title: Molecular engineering of organic sensitizers for solar cell applications.
abstract: Novel organic sensitizers comprising donor, electron-conducting, and anchoring groups were engineered at molecular level and synthesized. The functionalized unsymmetrical organic sensitizers 3-{5-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-thiophene-2-yl}-2-cyano-acrylic acid (JK-1) and 3-{5'-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-2,2'-bisthiophene-5-yl}-2-cyano-acrylic acid (JK-2), upon anchoring onto TiO2 film, exhibit unprecedented incident photon to current conversion efficiency of 91%. The photovoltaic data using an electrolyte having composition of 0.6 M M-methyl-N-butyl imidiazolium iodide, 0.04 M iodine, 0.025 M LiI, 0.05 M guanidinium thiocyanate, and 0.28 M tert-butylpyridine in a 15/85 (v/v) mixture of valeronitrile and acetonitrile revealed a short circuit photocurrent density of 14.0 +/- 0.2 mA/cm2, an open circuit voltage of 753 +/- 10 mV, and a fill factor of 0.76 +/- 0.02, corresponding to an overall conversion efficiency of 8.01% under standard AM 1.5 sunlight. DFT/TDDFT calculations have been performed on the two organic sensitizers to gain insight into their structural, electronic, and optical properties. Our results show that the cyanoacrylic acid groups are essentially coplanar with respect to the thiophene units, reflecting the strong conjugation across the thiophene-cyanoacrylic groups. Molecular orbitals analysis confirmed the experimental assignment of redox potentials, while TDDFT calculations allowed assignment of the visible absorption bands.
authors.affiliation: Department of Chemistry, Korea University, Jochiwon, Chungnam 339-700, Korea.
authors.forename: Sanghoon
authors.initials: S
authors.lastname: Kim
authors.forename: Jae Kwan
authors.initials: JK
authors.lastname: Lee
authors.forename: Sang Ook
authors.initials: SO
authors.lastname: Kang
authors.forename: Jaejung
authors.initials: J
authors.lastname: Ko
authors.forename: J-H
authors.initials: JH
authors.lastname: Yum
authors.forename: Simona
authors.initials: S
authors.lastname: Fantacci
authors.forename: Filippo
authors.initials: F
authors.lastname: De Angelis
authors.forename: D
authors.initials: D
authors.lastname: Di Censo
authors.forename: Md K
authors.initials: MK
authors.lastname: Nazeeruddin
authors.forename: Michael
authors.initials: M
authors.lastname: Grätzel