensitized solar cell sensitizers with thiophene π-bridges , 2012 .

[30]  A. Heeger,et al.  The synthesis and characterization of an efficient green electroluminescent conjugated polymer: poly[2,7-bis(4-hexylthienyl)-9,9-dihexylfluorene] , 2000 .

[31]  I. F. Perepichka,et al.  Electron acceptors of the fluorene series. Part 6. 1 Synthesis of 4,5-dinitro-9-X-fluorene-2,7-disulfonic acid derivatives, their charge transfer complexes with anthracene and sensitization of photoconductivity of poly-N-(2,3-epoxypropyl)carbazole , 1997 .

[32]  H. Tian,et al.  Efficient and stable organic DSSC sensitizers bearing quinacridone and furan moieties as a planar π-spacer , 2012 .

[33]  Peng Wang,et al.  Charge separation and efficient light energy conversion in sensitized mesoscopic solar cells based on binary ionic liquids. , 2005, Journal of the American Chemical Society.

[34]  Jiann T. Lin,et al.  New bithiazole-functionalized organic photosensitizers for dye-sensitized solar cells , 2013 .

[35]  L. Andrews,et al.  Photophysical processes in fluorenone , 1978 .

[36]  Anders Hagfeldt,et al.  Phenothiazine derivatives for efficient organic dye-sensitized solar cells. , 2007, Chemical communications.

[37]  P. Liska,et al.  A swift dye uptake procedure for dye sensitized solar cells. , 2003, Chemical communications.

[38]  Michael Grätzel,et al.  Recent advances in sensitized mesoscopic solar cells. , 2009, Accounts of chemical research.

[39]  Molecular Designs and Syntheses of Organic Dyes for Dye-Sensitized Solar Cells , 2009 .