AVS2008 Session EN+EM+NS+P+A+T+V-ThM: Energy: Tools and Approaches

Thursday, October 23, 2008 8:00 AM in Room 203

Thursday Morning

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8:00 AM	Invited	EN+EM+NS+P+A+T+V-ThM-1 Nano-Structured and Micro-Structured Semiconductors for Better Efficiency of Solar Cells C.-F. Lin, J.-S. Huang, S.-C. Shiu, J.-J. Chao, C.-Y. Hsiao, K.-H. Tsai (National Taiwan University) The foreseeable depletion of fossil fuel and the global warming caused by the carbon dioxide had led to the increasing attention of alternative renewable energy, especially photovoltaic. Therefore, crystalline Si-PV devices are quickly spreading. Unfortunately, the large consumption of Si materials hinders their vast applications. Many efforts have been switched to developing thin-film PV devices. In this talk, we will discuss the use of nano-structured and micro-structured semiconductors that enable the fabrication of thin-film solar cells with improved efficiency. Several types of such thin-film solar cells will be discussed, including the organic-semiconductor-nanowire composite film, organic-semiconductor micro-structure composite film, nano-wire semiconductor thin film, and micro-structured semiconductor thin film. In the thin-film solar cells using organic-semiconductor-nanorod composite film, different types of semiconductor nanowires such as ZnO, Si, and GaAs nanowires are used to replace the accepter-type organics for two purposes: increasing the electron mobility and assisting the formation of nano-morphology for better inter link between the donor organics and acceptor materials. The fabrication procedures of those nanowires as well as the formation of the organic-semiconductor-nanowire composite film with controlled nano-morphology will be presented. For the other solar cells using nano-structured and micro-structured semiconductors, we will particularly describe the technique of nanowire/micro-structure transfer. In our approach, the nanowires and micro-structures are made from the bulk semiconductors or epitaxial semiconductors, so they will have much better crystal quality than the usual thin-film materials. In addition, after nanowires and micro-structures are transferred to other transparent substrates, the original wafer can be reused, so the material cost can be lowered considerably. In addition, it offers the advantages of the bending flexibility, not being limited by the brittle property of semiconductors. Furthermore, in comparison with current III-V tandem solar cells taken by monolithic approach, which requires lattice match and current balance, our approach enables mechanically stacking. Thus each cell could be designed individually to match the entire solar spectrum for optimal solar usage. Therefore, such new-type thin-film solar cells are expected to be potentially efficient and low cost.
8:40 AM		EN+EM+NS+P+A+T+V-ThM-3 Endohedral Metallofullerenes as Improved Acceptor Materials for Organic Solar Cells M. Drees (Luna Innovations Incorporated); R. Ross (Georgetown University); C. Cardona (Luna Innovations Incorporated); E. Van Keuren (Georgetown University); D. Guldi (Friedrich-Alexander-Universitat Erlangen-Nurnberg, Germany); B.C. Holloway (Luna Innovations Incorporated) Cost factors in inorganic solar cells have opened up a new path to less expensive manufacturing techniques using bulk heterojunction polymer/fullerene based solar cells. Using empty cage fullerene derivatives as the acceptor material, state-of-the-art organic photovoltaics currently display ~5% overall conversion efficiency. One of the main factors limiting the efficiency in organic solar cells is the low open circuit voltage. The open circuit voltage is governed by the molecular orbitals of the donor and acceptor material; therefore better matching of the orbitals will lead to improved voltages. Here we present a novel acceptor material based on Trimetasphere® carbon nanomaterials (TMS). Trimetaspheres® are endohedral metallofullerenes that consist of a trimetal nitride cluster enclosed in a C80 cage. First-generation Trimetasphere® carbon nanomaterial derivatives have been synthesized and show behavior consistent with C60 but with improved molecular orbitals. Electrochemical data suggests a maximum voltage increase of up to 280 mV over C60-PCBM-based devices and photophysical characterization of shows efficient and stable charge separation. Initial bulk-heterojunction devices have been synthesized with open circuit voltages that are 280 mV higher than reference devices using C60-PCBM and conversion efficiencies exceeding 3.1%.
9:00 AM		EN+EM+NS+P+A+T+V-ThM-4 Morphology Study of Vacuum-Deposited Pentacene:C60 Mixed Thin Films for Photovoltaic Applications J. Xue, Y. Zheng, J.D. Myers, J. Ouyang (University of Florida) The efficiency of organic photovoltaic (PV) devices has gained steady increase in past 20 years, showing a potential to provide clean and low-cost electrical energy in the near future. Bulk heterojunction (HJ) composed of nanoscale percolation of donor and acceptor phase have been demonstrated to improve the efficiency of organic PV device. Such improvement is attributed to the creation of a spatially distributed interface, which enhances exciton dissociation, and the presence of continuous conducting paths for efficient charge collection. However, ideal nanoscale percolation is not readily achievable. Therefore, understanding the morphology inside the bulk heterojuncion plays an important role on achieving efficient PV device. Here, phase separation in donor-acceptor (D-A) mixture composed of pentacene:C60 and how it contributes to a percolated morphology are studied. The pentacene:C60 mixed films are fabricated by co-deposition of two molecules with vacuum thermal evaporation (VTE) method. The mixing ratio of pentacene and C60 is controlled by varying the deposition rate of each species. X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used to characterize the vacuum deposited pentacene:C60 mixed film. XRD patterns of pentacene:C60 mixed films indicate phase separation inside the mixture, which is reflected by appearance of characteristic diffraction peaks of thin film phase pentacene. SEM and AFM images reveal the change of surface morphology of the mixed films with varied mixing ratio and deposition rate, suggesting different degree of phase separation inside. Base on these information, PV devices are fabricated and their performance is investigated. It is found that by suppressing the phase separation between pentacene and C60 to nanoscale the PV performance is improved significantly. The open circuit voltage (Voc) and short circuit current (Jsc) increase from 0.45 V and 9.7 µA/cm2 in pentacene:C60 = 1:1 (by weight) device to 0.58 V and 1.3 mA/cm2 in pentacene:C60 = 1:5.5. All these suggest that degree of phase separation of molecular mixtures can be controlled by varying the process conditions, which may lead to new pathways to generate nanoscale percolation for application in efficient organic PV devices.
9:20 AM		EN+EM+NS+P+A+T+V-ThM-5 Tailoring the Morphology of Organic Solar Cells with Surface Templates S. O'Donnell (University of Virginia and The MITRE Corporation); P. Reinke (University of Virginia) One of the most important applications of fullerenes is their incorporation in organic solar cells, where they function as an electron acceptor in conjunction with photoactive molecules such as porphyrin. The photoyield is intimately linked to the morphology, which determines the efficiency of exciton diffusion and separation, and the effectiveness of charge transport to the electrodes. Control of the morphology across lengthscales, spanning the range from the molecule to the several hundred nm, is critical to optimization of solar cell functionality. We control the morphology by using tailored substrate templates on which we assemble ultrathin films with well-defined regions of acceptor and photoabsorber molecules. This approach enables us to measure the morphology and interface structure with atomic resolution with scanning probe methods, and to subsequently investigate the photocurrent distribution. A pattern with variable geometry is written on the surface of highly oriented pyrolitic graphite (HOPG), our model surface, with a focussed ion beam (Ga+, 30 keV ion energy), which creates regions with a high density of surface defects interspaced with largely undamaged graphite surface. The surface defect structure, its extension and density within the pattern is characterized prior to molecule deposition. Surface defects interact strongly with the fullerene molecules, and thus provide nucleation centers for the formation of fullerene islands whose position is in registry with the artificial pattern. The boundary of the ion damaged region serves as the primary nucleation center for the formation of C60 islands, whose shape is controlled by the pattern geometry and the diffusion length of the molecules. We will describe how the artificial pattern can be used to tailor the morphology across lengthscales and discuss the extension of this method to other, technically relevant surfaces such as quartz which possesses a natural patterning in the form of ledges. The complete 2D nanostructure can be built by deposition of fullerene on the templated HOPG, and the remaining "empty" graphite surface is then filled with photoabsorber molecules. We will show the movement of porphyrin molecules into the pattern, and how the interfacial region between fullerenes and porphyrins evolves, and discuss the resultant morphologies. This hierarchical assembly of organic solar cells will enable us to tailor morphologies and link them uniquely to the photophysical processes.
9:40 AM		EN+EM+NS+P+A+T+V-ThM-6 Photoemission Studies of Lead Sulfide Nanocrystals in Organic Films A.T. Wroble, D.J. Asunskis, A.M. Zachary, I.L. Bolotin (University of Illinois at Chicago); D.J. Wallace, M. Severson (University of Wisonsin-Madison); L. Hanley (University of Illinois at Chicago) Lead sulfide (PbS) nanocrystals have shown potential for use in optoelectronic applications including photovoltaics. PbS nanocrystals are grown directly into polymers or organic oligomer matrices to control the size and surface chemistry of the resulting nanocrystals. Transmission electron microscopy is used to determine the size distribution of PbS nanocrystals in organic films grown by either colloidal synthesis in polymer solutions or gaseous deposition using a cluster beam deposition source. Both the colloidal and cluster beam deposition methods are described in detail. Various techniques in photoemission spectroscopy are then applied to these PbS nanocrystal-organic films. X-ray photoelectron spectroscopy (XPS) confirms that PbS nanocrystals are present. Soft-XPS using 200 eV photon energies available at a synchrotron radiation source provides surface sensitivity to observe the interaction of the PbS nanocrystal surface with the organic matrix and is compared to XPS results obtained using 1487 eV photon energy. Little or no bonding between the PbS nanocrystals and the organic phase is observed. The core of the nanocrystals are found to be 1:1 Pb:S, but their surfaces are enriched in Pb. Finally, core level binding energy shifts in XPS under simulated solar irradiation are used for contact-free evaluation of element-specific photovoltaic electrical response of these PbS nanocrystal-organic thin films.
10:40 AM		EN+EM+NS+P+A+T+V-ThM-9 Rational Design of Nanostructured Hybrid Materials for Photovoltaics S.B. Darling, I. Botiz (Argonne National Laboratory); S. Tepavcevic, S.J. Sibener (The University of Chicago); T. Rajh, N. Dimitrijevic (Argonne National Laboratory) Efficient conversion of photons to electricity in organic and hybrid materials depends on optimization of factors including light absorption, exciton separation, and charge carrier migration. Bulk heterojunction devices target these processes, but disorder on the nanoscale results in inefficiencies due to exciton recombination and poor mobility. By rationally designing the morphology at appropriate length scales, one can enhance the effectiveness of internal processes and, therefore, the performance of photovoltaic devices. In this work, we have implemented this approach in two hybrid material systems—both of which may provide pathways to low-cost, large-area fabrication.¹ The first involves a rod-coil block copolymer which is used both as an optoelectronically active material and as a structure-directing agent to pattern active material into ordered nanostructures. The second system uses electrochemically prepared titania nanotube arrays in concert with in situ polymerization of electron-donating material. In both cases, the characteristic donor-acceptor length scale is controlled to be comparable to the exciton diffusion length throughout the active layer, and the domains are oriented perpendicular to the incident light direction to encourage efficient charge migration. ¹ Use of the Center for Nanoscale Materials was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract #DE-AC02-06CH11357. Parts of this work were also supported by the NSF-MRSEC at the University of Chicago.
11:00 AM		EN+EM+NS+P+A+T+V-ThM-10 Electronic Energy Level Alignment in Dye Sensitized Oxide Surfaces S. Rangan, J.P. Theisen, E. Bersch, R.A. Bartynski (Rutgers University) We have used direct and inverse photoemission to measure the occupied and unoccupied electronic states of N3 dye and determine their alignment with the band edges of single crystal and nanostructured TiO₂ and ZnO substrates. In dye-sensitized solar cell applications, the HOMO-LUMO gap of the dye molecule determines the useful portion of the solar spectrum, and charge transfer of photoexcited electrons to the substrate depends on the alignment of the LUMO to the substrate conduction band edge. We have compared the N3 dye properties on well characterized rutile TiO₂(110) and wurtzite ZnO single crystal surfaces to adsorption on more technologically relevant TiO₂ anatase nanoparticle and ZnO nanorod substrates. Samples were prepared and passivated with a pivalate layer in UHV, then sensitized ex-situ in a solution of N3 dye in acetonitrile. STM measurements show that the pivalic acid forms an ordered overlayer on the TiO₂(110) surface and that the N3 dye molecules can be imaged after sensitization. For N3 on TiO₂(110) as shown below, our spectroscopic measurements show that passivation significantly reduces contamination (presumably from water in the ambient) and that the N3 HOMO occurs at 0.9 eV above the TiO₂ valence band edge, while the LUMO is found 0.5 eV above the conduction band edge. On ZnO , the N3 HOMO occurs at 1.3 eV above the ZnO valence band edge but the N3 LUMO occurs 2.1 eV above the conduction band edge, much higher than what is measured on TiO₂. Comparison with experimental and theoretical values from the literature will be discussed.
11:20 AM		EN+EM+NS+P+A+T+V-ThM-11 Preparation of Nanoporous ZnO Photoelectrode using PEG Template for the Fabrication of Dye-Sensitized Solar Cells M.F. Hossain, S. Biswas, M. Shahjahan, T. Takahashi (University of Toyama, Japan) Recently, great attention has been paid to dye-sensitized solar cells (DSCs) due to their low fabrication cost. The high light-to-energy conversion efficiencies achieved with dye sensitized solar cells (DSCs) may be attributed to the nanoporous TiO₂ electrode. Zinc oxide (ZnO) is a wide band gap semiconducting material with a similar band gap and electron affinity to those of TiO₂ and has been considered as an alternative material in DSCs applications. Among the various techniques for the preparation of ZnO photo-electrode, the relatively simple sol gel method is the most widely used because of its ability to obtain films with tailored properties on large, curved substrates. In our present study, the nanoporous ZnO films were deposited on SnO₂:F coated glass by sol–gel technique with polyethylene glycol (PEG) as organic template, Zn(CH₃COO)₂.2H₂O as precursor, ethanol as solvent and NH(C₂H₂OH)2 as chelating agent. The ZnO films have been characterized by the TG-DTA, XRD, SEM AFM, FTIR and UV-VIS systems. The surface morphology of the nanoporous ZnO films strongly depend on the Zn(CH₃COO)₂ concentrations, PEG contents and number of coatings. It was revealed from optical study that the dye absorption increases with the increase of PEG concentrations. Incident photon-to-current conversion efficiency is calculated for all the solar cells with different ZnO thin films to evaluate the economic viability of this technique. The variation of photoelectric conversion efficiency of the solar cells, deposited with different Zn(CH₃COO)₂ and PEG concentrations are discussed with the analysis of different microstructure of the ZnO thin films and the corresponding dye-incorporations.
11:40 AM		EN+EM+NS+P+A+T+V-ThM-12 Metal / Polymer Interfaces: Ca on Polyfluorenes J.A. Farmer, J.H. Baricuatro (University of Washington); E. Zillner (Universitaet Erlangen-Nuernberg, Germany); J.F. Zhu (University of Science and Technology of China); C.T. Campbell (University of Washington) Conjugated polymers are being investigated for use in organic photovoltaic devices and organic electronics due to favorable cost and ease of processing compared to devices based on inorganic materials. The synthetic tunability of polymer-based devices makes them applicable to many technological applications. The creation of cheap organic photovoltaic devices would significantly improve our ability to harness solar energy and curb the use of fossil fuels. The development of organic LED and organic electronics may give rise to flexible computer displays and hardware that could revolutionize human interaction with computing devices. Crucial to the performance optimization of these devices is understanding the interaction between the metal electrodes and the polymer. The structure and energetics of the interface between Ca and two polyfluorenes, poly(9,9-di-n-hexylfluorenyl-2,7-diyl) (PDHF) and poly(9,9-di-n-hexylfluorenyl-2,7-vinylene) (PDHFV), were studied in ultrahigh vacuum using adsorption microcalorimetry, and low-energy ion scattering spectroscopy. The initial sticking probabilities of Ca on pristine PDHF and PDHFV at 300 K were 0.40 and 0.53, respectively. The sticking probability of Ca on PDHFV began decreasing after ~0.06 ML, and then increased toward unity after ~0.24 ML. Because no similar behavior was seen on PDHF, this decrease in the Ca sticking probability on PDHFV is tentatively ascribed to the presence of the vinyl group. At submonolayer coverages on both polymers, the integrated Ca ISS peak area increased slowly below 1 ML, with a value less than 1 % of a saturated Ca surface at 300 K. These results indicated that most of the Ca at low coverages were below the surface, and not visible to ISS. Beyond 1 ML the Ca peak area increased, and ultimately a continuous Ca film formed at ~50 ML. Based on the variation of Ca peak area with coverage, Ca grows as 3D islands on these polymer surfaces. The heat of adsorption of Ca on PDHF at 300 K was initially 240 kJ/mol and 315 kJ/mol on PDHFV. The heat of adsorption of Ca on PDHF decreased to the heat of sublimation of Ca in ~0.25 ML; the heat of sublimation was reached by ~0.50 ML for PDHFV. The interesting thermodynamic and sticking behavior below 0.50 ML, where Ca is interacting strongly with specific adsorption sites on the polymer will be discussed, and related to the use of these polyfluorenes in device applications.