Correlating Charge Transfer Dynamics with Interfacial Trap States in High-Efficiency Organic Solar Cells.

The charge transfer between the donor and acceptor determines the photogenerated carrier density in organic solar cells. However, a fundamental understanding regarding the charge transfer at donor/acceptor interfaces with high-density traps has not been fully addressed. Herein, a general correlation between trap densities and charge transfer dynamics is established by adopting a series of high-efficiency organic photovoltaic blends. It is found that the electron transfer rates are reduced with increased trap densities, while the hole transfer rates are independent of trap states. The local charges captured by traps can induce potential barrier formation around recombination centers, leading to the suppression of electron transfer. For the hole transfer process, the thermal energy provides a sufficient driving force, which ensures an efficient transfer rate. As a result, a 17.18% efficiency is obtained for PM6:BTP-eC9-based devices with the lowest interfacial trap densities. This work highlights the importance of interfacial traps in charge transfer processes and proposes an underlying insight into the charge transfer mechanism at nonideal interfaces in organic heterostructures.

Scalable synthesis of urchin- and flowerlike hierarchical NiO microspheres and their electrochemical property for lithium storage.

A nickel salt-urea-H2O ternary system has been developed for the large-scale synthesis of hierarchical α-Ni(OH)2 microspheres, the solid precursor for the subsequent topotactic transition to NiO upon calcination. In this facile synthetic system, hierarchical structure is self-assembled under the cooperative direction of urea and anions in nickel salts. Thus, simply tuning the Ni salts leads to the selective construction of urchin and flowerlike hierarchical α-Ni(OH)2 and NiO microspheres consisting of radial 1D nanowires and 2D nanoplates, respectively. The obtained NiO microspheres possessing accessible nanopores, excellent structural stability and large surface area up to 130 m(2)/g show promising electrochemical performance in anodic lithium storage for lithium-ion battery.

Unsymmetric platinum(II) bis(aryleneethynylene) complexes as photosensitizers for dye-sensitized solar cells.

Four new unsymmetric platinum(II) bis(aryleneethynylene) derivatives have been designed and synthesized, which showed good light-harvesting capabilities for application as photosensitizers in dye-sensitized solar cells (DSSCs). The absorption, electrochemical, time-dependent density functional theory (TD-DFT), impedance spectroscopic, and photovoltaic properties of these platinum(II)-based sensitizers have been fully characterized. The optical and TD-DFT studies show that the incorporation of a strongly electron-donating group significantly enhances the absorption abilities of the complexes. The maximum absorption wavelength of these four organometallic dyes can be tuned by various structural modifications of the triphenylamine and/or thiophene electron donor, improving the light absorption range up to 650 nm. The photovoltaic performance of these dyes as photosensitizers in mesoporous TiO(2) solar cells was investigated, and a power conversion efficiency as high as 1.57% was achieved, with an open-circuit voltage of 0.59 V, short-circuit current density of 3.63 mA cm(-2), and fill factor of 0.73 under simulated AM 1.5G solar illumination.

Platinum-based poly(aryleneethynylene) polymers containing thiazolothiazole group with high hole mobilities for field-effect transistor applications.

Two solution-processable platinum-acetylide polymers functionalized with the electron-deficient thiazolothiazole spacer are synthesized and show absorption features spanning from 320 to 600 nm and optical bandgaps of 2.15 and 2.05 eV. The spin-coated polymer thin films of both materials exhibit p-channel field-effect charge transport characteristics with impressive peak field-effect charge-carrier mobilities of (2.1-2.8) × 10(-2) cm(2) V(-1) s(-1) and on/off ratios of (0.8-1.0) × 10(5) for the holes. The high hole mobility value reported for one of the polymers is among the highest reported for metallopolyynes to date. It is also shown that the hole mobility can be notably increased by extending the conjugation length of the chain from the monothienyl to the bithienyl segment on each side of the thiazolothiazole ring.

Very-low-bandgap metallopolyynes of platinum with a cyclopentadithiophenone ring for organic solar cells absorbing down to the near-infrared spectral region.

Two solution-processable metallopolyynes of platinum functionalized with the electron-deficient 4H-cyclopenta[2,1-b:3,4-b']dithiophen-4-one spacer and their model molecular complexes were synthesized and developed for the applications of polymer solar cells. These metallated polymers possess extremely low bandgaps of 1.44-1.53 eV which extend toward the near-infrared (NIR) range of the solar spectrum, and represent the lowest optical bandgap yet reported for platinum(II) metallopolyynes to date. The structural flexibility, processibility, and good photovoltaic performance make cyclopentadithiophenone-containing polymers prominent candidates for NIR photovoltaic applications.

Polymer solar cells based on very narrow-bandgap polyplatinynes with photocurrents extended into the near-infrared region.

The synthesis, characterization and photophysics of some solution-processable intensely coloured polyplatinynes functionalized with the thienopyrazine-thiophene hybrid spacer and their model molecular complexes are described. These metallated polymers possess extremely low bandgaps of 1.47-1.50 eV, which extend towards the near-infrared (NIR) range of the solar spectrum, and represent the lowest optical bandgaps ever reported for metallopolyynes in the literature. Both polymers can be used to fabricate efficient solar cells with power conversion efficiencies (PCEs) of up to 0.63% under air mass (AM1.5) simulated solar illumination, and the possibility of covering the 600-900 nm solar-radiation range to harvest photocurrent has been demonstrated. The influence of the thienyl core as well as its substituent group, on the optical and photovoltaic behavior of these metallopolymers was investigated in detail. The power dependencies of the solar cell parameters (including the short-circuit current density, open-circuit voltage, fill-factor and PCE) were also studied. The present work offers an attractive avenue towards conjugated materials with broad solar absorptions and demonstrates the potential of metallopolyynes for both visible and NIR light power generation.

Tuning the absorption, charge transport properties, and solar cell efficiency with the number of thienyl rings in platinum-containing poly(aryleneethynylene)s.

The synthesis, characterization, and photophysics of a series of solution-processable and strongly visible-light absorbing platinum(II) polyynes containing bithiazole-oligo(thienyl) rings were presented. Tuning the polymer solar cell efficiency, as well as optical and charge transport properties, in soluble, low-band gap PtII-based conjugated poly(heteroaryleneethynylene)s using the number of oligothienyl rings is described. These materials are highly soluble in polar organic solvents due to the presence of solubilizing bithiazole moieties and show strong absorptions in the solar spectra, rendering them excellent candidates for bulk heterojunction polymer solar cells. Their photovoltaic responses and power conversion efficiencies (PCEs) depend to a large extent on the number of thienyl rings along the main chain, and some of them can be used to fabricate highly efficient solar cells with PCEs of up to 2.7% and a peak external quantum efficiency to 83% under AM1.5 simulated solar illumination, which is comparable to that of poly(3-hexylthiophene)-based devices fabricated without additional processing (annealing or TiO(x) layer). The influence of the number of thienyl rings and the metal group on the performance parameters and optimization of solar cell efficiency was evaluated and discussed in detail. At the same blend ratio of 1:4, the light-harvesting ability and PCE increase sharply as the thienyl chain length increases. The present work provides an attractive approach to developing conjugated metallopolymers offering broad solar absorptions and tunable solar cell efficiency and demonstrates the potential of metalated conjugated polymers for efficient power generation.

Metallated conjugated polymers as a new avenue towards high-efficiency polymer solar cells.

Bulk heterojunction solar cells have been extensively studied owing to their great potential for cost-effective photovoltaic devices. Although recent advances resulted in the fabrication of poly(3-hexylthiophene) (P3HT)/fullerene derivative based solar cells with efficiencies in the range 4.4-5.0%, theoretical calculations predict that the development of novel donor materials with a lower bandgap is required to exceed the power-conversion efficiency of 10%. However, all of the lower bandgap polymers developed so far have failed to reach the efficiency of P3HT-based cells. To address this issue, we synthesized a soluble, intensely coloured platinum metallopolyyne with a low bandgap of 1.85 eV. The solar cells, containing metallopolyyne/fullerene derivative blends as the photoactive material, showed a power-conversion efficiency with an average of 4.1%, without annealing or the use of spacer layers needed to achieve comparable efficiency with P3HT. This clearly demonstrates the potential of metallated conjugated polymers for efficient photovoltaic devices.