Eray S. Aydil

Growth of Oriented Single-Crystalline Rutile TiO2 Nanorods on Transparent Conducting Substrates for Dye-Sensitized Solar Cells

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.

Nanowire-based dye-sensitized solar cells

We describe the design and performance of a ZnO nanowire-based dye-sensitized solar cell. ZnO nanowires with a branched structure were employed as the wide-band-gap semiconductor to construct dye-sensitized solar cells which exhibit energy conversion efficiencies of 0.5% with internal quantum efficiencies of 70%. The nanowires provide a direct conduction path for electrons between the point of photogeneration and the conducting substrate and may offer improved electron transport compared to films of sintered nanoparticles. The devices have light harvesting efficiencies under 10%, indicating that current densities and efficiencies can be improved by an order of magnitude by increasing the nanowire surface area.

Hot-electron transfer from semiconductor nanocrystals.

Hot on the Trail Solar cells essentially operate by absorbing light, which needs to be above a certain energy threshold. The absorbed light then liberates charges within the solar cell to carry electrical current. Unfortunately, the liberated charges behave the same way whether they are excited right at the threshold (e.g., by visible light) or well above it (by ultraviolet light), which leads to any excess energy being dissipated as waste heat. Tisdale et al. (p. 1543) have documented a potential first step toward resolving this inefficiency. Specifically, electrons excited by light absorption in lead selenide nanocrystals were able to migrate to an adjacent titanium dioxide surface without releasing their excess energy to heat. The next step will be to devise a means of harnessing the stored energy in a circuit. Extraction of highly excited electrons formed in a light-absorbing material may make solar cells more efficient. 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.

Polyethylene glycol-coated biocompatible surfaces.

Surfaces covered with polyethylene glycol (PEG; HO-(CH(2)-CH(2)-O)(n)-H) have been shown to be biocompatible because PEGs 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.

Synthesis and characterization of ZnO nanowires and their integration into dye-sensitized solar cells

ZnO nanowires, grown on transparent conducting oxide substrates from aqueous solutions of methenamine and Zn(NO3)2, were integrated as the wide band gap semiconductor into dye-sensitized solar cells. ZnO nanowires and their growth mechanisms were studied using electron microscopy, x-ray diffraction and photoluminescence measurements. The solution growth method forms dense arrays of long nanowires oriented normal to the substrate surface because nanowires growing at off-normal angles are prevented from growing further when they run into neighbouring wires. Dye-sensitized solar cells with ZnO nanowires were assembled and characterized using optical and electrical measurements. Short circuit current densities of 1.3?mA?cm?2, and overall power conversion efficiencies of 0.3% were achieved with 8??m long nanowires. Photocurrent and efficiency increase with increasing nanowire length and improved light harvesting. Low surface area and a shunt that appears under light illumination limit the solar cell performance. Internal quantum efficiencies were similar for nanowires of all lengths, indicating that electron transport is not limited by the nanowire dimensions for aspect ratios less than 70.

Mechanism of hydrogen-induced crystallization of amorphous silicon

Hydrogenated amorphous and nanocrystalline silicon films manufactured by plasma deposition techniques are used widely in electronic and optoelectronic devices. The crystalline fraction and grain size of these films determines electronic and optical properties; the nanocrystal nucleation mechanism, which dictates the final film structure, is governed by the interactions between the hydrogen atoms of the plasma and the solid silicon matrix. Fundamental understanding of these interactions is important for optimizing the film structure and properties. Here we report the mechanism of hydrogen-induced crystallization of hydrogenated amorphous silicon films during post-deposition treatment with an H2 (or D2) plasma. Using molecular-dynamics simulations and infrared spectroscopy, we show that crystallization is mediated by the insertion of H atoms into strained Si–Si bonds as the atoms diffuse through the film. This chemically driven mechanism may be operative in other covalently bonded materials, where the presence of hydrogen leads to disorder-to-order transitions.

Solar Cells Based on Junctions between Colloidal PbSe Nanocrystals and Thin ZnO Films

We report a new type of excitonic solar cell based on planar heterojunctions between PbSe semiconductor nanocrystals and thin ZnO films. These solar cells generate large photocurrents and higher photovoltages compared to Schottky cells assembled with similar nanocrystal films. When illuminated with 100 mW/cm(2) simulated AM1.5 spectrum, these solar cells exhibit short-circuit currents between 12 and 15 mA/cm(2), open-circuit voltages up to 0.45 V, and a power conversion efficiency of 1.6%. The photovoltage depends on the size of the nanocrystals, increasing linearly with their effective band gap energy.

Photovoltaic manufacturing: Present status, future prospects, and research needs

In May 2010 the United States National Science Foundation sponsored a two-day workshop to review the state-of-the-art and research challenges in photovoltaic (PV) manufacturing. This article summarizes the major conclusions and outcomes from this workshop, which was focused on identifying the science that needs to be done to help accelerate PV manufacturing. A significant portion of the article focuses on assessing the current status of and future opportunities in the major PV manufacturing technologies. These are solar cells based on crystalline silicon (c-Si), thin films of cadmium telluride (CdTe), thin films of copper indium gallium diselenide, and thin films of hydrogenated amorphous and nanocrystalline silicon. Current trends indicate that the cost per watt of c-Si and CdTe solar cells are being reduced to levels beyond the constraints commonly associated with these technologies. With a focus on TW/yr production capacity, the issue of material availability is discussed along with the emerging technologies of dye-sensitized solar cells and organic photovoltaics that are potentially less constrained by elemental abundance. Lastly, recommendations are made for research investment, with an emphasis on those areas that are expected to have cross-cutting impact.

Imaging and phase identification of Cu2ZnSnS4 thin films using confocal Raman spectroscopy

Copper zinc tin sulfide (Cu2ZnSnS4 or CZTS) is a potential candidate for next generation thin film solar cells because it contains abundant and nontoxic elements and exhibits high light absorption. Thin films of CZTS are typically synthesized by sulfidizing a stack of zinc, copper, and tin films. In addition to CZTS, a variety of binary and ternary metal sulfides can form and distinguishing among phases with similar crystal structure can be difficult. Herein, the authors show that confocal Raman spectroscopy and imaging can distinguish between CZTS and the other binary and ternary sulfides. Specifically, Raman spectroscopy was used to detect and distinguish between CZTS (338 cm−1), Cu2SnS3 (298 cm−1), and Cu4SnS4 (318 cm−1) phases through their characteristic scattering peaks. Confocal Raman spectroscopy was then used to image the distribution of coexisting phases and is demonstrated to be a useful tool for examining the heterogeneity of CZTS films. The authors show that, during sulfidation of a zinc/copp...

Doping high-surface-area mesoporous TiO2 microspheres with carbonate for visible light hydrogen production

First-principles calculations suggest that doping TiO2 with carbonate can effectively reduce the bandgap of TiO2, thus making TiO2 photoactive in the visible region of the solar spectrum. Herein we report a simple “one-pot” solvothermal method for synthesizing brown carbonate-doped TiO2 microspheres. The diameter of the TiO2 microsphere is tunable from ∼0.5 to 4 μm with the nanopore size in the range of 3–11 nm. Remarkably, the specific surface area of these nanoporous anatase TiO2 microspheres can be as high as 500 m2 g−1. A controllable amount of carbonate could be incorporated into TiO2 through low-temperature post-synthesis annealing, which extends the light absorption of the TiO2 microspheres from the ultraviolet to the visible region of the solar spectrum. Very high photocatalytic activity of these carbonate-doped TiO2 microspheres was demonstrated in the visible light region for both photocatalytic production of hydrogen from water and degradation of methyl orange. Under 3 Sun visible-light illumination (λ ≥ 400 nm), the carbonate-doped TiO2 microspheres can produce 0.2 mmol H2 h−1 g−1 of photocatalyst, which is significantly higher than those from various other TiO2 photocatalysts.