Synthesis, Photophysics, and Photovoltaic Studies of Ruthenium Cyclometalated Complexes as Sensitizers for p-Type NiO Dye-Sensitized Solar Cells

We report the first application of cyclometalated ruthenium complexes of the type Ru[(N∧N)2(C∧N)]+ as sensitizers for p-type NiO dye-sensitized solar cells (NiO p-DSCs). These dyes exhibit broad absorption in the visible region. The carboxylic anchoring group is attached to the phenylpyridine ligand, which results in efficient hole injection. Moreover, the distance between the Ru[(N∧N)2(C∧N)]+ core and the carboxylic anchoring group is systematically varied by inserting rigid phenylene linkers. Femtosecond transient absorption (TA) studies reveal that the interfacial charge recombination rate between reduced sensitizers and holes in the valence band of NiO decreases as the number of phenylene linkers increases across the series. As a result, the solar cell made of the dye with the longest spacer (O12) exhibits the highest efficiency with both increased short-circuit current (Jsc) and open-circuit voltage (Voc). The incident photon-to-current conversion efficiency (IPCE) spectra match well with the absorpt...

[1]  E. Blart,et al.  Ultrafast recombination for NiO sensitized with a series of perylene imide sensitizers exhibiting Marcus normal behaviour. , 2012, Chemical communications.

[2]  Anders Hagfeldt,et al.  Visible light driven hydrogen production from a photo-active cathode based on a molecular catalyst and organic dye-sensitized p-type nanostructured NiO. , 2012, Chemical communications.

[3]  Zhongjie Huang,et al.  p-Type Dye-Sensitized NiO Solar Cells: A Study by Electrochemical Impedance Spectroscopy , 2011 .

[4]  Paolo G. Bomben,et al.  A trisheteroleptic cyclometalated Ru(II) sensitizer that enables high power output in a dye-sensitized solar cell. , 2011, Angewandte Chemie.

[5]  Zhongjie Huang,et al.  Linker effect in organic donor–acceptor dyes for p-type NiO dye sensitized solar cells , 2011 .

[6]  G. Boschloo,et al.  Synthesis, photophysical and photovoltaic investigations of acceptor-functionalized perylene monoimide dyes for nickel oxide p-type dye-sensitized solar cells , 2011 .

[7]  M. Boujtita,et al.  Ruthenium polypyridine complexes as sensitizers in NiO based p-type dye-sensitized solar cells: Effects of the anchoring groups , 2011 .

[8]  Paolo G. Bomben,et al.  Strategies for Optimizing the Performance of Cyclometalated Ruthenium Sensitizers for Dye-Sensitized Solar Cells , 2011 .

[9]  J. McCusker,et al.  Synthesis and spectroscopic characterization of CN-substituted bipyridyl complexes of Ru(II). , 2011, Inorganic chemistry.

[10]  C. Su,et al.  Highly efficient N-heterocyclic carbene/pyridine-based ruthenium sensitizers: complexes for dye-sensitized solar cells. , 2010, Angewandte Chemie.

[11]  G. Koten,et al.  A Redox Asymmetric, Cyclometalated Ruthenium Dimer: Toward Upconversion Dyes in Dye-Sensitized TiO2 Solar Cells , 2010 .

[12]  E. Blart,et al.  New photovoltaic devices based on the sensitization of p-type semiconductors: challenges and opportunities. , 2010, Accounts of chemical research.

[13]  Anders Hagfeldt,et al.  Double‐Layered NiO Photocathodes for p‐Type DSSCs with Record IPCE , 2010, Advanced materials.

[14]  T. Brinck,et al.  Synthesis and Mechanistic Studies of Organic Chromophores with Different Energy Levels for p-Type Dye-Sensitized Solar Cells , 2010 .

[15]  U. Bach,et al.  Highly efficient photocathodes for dye-sensitized tandem solar cells. , 2010, Nature materials.

[16]  Yun Chi,et al.  Neutral, panchromatic Ru(II) terpyridine sensitizers bearing pyridine pyrazolate chelates with superior DSSC performance. , 2009, Chemical communications.

[17]  Paolo G. Bomben,et al.  On the viability of cyclometalated Ru(II) complexes for light-harvesting applications. , 2009, Inorganic chemistry.

[18]  Anders Hagfeldt,et al.  High Incident Photon‐to‐Current Conversion Efficiency of p‐Type Dye‐Sensitized Solar Cells Based on NiO and Organic Chromophores , 2009 .

[19]  Junji Kido,et al.  Structure–Property Relationship of Pyridine‐Containing Triphenyl Benzene Electron‐Transport Materials for Highly Efficient Blue Phosphorescent OLEDs , 2009 .

[20]  Ivano Tavernelli,et al.  New paradigm in molecular engineering of sensitizers for solar cell applications. , 2009, Journal of the American Chemical Society.

[21]  Duncan M. Tooke,et al.  Consequences of N,C,N'- and C,N,N'-coordination modes on electronic and photophysical properties of cyclometalated aryl ruthenium(II) complexes. , 2009, Inorganic chemistry.

[22]  Eiji Suzuki,et al.  Syntheses of NiO nanoporous films using nonionic triblock co-polymer templates and their application to photo-cathodes of p-type dye-sensitized solar cells , 2008 .

[23]  Tomas Edvinsson,et al.  Design of an organic chromophore for p-type dye-sensitized solar cells. , 2008, Journal of the American Chemical Society.

[24]  G. Boschloo,et al.  Coumarin 343-NiO Films as Nanostructured Photocathodes in Dye-Sensitized Solar Cells: Ultrafast Electron Transfer, Effect of the I3-/I- Redox Couple and Mechanism of Photocurrent Generation , 2008 .

[25]  Tomas Edvinsson,et al.  Improved Photon-to-Current Conversion Efficiency with a Nanoporous p-Type NiO Electrode by the Use of a Sensitizer-Acceptor Dyad , 2008 .

[26]  A. Spek,et al.  Cyclometalated ruthenium complexes for sensitizing nanocrystalline TiO2 solar cells. , 2007, Chemical communications.

[27]  E. Galoppini,et al.  Ru(II)-Bpy Complexes Bound to Nanocrystalline TiO2 Films through Phenyleneethynylene (OPE) Linkers: Effect of the Linkers Length on Electron Injection Rates , 2007 .

[28]  Giacomo Bergamini,et al.  Photochemistry and Photophysics of Coordination Compounds: Ruthenium , 2007 .

[29]  B. Albinsson,et al.  Triplet excitation energy transfer in porphyrin-based donor--bridge--acceptor systems with conjugated bridges of varying length: an experimental and DFT study. , 2006, The journal of physical chemistry. B.

[30]  Anders Hagfeldt,et al.  Sensitized hole injection of phosphorus porphyrin into NiO: toward new photovoltaic devices. , 2005, The journal of physical chemistry. B.

[31]  Anders Hagfeldt,et al.  Photoinduced ultrafast dynamics of coumarin 343 sensitized p-type-nanostructured NiO films. , 2005, The journal of physical chemistry. B.

[32]  C. Yu,et al.  Interfacial electron-transfer kinetics of ferrocene through oligophenyleneethynylene bridges attached to gold electrodes as constituents of self-assembled monolayers: observation of a nonmonotonic distance dependence. , 2004, Journal of the American Chemical Society.

[33]  J. McCusker.  Femtosecond absorption spectroscopy of transition metal charge-transfer complexes. , 2003, Accounts of chemical research.

[34]  N. Lewis,et al.  Effects of bridging ligands on the current-potential behavior and interfacial kinetics of ruthenium-sensitized nanocrystalline TiO2 photoelectrodes , 2003 .

[35]  Nathan S. Lewis,et al.  Electron Transfer Dynamics in Nanocrystalline Titanium Dioxide Solar Cells Sensitized with Ruthenium or Osmium Polypyridyl Complexes , 2001 .

[36]  J. Hupp,et al.  In Search of the Inverted Region: Chromophore-Based Driving Force Dependence of Interfacial Electron Transfer Reactivity at the Nanocrystalline Titanium Dioxide Semiconductor/Solution Interface† , 2000 .

[37]  Jianjun He,et al.  Dye-Sensitized Nanostructured p-Type Nickel Oxide Film as a Photocathode for a Solar Cell , 1999 .

[38]  C. Kelly,et al.  Cation-Controlled Interfacial Charge Injection in Sensitized Nanocrystalline TiO2 , 1999 .

[39]  John B. Asbury,et al.  Femtosecond IR Study of Excited-State Relaxation and Electron-Injection Dynamics of Ru(dcbpy)2(NCS)2 in Solution and on Nanocrystalline TiO2 and Al2O3 Thin Films , 1999 .

[40]  G. Calogero,et al.  A cyclometallated ruthenium(ii) complex with a sterically hinderedligand displaying a long-lived MLCT excited state , 1997 .

[41]  M. Grätzel,et al.  A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films , 1991, Nature.

[42]  Y. Gondo,et al.  Resonance Raman spectrum of the 4, 4′‐bipyridine radical anion , 1986 .