Dye-sensitized solar cells (DSSCs) made from oriented, one-dimensional semiconductor nanostructures such as nanorods, nanowires, and nanotubes are receiving attention because direct connection of the point of photogeneration with the collection electrode using such structures may improve the cell performance. Specifically, oriented single-crystalline TiO(2) nanorods or nanowires on a transparent conductive substrate would be most desirable, but achieving these structures has been limited by the availability of synthetic techniques. In this study, a facile, hydrothermal method was developed for the first time to grow oriented, single-crystalline rutile TiO(2) nanorod films on transparent conductive fluorine-doped tin oxide (FTO) substrates. The diameter, length, and density of the nanorods could be varied by changing the growth parameters, such as growth time, growth temperature, initial reactant concentration, acidity, and additives. The epitaxial relation between the FTO substrate and rutile TiO(2) with a small lattice mismatch plays a key role in driving the nucleation and growth of the rutile TiO(2) nanorods on FTO. With TiCl(4)-treatment, a light-to-electricity conversion efficiency of 3% could be achieved by using 4 mum-long TiO(2) nanorod films as the photoanode in a DSSC.
In typical semiconductor solar cells, photons with energies above the semiconductor bandgap generate hot charge carriers that quickly cool before all of their energy can be captured, a process that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated. We used time-resolved optical second harmonic generation to observe hot-electron transfer from colloidal lead selenide (PbSe) nanocrystals to a titanium dioxide (TiO2) electron acceptor. With appropriate chemical treatment of the nanocrystal surface, this transfer occurred much faster than expected. Moreover, the electric field resulting from sub-50-femtosecond charge separation across the PbSe-TiO2 interface excited coherent vibrations of the TiO2 surface atoms, whose motions could be followed in real time.
We combine CdSe semiconductor nanocrystals (or quantum dots) and single-crystal ZnO nanowires to demonstrate a new type of quantum-dot-sensitized solar cell. An array of ZnO nanowires was grown vertically from a fluorine-doped tin oxide conducting substrate. CdSe quantum dots, capped with mercaptopropionic acid, were attached to the surface of the nanowires. When illuminated with visible light, the excited CdSe quantum dots injected electrons across the quantum dot-nanowire interface. The morphology of the nanowires then provided the photoinjected electrons with a direct electrical pathway to the photoanode. With a liquid electrolyte as the hole transport medium, quantum-dot-sensitized nanowire solar cells exhibited short-circuit currents ranging from 1 to 2 mA/cm2 and open-circuit voltages of 0.5-0.6 V when illuminated with 100 mW/cm2 simulated AM1.5 spectrum. Internal quantum efficiencies as high as 50-60% were also obtained.
Surfaces covered with polyethylene glycol (PEG; HO-(CH(2)-CH(2)-O)(n)-H) have been shown to be biocompatible because PEG's properties yield nonimmunogenicity, nonantigenicity, and protein rejection. To produce a biocompatible surface coating, we have developed a method for grafting PEG onto activated silica films. We first deposited an amorphous silica film by plasma-enhanced chemical vapor deposition from SiH(4) and O(2) gases, which provided the flexibility to coat diverse materials with different chemistries and shapes. The silica films were activated by exposure to water plasma, increasing the number of silanol groups (Si-OH) on their surface. The surface silanol groups were then chemically reacted with the hydroxyl end of PEG to form an ester bond, Si-O-C, and to cover the surface with PEG. The surface reactions were monitored using attenuated total reflection Fourier transform infrared spectroscopy. The vibrational absorption bands of the C-O and -CH(2) bonds increased with time and saturated, indicating that PEG was adsorbed to saturation coverage on the surface. Simultaneously, the Si-OH absorption band decreased, showing that the surface silanols reacted with PEG and were depleted. The PEG-covered surfaces were physically characterized by atomic force microscopy, Auger electron spectroscopy, ellipsometry, and contact angle measurements. These characterization techniques provided additional evidence for the existence of chemically bonded PEG on the surfaces. Efficacy of protein rejection on PEG-covered surfaces was studied through measurements of the fluorescence intensity of Texas red-labeled bovine serum albumin brought in contact with such surfaces in solution. Significantly less protein adsorption was observed on surfaces covered with PEG compared to uncovered surfaces.
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