A high surface area pn-heterojunction between TiO 2 and an organic p-type charge transport material (spiro-OMeTAD) was sensitized to visible light using lead sulfide (PbS) quantum dots. PbS quantum dots were formed in situ on a nanocrystalline TiO 2 electrode using chemical bath deposition techniques. 1 The organic hole conductor was applied from solution to form the sensitized heterojunction. The structure of the quantum dots was analyzed using HRTEM technique. Ultrafast laser photolysis experiments suggested the initial charge separation to proceed in the subpicosecond time range. Transient absorption laser spectroscopy revealed that interfacial charge recombination of the initially formed charge carriers is much faster than in comparable dye-sensitized systems. 2,3 The sensitized heterojunction showed incident photon-to-electron conversion efficiencies (IPCE) of up to 45% and energy conversion efficiencies under simulated sunlight AM1.5 (10 mW/cm2) of 0.49%.
The performance of solid-state dye-sensitized solar cells based on spiro-MeOTAD was considerably improved by controlling charge recombination across the interface of the heterojunction. This was achieved by blending the hole conductor matrix with a combination of 4-tert-butylpyridine (tBP) and Li[CF3SO2]2N. Open circuit voltages Uoc over 900 mV and short circuit currents Isc up to 5.1 mA were obtained, yielding an overall efficiency of 2.56% at AM1.5 illumination. These values have been fully confirmed at the National Renewable Energy Laboratories for a device with an active area of 1.07 cm2, signifying a dramatic improvement compared to previously reported values for a similar device.
Solid-state dye-sensitized solar cells employing spiro-MeOTAD [2,2′7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene] as a hole transport phase were studied by intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS) over a wide range of illumination intensity. The IMPS and IMVS responses provide information about charge transport and electronhole recombination, respectively. For the range of light intensities investigated, the dynamic photocurrent response appears to be limited by the transport of electrons in the nanocrystalline TiO 2 film rather than by the transport of holes in the spiro-MeOTAD. The diffusion length of electrons in the TiO 2 was found to be 4.4 × 10 -4 cm. This value was almost independent of light intensity as a consequence of the fact that the electron diffusion coefficient and the rate constant for electron-hole recombination both increase in the same way with light intensity (proportional to I 0 0.64 ).
The photovoltaic performance of solid-state dye-sensitized solar cells based on 2,2′7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9′-spiro-bifluorene has been improved to 3.2% overall conversion efficiency under air mass (AM) 1.5 illumination by performing the dye adsorption in the presence of silver ions in the dye solution. The enhancement in overall device efficiency is a result of increased open circuit potential and short circuit current. Different spectroscopic methods, such as x-ray photoelectron, Fourier-transform infrared and UV-visible spectroscopy have been employed to scrutinize the impact of the silver on the dye-sensitized device. From spectroscopic evidence it is inferred that the silver is mainly binding to the sensitizer via the amphidentate thiocyanate, allowing the formation of ligand-bridged dye complexes.
We compared reading speed with two fonts, Dutch (serif) and Swiss (sans serif). Text was displayed on a computer monitor, white letters on black, with the RSVP method. Luminance of the letters was either 146.0 or 0.146 cd m-2. Lower-case x-height of the fonts was approximately 5.5 times as large as letter acuity. At the high luminance, there was no difference between reading rates. There was a significant advantage for the Swiss font at the low luminance. The acuity reserve for Swiss was higher than for Dutch at the low luminance, which may account for the difference in reading speeds.
The terminal oxidase content of Bacillus firmus OF4, a facultative alkaliphile that grows well over the pH range of 7.5 to 10.5, was studied by difference spectroscopy. Evidence was found for three terminal oxidases under different growth conditions. The growth pH and the stage of growth profoundly affected the expression of one of the oxidases, cytochrome d. The other two oxidases, cytochrome caa3 and cytochrome o, were expressed under all growth conditions tested, although the levels of both, especially cytochrome caa3, were higher at more alkaline pH (P.G. Quirk, A.A. Guffanti, R.J. Plass, S. Clejan, and T.A. Krulwich, Biochim. Biophys. Acta, in press). These latter oxidases were identified in everted membrane vesicles by reduced-versus-oxidized difference spectra (absorption maximum at 600 nm for cytochrome caa3) and CO-reduced-versus-reduced difference spectra (absorption maxima at 574 and 414 nm for cytochrome o). All three terminal oxidases were solubilized from everted membranes and partially purified. The difference spectra of the solubilized, partially purified cytochrome caa3 and cytochrome o complexes were consistent with these assignments. Cytochrome d, which has not been identified in a Bacillus species before, was tentatively assigned on the basis of its absorption maxima at 622 and 630 nm in reduced-versus-oxidized and CO-reduced-versus-reduced difference spectra, respectively, resembling the maxima exhibited by the complex found in Escherichia coli. The B. firmus OF4 cytochrome d was reducible by NADH but not by ascorbate-N,N,N',N'-tetramethyl-p-phenylenediamine in everted membrane vesicles. Cytochrome d was expressed under two conditions: in cells growing exponentially at pH 7.5 (but not at pH 10.5) and in cells stationary phase at either pH 7.5 or 10.5. Protein immunoblots with antibodies against subunit I of the E. coli cytochrome d complex reacted only with membrane vesicles that contained spectrally identifiable cytochrome d. Additional evidence that this B. firmus OF4 cytochrome is related to the E. coli complex was obtained with a solubilized, partially purified fraction of cytochrome d that also reacted with antibodies against the subunits of the E. coli cytochrome d.
The performance of solid-state dye-sensitized solar cells based on spiro-MeOTAD (2,2'7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene) was considerably improved by decreasing charge recombination across the interface of the heterojunction. This was achieved by blending the hole conductor matrix with a combination of 4-tert-butylpyridine (tBP) and Li[CF3SO2]2N. Open circuit voltages (Uoc) over 900mV and short circuit currents (Isc) up to 5.1 mA were obtained, yielding an overall efficiency of 2.56 % at AM1.5 illumination. Further improvement of the device performance was observed when conducting stripes of silver were deposited onto the devices as charge collector. The beneficial effect however could be assigned to the contamination of the dye-sensitized TiO2 film with silver during the dyeing process.
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