Robert L. Opila, University of Delaware
Federico Rosei, INRS
Peter Sheldon, National Renewable Energy Laboratory
Symposium Support Elsevier
RBD Instruments, Inc.
GG2: Water Splitting
Monday PM, December 02, 2013
Hynes, Level 3, Room 312
2:30 AM - *GG2.01
Design of Catalysts and Electrocatalysts for Energy Applications
Jingguang G. Chen 1
1Columbia University New York USAShow Abstract
In the current talk we will use two examples to demonstrate the importance of using surface science studies to identify catalysts and electrocatalysts. Our research approaches involve parallel efforts in density functional theory (DFT) calculations, surface science experiments on model systems, and synthesis and evaluation of supported catalysts under thermochemical or electrochemical conditions. We will first use water electrolysis to demonstrate the feasibility of using monolayer Pt on tungsten carbide (WC) to achieve the same activity as bulk Pt. We will present DFT calculations of similar electronic and chemical properties between monolayer Pt/WC and Pt, synthesis and characterization of monolayer Pt/WC films, and electrochemical evaluation of the activity and stability of Pt/WC for water electrolysis. Comparing to the leading Pt electrocatalyst, the monolayer Pt/WC represents a reduction by a factor of ten in Pt loading [1,2].
We will then use the conversion of biomass-derived oxygenates to illustrate the advantages of using bimetallic catalysts. Bimetallic catalysts often show unique activity and selectivity over their parent metals due to the electronic modification and strain effect [3,4]. We will present our results on the characterization of Ni/Pt bimetallic surfaces and catalysts under in-situ reaction conditions, further highlighting the importance of using the combined approaches of DFT calculations, surface science experiments, and reactor evaluations [5,6].
 D.V. Esposito, S.T. Hunt, K.D. Dobson, B.E. McCandless, R.W. Birkmire and J.G. Chen, “Low-Cost
Hydrogen Evolution Catalysts Based on Monolayer Platinum on Tungsten Monocarbide Substrates”, AngewandteChemie International Edition, 49 (2010) 9859-9862
 D.V. Esposito, S.T. Hunt, Y.C. Kimmel and J.G. Chen, “A New Class of Electrocatalysts for Hydrogen Production from Water Electrolysis: Metal Monolayers Supported on Low-Cost Transition Metal Carbides”, Journal of the American Chemical Society, 134 (2012) 3025-3033.  W. Yu, M.D. Porosoff and J.G. Chen, “Pt-based Bimetallic Catalysis: From Model Surfaces to
Supported Catalysts”, Chemical Reviews, (2012) DOI: 10.1021/cr300096b.
 D.A. Hansgen, D.G. Vlachos and J.G. Chen, “Using First Principles to Predict Bimetallic Catalysts
for the Ammonia Decomposition Reaction”, Nature Chemistry, 2 (2010) 484-489.
 M. Salciccioli, W. Yu, M.A. Barteau, J.G. Chen, D.G. Vlachos, “Differentiation of O-H and C-H
Bond Scission Mechanisms of Ethylene Glycol on Pt and Ni/Pt Using Theory and Isotopic Labeling Experiments”, Journal of the American Chemical Society, 133 (2011) 7996-8004.
 W. Yu, M.A. Barteau and J.G. Chen, “Glycolaldehyde as a Probe Molecule for Biomass-derivatives:
Reaction of C-OH and C=O Functional Groups on Monolayer Ni Surfaces”, Journal of the American Chemical Society, 133 (2011) 20528-20535.
3:00 AM - GG2.02
In situ Transient Optical Spectroscopy of Photo-Excited Charge Carriers at the SrTiO3/Electrolyte Interface
Matthias M Waegele 1 Xihan Chen 1 David Herlihy 1 Tanja Cuk 1 2
1University of California Berkeley USA2Lawrence Berkeley National Laboratory Berkeley USAShow Abstract
While recent efforts to enhance photon-to-O2 conversion of photoanodes for water splitting have attracted much attention, linking the resulting apparent catalytic activities to the microscopic processes of electron-hole dynamics and interfacial hole transfer remains difficult. Herein, we investigate the kinetics of photo-excited carriers within the space charge layer of Nb-doped SrTiO3 anodes under working conditions by means of time-resolved optical spectroscopy. By probing the dependence of the dynamics on various variables, including electrochemical potential, electrolyte composition, and doping concentration, we are able to quantify the kinetics of electron-hole separation in the space charge layer, and monitor hole transfer across the SrTiO3/electrolyte interface. We discuss the relevance of our results in regards to the early steps in water oxidation at the SrTiO3 interface, as well as to the design of novel photoanodes.
3:15 AM - *GG2.03
Engineered Photoanodes for High Efficiency Dye- and Quantum Dot-Sensitized Solar Cells
Gurpreet Singh Selopal 3 1 K. Therese Dembele 2 Riccardo Milan 3 1 Isabella Concina 1 3 Giorgio Sberveglieri 3 1 Alberto Vomiero 1 2 3
1CNR SENSOR Lab Brescia Italy2INRS EMT Varennes Canada3University of Brescia Brescia ItalyShow Abstract
The typical photoanode in dye- and quantum dot- sensitized solar cells is composed of a wide band gap semiconductor, which acts as electron transporter for the photoelectrochemical system. Anatase TiO2 nanoparticles are one of the most used oxides and are able to deliver the highest photoconversion efficiency in this kind of solar cells, but intense research in the last years was also addressed to ZnO and other composite systems. Modulation of the composition and shape of nanostructured photoanodes is key element to tailor the physical chemical processes regulating charge dynamics and, ultimately, to boost the efficiency of the end user device, by favoring charge transport and collection, while reducing charge recombination.
We investigated several systems: (i) TiO2 nanoparticles / ZnO nanowires ; (ii) Multiwall carbon nanotubes (MWCNTs) / TiO2 nanoparticles ; (iii) TiO2 nanotubes [3-4]; (iv) Hierarchically self-assembled ZnO sub-microstructures . Both dye molecules and semiconducting quantum dots were applied as light harvesters. Possible tailoring of structure and morphology of the photoanodes, and their implication in improving the functional properties of these kinds of excitonic solar cells will be discussed.
 A. Vomiero, I. Concina, M.M. Natile, E. Comini, G. Faglia, M. Ferroni, I. Kholmanov, G. Sberveglieri, Applied Physics Letters 95 (2009) 193104.
 K.T. Dembele, R. Nechache, L. Nikolova, A. Vomiero, C. Santato, S. Licoccia, F. Rosei J. Power Sources 233 (2013) 93-97.
 A. Vomiero, V. Galstyan, A. Braga, I. Concina, M. Brisotto, E. Bontempi, G. Sberveglieri, Energy and Environmental Science 4 (2011) 3408-3413.
 V. Galstyan, A. Vomiero, I. Concina, A. Braga, M. Brisotto, E. Bontempi, G. Faglia, G. Sberveglieri, Small 7 (2011) 2437-2442.
 N. Memarian, I. Concina, A. Braga, S. M. Rozati, A. Vomiero, G. Sberveglieri, Angewandte Chemie In Ed 50 (2011) 12321-12325.
4:00 AM - *GG2.04
Hydrogen Production from Formic Acid: An Important Catalytic Reaction for Biomass Conversion
Manos Mavrikakis 1 James Dumesic 1 Jessica Scaranto 1 Suyash Singh 1 Ronald Carrasquillo 1 Brandon O'Neill 1 Sha Li 1 Luke Roling 1 Jeff Herron 1 Guowen Peng 1
1University of Wisconsin - Madison Madison USAShow Abstract
Formic acid (HCOOH) is a simple molecule that is an abundant product of biomass processing and can serve as an internal source of hydrogen for oxygen removal and upgrading of biomass to chemicals and fuels. In addition, HCOOH can be used as a fuel for low temperature direct fuel cells. We present a systematic study of the HCOOH decomposition reaction mechanism starting from first-principles and including reactivity experiments and microkinetic modeling. In particular, periodic self-consistent Density Functional Theory (DFT) calculations are performed to determine the stability of reactive intermediates and activation energy barriers of elementary steps. In addition, pre-exponential factors are determined from vibrational frequency calculations. Mean-field microkinetic models are developed and calculated reaction rates, orders, etc are then compared with experimentally measured ones. These comparisons provide useful insights on the nature of the active site, most-abundant surface intermediates as a function of reaction conditions and feed composition. Trends across metals on the fundamental atomic-scale level up to selectivity trends will be discussed. Finally, we identify from first-principles alloy surfaces, which may possess better catalytic properties for selective dehydrogenation of HCOOH than monometallic surfaces, thereby guiding synthesis towards promising novel catalytic materials.
4:30 AM - GG2.05
Study of Hydrogen Evolving Catalyst at the Light Absorber/Electrolyte Interface Using X-Ray Absorption Spectroscopy and Micro-Focused X-Ray Fluorescence
Eitan Anzenberg 1 Alexandra Krawicz 1 Gary F Moore 1 Junko Yano 1
1Lawrence Berkeley National Lab Berkeley USAShow Abstract
Studying and improving activity and stability of earth-abundant catalysts at the light absorber/electrolyte interface to drive hydrogen production reaction is an important challenge for solar fuel generation in artificial photosynthesis. We have used X-ray Absorption Spectroscopy (XAS) and micro-focused X-ray Fluorescence (MXRF) mapping at the Advanced Light Source (ALS) to characterize molecular surface-linked catalysts at the interface. The electronic and structural properties of the metal core or ligand were probed before, during, and after electro- and photoelectro-chemical (PEC) operation with ex- and in-situ detection techniques. Using Co K-edge XAS, we have shown that a Co(dmgH)2PrCl molecular catalyst remains electronically and structurally intact after attachment through the pyridine ligand to a polymer chain linked to a light absorbing surface . Using the Co fluorescence signal, we have also studied the stability of a cobaloxime-modified photocathode after rigorous PEC operation.
 Krawicz, Yang, Anzenberg, Yano, Sharp, Moore, Photofunctional Construct that Interfaces Molecular Cobalt-based Catalysts for H2 Production to a Visible-light Absorbing Semiconductor, Journal of the American Chemical Society, (submitted)
4:45 AM - GG2.06
Surface Structure-Activity Relationship in Ceria-Based Catalysts Studied by Surface X-Ray Diffraction on Atomically Flat Thin Films
Yezhou Shi 1 2 Chuntian Cao 1 Zhuoluo A. Feng 1 Michael F. Toney 2 William C. Chueh 1 2
1Stanford University Stanford USA2SLAC National Accelerator Laboratory Menlo Park USAShow Abstract
Ceria (CeO2) is one of the most active oxide electro-catalysts for hydrogen oxidation and water-splitting reactions at elevated temperatures. The surface concentration of oxygen vacancies and Ce3+ species were found to be significantly greater than the bulk, and can plausibly explain ceria&’s high electro-catalytic activity. Furthermore, the activities of ceria are expected to depend strongly on the surface termination, as already observed in nanostructured ceria with different facets. To better understand electrochemical reaction mechanisms and the structure-property relationship on the ceria surface, we investigated how the surface crystal structure of doped ceria differed from its bulk crystal. Specifically, we employed in-situ surface X-ray diffraction (SXRD) to study the atomic arrangements of (100)-and (111)-terminated ceria surfaces. We successfully fabricated atomically flat ceria films on yttria-stabilized zirconia substrates by pulsed laser deposition and confirmed that these films had well-defined step terraces using atomic force microscopy. We correlated the surface structure under both reducing and oxidizing atmosphere to the different catalytic activities of the (100)- and (111)-terminated films.
5:00 AM - GG2.07
Synthesis of Core-Shell Ferrite Nanoparticles for Thermochemical H2 Generation from Water-Splitting
Vinod Amar 1 Jan Puszynski 1 Rajesh V Shende 1
1South Dakota School of Mines amp; Technology Rapid City USAShow Abstract
Thermochemical water-splitting is a two-step process where in step-1, redox material is heated at higher temperature creating oxygen vacancies, whereas in step-2, this partially reduced material is exposed to steam leading to H2 generation by scavenging the oxygen. As these steps are performed at very high temperatures, materials experience grain growth. As a result, surface area and porosity decrease, which translate into lower H2 volume generation with increase in thermochemical water-splitting cycles. Therefore, there is a need to thermally stabilize the redox materials with the viewpoint of mitigating the grain growth and achieving steady H2 production. In this study, Ni-ferrite nanoparticles were synthesized using the sol-gel method and later these nanopartices were utilized to prepare porous core-shell nanoparticles with Y2O3 stablized ZrO2 (YSZ). The H2 generation ability of core-shell Ni-ferrite/YSZ nanoparticles was investigated by performing five consecutive thermochemical cycles in the Inconel packed-bed reactor where water-splitting and regeneration steps were carried out at 650o-1100oC. Specific surface area (SSA) and porosity of these materials were analyzed before and after the thermochemical water-splitting reaction using BET surface area analyzer. Additionally scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the grain growth. The results suggest grain growth mitigation in core-shell Ni-ferrite/YSZ nanoparticles that resulted in relatively steady H2 volume in multiple thermochemical water-splitting cycles. The H2 volume observed with core-shell ferrite nanoparticles was higher than ferrite nanoparticles. Characterization of core-shell nanoparticles and the results obtained on H2 volume generation with ferrite and core-shell ferrite nanoparticles will be presented.
5:15 AM - GG2.08
Hydrogen Storage in Orthorhombic Mg Hydride at Ultra-Low Temperature
Byoungsoo Ham 1 Anchalee Junkaew 1 Raymundo Arroyave 1 Haiyan Wang 2 Peng Wang 3 Jerek Majewski 3 Jinhee Park 4 Hongcai Zhou 4 Yang Ren 5 Xinghang Zhang 1
1Texas Aamp;M College Station USA2Texas Aamp;M College Station USA3Los Alamos National Laboratory Los Alamos USA4Texas Aamp;M College Station USA5Argonne National Laboratory Argonne USAShow Abstract
Mg can store up to ~7 wt.% hydrogen and is an appealing candidate as light weight and low cost hydrogen storage material. However hydrogen desorption in Mg hydride typically requires unfavorably high temperature of ~ 573 K due to its high thermodynamic stability, whereas the target operation temperature of fuel cells in automobiles is ~ 373 K or less. Furthermore the kinetics of H sorption in Mg is typically slow. Here we investigate hydrogen sorption behavior of Mg/Nb multilayers. Stress-induced orthorhombic Mg hydride (O-MgH2) is thermodynamically destabilized at ~ 373 K or lower. Such drastic destabilization arises from large tensile stress in single layer O-MgH2 bonded to rigid substrate, or compressive stress due to large volume change incompatibility in Mg/Nb multilayers. Ab inito calculations were performed to analyze the influence of interfaces on H sorption in Mg films. These studies provide insight on the mechanisms that may expedite the kinetics of H sorption in Mg.
5:30 AM - *GG2.09
Conjugated Porous Organic Polymers Possessing High Hydrogen Sorption Capacity
Baohang Han 1
1National Center for Nanoscience and Technology Beijing ChinaShow Abstract
Conjugated organic polymers, possessing intrinsic properties of large surface areas, high thermal and chemical stabilities, and low skeleton density, exhibit potential applications in gas storage and separation. Based on special spirocyclic or propeller-like monomers, various organic microporous polymers were prepared through a wide variety of C-C coupling reactions and further characterized at the molecular level by 13C CP/MAS NMR spectrum, as well as other techniques. All the obtained polymers are chemically stable. Thermal analysis shows that the materials are stable up to 350 °C under nitrogen. The fluorescent emission of the obtained conjugated polymers is tunable, ranging from 440 to 600 nm depending on the molecular structure of the monomer and coupling strategy. According to the obtained nitrogen physisorption isotherms, the Brunauer-Emmett-Teller (BET) specific surface area for these polymers varies between 700 and 2200 m<2> g<-1>. Adsorption isotherms show the polymers possess nice adsorption capacity to hydrogen and carbon dioxide, showing a good gas separation of carbon dioxide over methane.
GG3: Poster Session I
Robert L. Opila
Monday PM, December 02, 2013
Hynes, Level 1, Hall B
9:00 AM - GG3.01
High Efficiency and Enhanced Fill Factor of Solution Processed Small-Molecule Solar Cells with p-DTS(FBTTh2)2:PC71BM Bulk Heterojunction
Dong Hwan Wang 1 2 Aung Ko Ko Kyaw 1 Jong Hyeok Park 2 Alan J. Heeger 1
1University of California Santa Barbara Santa Barbara USA2Sungkyunkwan University Suwon Republic of KoreaShow Abstract
Bulk-heterojunction (BHJ) solar cells based on phase-separated blends of organic materials of donor and acceptor (fullerene derivative) have been in continuous development over the past two decades.(1)-(3) Recently, solution-processable small molecule-based BHJ solar cells exhibiting comparable power conversion efficiency (PCE) of near 7% to the polymers with high potential under simple and optimized processing conditions.(4)-(6) The small-molecule donors have attractive features, including relatively simple synthesis and purification steps, mono-dispersity, and improved batch-to-batch reproducibility.
Here, we demonstrated solution-processed small-molecule p-DTS(FBTTh2)2:PC71BM BHJ solar cells with a PCE over 8 %. The fill factor (FF) is sensitive to the thickness of a calcium buffer layer between the BHJ active film and the Al cathode; for 20 nm Ca thickness, the FF is 73%, the highest value reported for an organic solar cell. The maximum external quantum efficiency exceeds 80%. After correcting for the total absorption in the cell through the normal incidence reflectance measurements, the internal quantum efficiency approach 100% in the spectral range of 600 to 650 nm and well over 80% across the entire spectral range from 400 to 700 nm. Analysis of the current-voltage (J-V) characteristics at various light intensities provides information on the different recombination mechanisms in the BHJ solar cells with various thicknesses of the Ca layer. Also, we can fabricate improved efficiency of small-molecule solar cells with PCE of 8.24% with enhanced JSC and FF using a low sheet resistance of ITO (5 Omega;/square) substrate (ITO thickness of 450 nm) which exhibits transmittance of 90% at 550 nm. The increased JSC and FF originate from the reduced series resistance (Rs). In summary, the PCE and FF of small molecule based bulk-heterojunction solar cells can be increased by optimized thickness of Ca interlayer and low sheet resistance of ITO substrate.
(1) G. Yu, J. Gao, J.C. Hummelen, F. Wudl, and A.J. Heeger, Science 270 (1995) 1789.
(2) S.H. Park, A. Roy, S. Beaupre, S. Cho, N. Coates, J.S. Moon, D. Moses, M. Leclerc, K. Lee, A.J. Heeger, Nat. Photonics 3 (2009) 297.
(3) G. Li, V. Shrotriya, J. Huang, Y. Yao, T. Moriarty, K. Emery, Y. Yang, Nat. Mater. 4 (2005) 864.
(4) Y. Sun, G. C. Welch, W. L. Leong, C. J. Takacs, G. C. Bazan, A. J. Heeger, Nat. Mater. 11 (2012) 44.
(5) C. J. Takacs, Y. Sun, G. C. Welch, L. A. Perez, X. Liu, W. Wen, G. C. Bazan, A. J. Heeger, J. Am. Chem. Soc. 134 (2012) 16597.
(6) A. K. K. Kyaw, D. H. Wang, V. Gupta, J. Zhang, S. Chand, G. C. Bazan, A. J. Heeger, Adv. Mater. DOI: 10.1002/adma.201300295.
9:00 AM - GG3.02
Exfoliated Graphene-Supported Pt and Pt-Based Alloys as Electrocatalysts for Direct Methanol Fuel Cells
Wen Qian 1
1Portland State University Portland USAShow Abstract
To greatly improve the electrocatalytic activity for methanol oxidation, high-quality exfoliated graphene decorated with uniform Pt nanocrystals (NCs) (3 nm) have been prepared by a very simple, low-cost and environmentally benign process. During the entire process, no surfactant and no halide ions were involved, which not only enabled very clean surface of Pt/graphene leading to excellent conductivity, but also greatly improved the electrocatalyst tolerance to carbon monoxide poisoning (Pt/graphene, If/Ib= 1.197), compared to commercial Pt/C (If/Ib= 0.893) catalysts. To maximize the electrocatalytic performance and minimize the amount of precious Pt, Pt-M/graphene (M=Pd, Co) hybrids have also been prepared, and these hybrids have much larger electrochemically active surface areas (ECSA), which are 4 (PtPd/graphene) and 3.3 (PtCo/graphene) times as those of commercial Pt/C. The PtPd/graphene and PtCo/graphene hybrids also have remarkably increased activity toward methanol oxidation (If/Ib= 1.218 and 1.558). Furthermore, density functional theory (DFT) simulations demonstrate that an electronic interaction occurred between Pt atoms and graphene, indicating that graphene substrate plays a crucial role in regulating the electron structure of attached Pt atom, which confirmed that the increased efficiency of methanol oxidation was due to the synergetic effects of the hybrid structure.
9:00 AM - GG3.03
Large Impact of Molecular Orientation on Ionization Energy: Picene Film
Rintaro Makino 1 Keiichirou Yonezawa 1 Kengo Kato 1 Alexander Hinderhofer 1 Takuya Hosokai 2 Koji Okudaira 1 Nobuo Ueno 1 Satoshi Kera 1
1Chiba University Chiba Japan2Iwate University Morioka JapanShow Abstract
To improve the performance of organic photovoltaic cells, mechanisms of charge transfer/transport and charge separation have been widely investigated. These studies need acculate information on the electronic structure responsible to the processes. In general, however, it is not easy to reveal the electronic structure not only at metal-molecule interfaces but also of the molecular film itself due to large structural anisotropy of the molecule and their orientation in the film. Ionization energy (Ei) of the film depends on the molecular orientation, crystal structure and packing density . In this study, we investigated the electronic structure and the molecular orientation of picene (C22H14) films prepared on SiO2 and graphite (HOPG) substrates by using ultraviolet photomission spectroscopy (UPS) and metastable atom electron spectroscopy (MAES) .
Picene molecules were vacuum deposited step-by-step (upto ~10nm) on clean SiO2 and HOPG under UHV. The deposition rate was ~1.7 Å/min on the SiO2 and ~1.1 Å/min on the HOPG. All experiments were conducted at RT (293K).
We clarified using MAES from monolayer to multilayer that the molecules stand upright on the SiO2 (long axis of the molecule is normal to the surface), while they lie flat on the HOPG (short axis of the molecule is slightly tilted w.r.t. the surface). Normal-emission UPS spectra of the standing and lying films are largely different due to the orientation dependent photoelectron angular distribution and intermolecular interaction. The valence band features of the lying film correspond well to the density-of-states from DFT of an isolated molecule, while those of the standing film represent similarlity with the result of the single crystal .
We determined Ei for the HOMO onset and peak after peak fitting analyses of the HOMO features. The Ei of the standing film at the peak position (EiPEAK= 6.06eV) is smaller by 0.74eV than that of the lying film (EiPEAK = 6.80eV), giving the energy difference ΔEiPEAK = 0.74 eV (ΔEiONSET = 0.66 eV). These ΔEi are much greater than that of pentacene (ΔEiPEAK= 0.43eV ) as well as other pi-conjugated molecules (ΔEiPEAK = 0.40eV for DIP and 0.40eV for CuPc). Effects of electronic coupling at the picene/substrate interfaces on the UPS features can be neglected because of weak molecule-substrate interaction. We also suggest that for picene the molecular dipole and energy-band dispersion do not contribute much on ΔEi. Hence we can evaluate main origin of orientation dependent Ei by considering surface electrostatic potential produced by local dipoles (>C-H+) in picene. At the conference, we will report results of the electrostatic potential culculation and gas phase spectra of picene to discuss the orientation dependence of Ei.
 S. Duhm et al, Nature Mater. 7, 326 (2008).
 Y. Harada et al, Chem. Rev. 97, 1897 (1997).
 Q. Xin et al, Phys. Rev. Lett. 108, 226401 (2012).
 H. Fukagawa et al, Phys. Rev. B 73, 245310 (2006).
9:00 AM - GG3.04
Activation of the CO2 Molecule, A Theoretical Study
Shin Nakamura 1 Katsushi Fujii 2 Koji Ogata 1 Makoto Hatakeyama 1 Yuanqing Wang 1 Xu Zeng 3 Fangming Jin 3
1RIKEN Wako Japan2The Univ Tokyo Tokyo Japan3Jiao Tong University Shanghai ChinaShow Abstract
On the CO2 activation a theoretical study is presented. On the basis of the quantum chemical calculations, the order of magnitude in the activation is described. Taking as a reference of the CO2 molecule in dilute gas phase or in vacuum, the activated states in electronic structure (wave functions) as well as in geometrical changes are described by the degree of modifications relative to the reference state.
The DFT calculations are performed to visualize this degree of activation as a function of the environmental effect on CO2; gas phase, liquid phase (especially as a function of pH), and coordination on transition metals. Special attention is paid on the activation by abundant metals such as Zn. The experimental and theoretical examples of reactions of the activated CO2 are presented in hydrothermal condition with transition metal atoms.
9:00 AM - GG3.06
Engineering ZnO@SnO2 Multilayer Structures as Photoanodes for High Efficiency Photovoltaic Devices
Riccardo Milan 1 Gurpreet Singh Selopal 1 Mauro Epifani 2 Alberto Vomiero 1 Giorgio Sberveglieri 1 Guido Faglia 1 Isabella Concina 1
1University of Brescia amp; SENSOR Lab Brescia Italy2Consiglio Nazionale delle Ricerche Istituto per la Microelettronica ed i Microsistemi Lecce ItalyShow Abstract
Excitonic solar cells (XSCs) are appealing candidates as alternative devices for solar energy conversion, being in principle low cost, rather environmental friendly and suitable for exploiting also the near infrared (NIR) region of solar spectrum. 1
Nanoparticulate TiO2 is currently the most known and exploited semiconductor metal oxide (SMO) applied as photoanode in both dye- and quantum dot-sensitized solar cells (DSCs and QDSCs), but other SMOs, such as ZnO and SnO2, are attracting a broad interest, due to higher electron mobility and band structure suitable for NIR-absorbing light harvesters, respectively. 2,3,4
Strategies devoted to either completely inhibit or at least reduce recombination of photogenerated free charges, which is still one open issue in photoconverison efficiency, are still requested.
In this work, nano-SnO2, with different particles sizes (4 to 20 nm) and tunable amount of oxygen vacancies, was applied as main active layer in photoanodes for XSCs together with ZnO (as polidisperse nano- and micro-structures or hierarchical structures) in order to engineer the global band structures involved in charge injection.
A careful optimization of different parameters, such as relative layered composition of ZnO@SnO2 interfaces and dye loading time, allows demonstrating the highly beneficial role of ZnO as blocking layer towards the exciton recombination at SnO2-light harvester-electrolyte interfaces, thus reaching high functional performances in terms of injected photocurrent and photo conversion efficiency (JSC=14.78 mA/cm2 PCE=4.96%).
Strategies successful in optimizing the functional performances of XCSs (both DSCs and QDSCs) through material interface engineering will be presented and discussed.
1 B. O&’Regan, M. Gratzel, Nature 1991, 353, 737
2 E. Guillén, L. M. Peter, J. A. Anta J. Phys. Chem. C, 2011, 115, 2262
3 N. Memarian, I. Concina, A. Braga, SM Rozati, A Vomiero, G Sberveglieri, Angew Chem 2011, 51, 12321
4 A. Hossain, JR Jenning, Z.Y. Koh,Q. Wang, ACS Nano, 2011, 5, 3172
9:00 AM - GG3.08
The Effect of Molecular Adsorption-Geometry on the Binding Energy of Interface States
K. Kato 1 K. Sato 1 K. Yonezawa 1 Y. Liu 1 T. Hosokai 2 S. Yanagisawa 3 K. R Koswattage 1 N. Ueno 1 S. Kera 1
1Graduate School of Advanced Integration Science Chiba 263-8522 Japan2Department of Materials Science and Technology, Iwate University Morioka 020-8551 Japan3Depertment of Physics and Earth Sciences, Ryukyu University Okinawa 903-0213 JapanShow Abstract
Energy level alignment at organic/metal interfaces determines the performance of organic devices. To clarify the energy level alignment it is desired to obtain precise information of electronic states, in particular the highest occupied molecular orbital (HOMO) related states, at a complicated interface that consists of functional molecules. We studied the electronic structure and geometric structure of diindenoperylene (DIP: C32H16) monolayer (ML) on a Cu (111) surface by using angle-resolved ultraviolet photoelectron spectroscopy (ARUPS). It is known that DIP molecules form two different 2-dimensional lattice structures on Cu (111) .
A Cu (111) single crystal was cleaned by repeated Ar-ion sputtering and annealing cycles. The DIP ML film was prepared on the Cu (111) substrate by vacuum evaporation. ARUPS spectra were then measured at photon incidence angle α=45°, hv=28 eV and T=295 K at UVSOR facility (BL8B) at the Institute for Molecular Science. To study geometric structure as well as HOMO derived interface states we measured azimuthal angle (phi;) dependence by rotating the sample around the surface normal and photoelectron emission angle (theta;) dependence of the spectra of the ML.
ARUPS spectra of the DIP (ML)/Cu (111) show two prominent bands in the sp-band region of Cu (111). The first band is broad and located at binding energy (EB: from the Fermi level) of ~0.7eV, which is ascribed to the former LUMO with electrons transferred from the substrate as in the case of PTCDA . The second band consists of two features that are located at EB=1.5 and 1.8 eV. We observed these two features show different phi; dependences at theta;=37°. Assuming that these two features come from DIP HOMO and using the two molecular adsorption geometries observed with STM (the short-range and the long-range ordered structures) , we computed phi; dependences of the photoelectron intensity from the two features for the two geometries, and compared with the observed phi; dependences. The agreement between the observed and computed phi; dependences is obtained when the 1.5-eV feature is originated from the long-range ordered structure and the 1.8-eV feature is from the short-range ordered structure. We can thus ascribe both of these two features at 1.5 and 1.8 eV to HOMO-derived states.
 D. G. de Oteyza et al, Phys.Chem.Chem.Phys. 11, 8741 (2009)
 S. Duhm et al, Org. Electro. 9, 111 (2008)
9:00 AM - GG3.09
Transmission Electron Backscatter Diffraction (t-EBSD) for Characterizing Ultrathin Films in the SEM
Katherine Rice 1 Roy Geiss 1 Robert Keller 1
1NIST Boulder USAShow Abstract
Transmission electron backscatter diffraction (t-EBSD) is a new technique of materials characterization using a standard scanning electron microscope (SEM). By changing the sample-detector geometry so that electrons pass through a thin specimen prior to entering a commercial EBSD detector, an interaction volume significantly smaller than that typically associated with conventional EBSD can be achieved. As a result, electron diffraction data in the form of Kikuchi patterns can be collected from extremely fine-scale films and particles, down to the sub-10 nm dimensional scale. In conventional EBSD, incident electrons are thought to undergo Kikuchi scattering in the top 10 to 40 nanometers of a film, thereby requiring a film at least that thick to produce a diffraction pattern, while achieving a lateral spatial resolution in the typical range of 20 nm to 35 nm parallel to the tilt axis and 80 nm to 90 nm perpendicular to the tilt axis. Here we present recent results and electron scattering simulations associated with probing the sampling limits of the t-EBSD technique for semiconductor industry-relevant films as thin as 5 nm, while maintaining single-nanometer lateral spatial resolution.
Transmission EBSD, performed at ~ 20 keV, provides information from large areas of ultrathin films, while requiring only little material volume, by capturing forward-scattered electrons in transmission with standard EBSD equipment. Monte Carlo simulations support experimental results on the maximum thicknesses that can be reliably characterized with this method, by giving estimates of the energy losses of the electrons as they pass through increasing film thicknesses, and practical limits of the technique are investigated in terms of the mass-thickness of the sample, regardless of composition.
9:00 AM - GG3.10
Improved Raman Spectra of Materials Using a Schmidt-Czerny-Turner Spectrograph
Brian Charles Smith 1
1Princeton Instruments Acton USAShow Abstract
For decades Czerny-Turner (CT) spectrographs have been used to measure Raman spectra of materials. Inherent in the design of the CT spectrograph are optical aberrations including astigmatism, coma, and spherical aberration. These aberrations can cause Raman spectral peaks to be measured which are poorly resolved, have a low signal-to-noise ratio (SNR), and an asymmetric peak shape. The Schmidt-Czerny-Turner (SCT) spectrograph uses a unique optical design that completely eliminates astigmatism at all wavelengths and at all points on the focal plane, and greatly reduces coma and spherical aberration. The net result is Raman peaks of materials with improved spectral resolution, better SNR, and a symmetric peak shape. The use of a SCT spectrograph to obtain improved Raman spectra on a variety of materials will be discussed.
9:00 AM - GG3.11
Role of Strontium Dopant Concentration on the La1-xSrxCo0.2Fe0.8O3-delta; Cathode Performance in Solid Oxide Fuel Cells
Deniz Cetin 1 Yang Yu 1 Uday Pal 1 2 Soumendra Basu 1 2 Srikanth Gopalan 1 2
1Boston University Boston USA2Boston University Boston USAShow Abstract
One of the main current research goals in the solid oxide fuel cell (SOFC) industry is to reduce the operating temperatures of the SOFCs from 800-1000 °C to 600-800 °C. Reducing the operating temperature of SOFCs will obviate the need for expensive specialty alloys or ceramics for interconnects. However lower operating temperatures slow down the rates of electrochemical electrode reactions resulting in lower overall system efficiencies.
Using electrochemical impedance spectroscopy (EIS) on cells of the configuration LSCF (La1-xSrxCo0.2Fe0.8O3-δ)/ gadolinium-doped ceria (GDC) barrier layer/yttria-stabilized zirconia (YSZ)/porous LSM-YSZ counter electrode, the effect of Sr dopant concentration on the performance of LSCF cathodes was investigated. The effect of temperature on cathode performance was also investigated. The eventual goal is to obtain correlations between the electrochemical performance of LSCF cathodes and cation surface segregation effects.
9:00 AM - GG3.12
Tetrathiafulvalene as an Electron Acceptor for Surface Charge Induction on Silver Nanoparticles for Facilitated Olefin Transport
Hyung Woo Choi 1 Jung Hyun Lee 1 Young Rae Kim 1 Yong Soo Kang 1
1Hanyang University Seoul Republic of KoreaShow Abstract
Tetrathiafulvalene (TTF) is an organic semiconductor acting as an electron donor in charge-transfer complexes with an electron acceptor such as 7,7&’,8,8&’-tetracyanoquinodimethane (TCNQ) and also in metal-organic interfaces. On the contrary, we found that TTF was also able to act as an electron acceptor to the surface of silver nanoparticles (Ag NPs), which was consistent with the previous report to ZnO(0001) surface. Therefore it could be expected that TTF may act as an electron acceptor to induce partial positive charge on the surface of Ag NPs, similar to a well-known electron acceptor TCNQ.
We have previously reported various kinds of chemically modified Ag NPs as olefin carriers, which can interact with olefin gas specifically and reversibly but not with paraffin, consequently resulting in facilitated olefin transport. For instance, surface energy-level of Ag NPs was tuned to have partial positive charge on their surface by introducing electron acceptor such as p-benzoquinone (p-BQ) and TCNQ. The chemically activated Ag NPs have specific interactions only with propylene, resulted in the high selectivity of propylene over propane and high propylene permeance for the separation of olefin/paraffin mixture gases.
Herein, we adopted TTF to activate the surface of Ag NPs for olefin carriers, and their work function and binding energy were investigated by both UV photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was interestingly found that TTF was able to act as an electron acceptor and induce surface positive charge of Ag NPs, which can interact with olefin specifically, resulting in the high separation performance for olefin/paraffin mixtures.
9:00 AM - GG3.13
Effect of Air Exposure of MoO3 Film Underneath Thin Organic Film
Chenggong Wang 1 Yongli Gao 1
1University of Rochester Rochester USAShow Abstract
We have investigated the thickness dependence of air exposure of Copper Phthalocyanine (CuPc) and C60 layers on molybdenum trioxide (MoO3) with ultraviolet photoemission spectroscopy (UPS). It was found that after the air exposure, the WF of MoOx dropped severely. Meanwhile, with sim;10 ÅCuPc thin films covered on the top, there is no big change of the MoOx WF before and after the air exposure. We also noticed that sim;10 Å C60 thin film could also protect the WF drop of MoO3 from air exposure. Our ultraviolet photoemission spectroscopy date indicated the MoO3 surface which was covered by approximately two monolayers of organic thin films are not active to air.
9:00 AM - GG3.14
Passivating the Surface States of Iron Pyrite Nanostructures by Epitaxial Zinc Sulfide Coating to Improve Its Solar Performance
Dong Liang 1 Nicholas S Kaiser 1 Miguel Caban-Acevedo 1 Song Jin 1
1University of Wisconsin-Madison Madison USAShow Abstract
Iron pyrite (cubic β-FeS2), an earth abundant and nontoxic semiconductor, has been attracting resurgent attention as a promising candidate for solar energy conversion due to its suitable band gap (0.95 eV indirect, 1.03 eV direct), high absorption coefficient (~6×10^5 cm^-1), and high mobility in single crystals (> 300 cm^2/V s). However, the application of pyrite for solar cells has been hindered by its low open circuit voltage (up to 200 mV) and thus low efficiency (~3%), which has been attributed to rich band gap states located at pyrite/electrolyte and pyrite/metal interfaces. To improve the performance of pyrite solar cell, the understanding and effective passivation of pyrite surface is urgently desired. Using the phase-pure single crystal pyrite nanorods (NRs) and other nanostructures as the model system, we develop chemical vapor deposition of epitaxial zinc sulfide (ZnS) on pyrite NRs to passivate surface states. The heteorepitaxial interface between pyrite and ZnS has been confirmed with detailed transmission electron microscopy study. Employing field effect transistor (FET), scanning probe microscopy (SPM) measurements and other surface analysis techniques, we investigate the changes of surface potential dominated by surface defects and other semiconductor characteristics upon the passivation treatment. These results can be important for improving pyrite single crystal and thin film structures for solar energy applications.
9:00 AM - GG3.15
Enhance the Efficiency of Bulk Heterojunction Solar Cell by Constructing Self-Assembled Columnar Structure in the Active Layer
Cheng Pan 1 Hongfei Li 1 Zhenhua Yang 1 Bulent Akgun 2 Sushil Satija 2 Dilip Gersappe 1 Yimei Zhu 3 Jaseung Koo 4 Miriam Rafailovich 1
1Stony Brook University Stony Brook USA2National Institute of Standards and Technology Gaithersburg USA3Brookhaven National Laboratory Upton USA4Korea Atomic Energy Research Institute Yuseong-gu Republic of KoreaShow Abstract
Bulk heterojunction (BHJ) polymer solar cells are an area of intense interest because of their flexibility, relatively low cost and ease of processing. However, in the active layer of a conventional BHJ solar cell, most of the donor or acceptor domains are isolated or far from the electrodes. This morphology leads to a long conduction path which causes possible recombination of the electron and hole pairs and lowers the efficiency of the cell.
Our approach is a very simple way to build up highly ordered columnar structures within the active layer by introducing a second polymer, poly(methyl methacrylate) (PMMA), which is immiscible with poly(3-hexylthiophene) (P3HT), causing lateral phase segregation into columnar structures. Furthermore, studies have shown that when nanoparticles are present in an immiscible blend, they preferentially segregate to the interfaces, allowing the interface to produce a template for the particle segregation. We therefore postulated that if one or both of the phases were photoactive polymers, then if carrier particles, such as [6,6]-Phenyl C61 butyric acid methyl ester (PCBM), were added, a structure for heterojunction solar cells could be formed where a direct pathway to the electrodes could be templated for the carrier particles. We first tested this concept by modeling the system using a Molecular Dynamics (MD) simulation, which defined the regime in phase space in which the parameters would be in the correct range for generating phase segregated structures and then characterized the actual samples, using a variety of complementary techniques to confirm the columnar structure. Finally, the devices were constructed using these structures, which showed a marked improvement in efficiency over the normal BHJ cells.
9:00 AM - GG3.16
Qualitative Characterization of Hydrophobicity in the Presence of High Adhesion Using AFM Force Curves
Christopher Benedikt Pilscheur 1 Matteo Chiesa 1 Sergio Santos 1 Carlo Amadei 1 Karim Gadelrab 1 Marco Stefancich 1
1Masdar Institute of Science and Technology Abu Dhabi United Arab EmiratesShow Abstract
In atomic force microscope (AFM), force curves are widely used to investigate surface properties in the nanoscale. Besides having a proper calibration of the AFM, the experimental parameters have to be kept constant during the entire experiment. This is especially difficult for highly adhering samples due to tip contamination. In case of the appearance of tip contamination, the experimental parameters change and the results can not be used. The contamination of the tip happens because the interacting forces between tip and sample are too high. Since a lot of information about the surfaces properties is recorded in the first part of the force curve. Here a technique is presented, where only the first five to ten percent of the force curve need to be recorded, in order to get qualitative information about the hydrophobicity of one sample compared to a reference sample. This prevents the tip from contamination, because the force acting between the tip and the surface are kept so low, that the tip does not get contaminated.
9:00 AM - GG3.17
Surface Stabilities of n-Type GaN Dependent on Electrolyte under Photoelectrochemical Reactions
Kayo Koike 1 Akihiro Nakamura 1 Masakazu Sugiyama 1 Yoshiaki Nakano 1 Katsushi Fujii 2
1The University of Tokyo Tokyo Japan2The University of Tokyo Tokyo JapanShow Abstract
Photoelectrochemical water splitting is one of the candidates for hydrogen gas generation from water. GaN is suitable for the photoelectrochemical electrode due to the band-edge energies. However, the n-type GaN has stability problem that the surface anodic corrosion during the photoelectrochemical reaction. There are some reports described the electrolyte dependences, that is, the flatband potential dependences on the pH of electrolytes , however, the details have not been investigated. We discuss the photoelectrochemical surface stabilities of n-type GaN dependent on the electrolytes in this report.
The working electrode was n-type GaN grown on (0001) sapphire substrates by metal-organic vapor phase epitaxy (MOVPE). The GaN layer was 1.0 µm n-type layer on 2.0 µm undoped layer. The carrier concentration of n-type GaN layer was 1.6×1017 cm-3. The counter and reference electrode, which were made of Pt, and Ag/AgCl/NaCl, respectively, were used for electrochemical evaluations. The light intensity was controlled as 100 mW/cm2 by using of 500 W Xe-lamp. The electrolytes were 0.5 mol/L H2SO4 (pH 0.8), 1.0 mol/L HCl (pH 0.2), 1.0 mol/L KOH (pH 13.8), and 1.0 mol/L NaOH (pH 13.8). The surface morphology of GaN was observed by Normarski microscope and Atomic force microscope (AFM).
The flatband potential in HCl obtained from Mott-Schottky plot shifted 0.1 V to positive direction compared with that in H2SO4. The potential usually changes along with the Nernstian relationship of water, because the dominant adsorbed materials at the electrode surface are H+, OH-, and water. The results show that the potential do not only depend on pH, that is, the absorption materials on the GaN surface changing with the electrolytes.
Cyclic voltammetry with light illumination was evaluated in order to clarify the photoelectrochemical properties. The over potential decreased in HCl electrolyte compared with that in H2SO4 estimated from the anodic and cathodic turn-on voltage difference. The variation of anodic current of 1 to 3 cycles in H2SO4 was much larger than that of HCl, NaOH and KOH.
The GaN surface after the reaction in H2SO4 was changed to rough. In contrast, mirror-like surfaces were remained after the reaction in HCl, NaOH and KOH. From these results, the reaction mechanism in H2SO4 is expected to be different from that of the other solutions.
In summary, the selection of electrolyte affects the surface stability probably due to the difference of the adsorbed materials on the photoelectrode surface.
 K. Fujii, K. Ohkawa, J. Electrochem. Soc. 153 (2006) A468.
9:00 AM - GG3.19
Columnar P3HT Structure Obtained from Self-Assembly Templates in Bulk Heterojunction Solar Cell
Hongfei Li 1 Cheng Pan 1 Zhenhua Yang 1 Bulent Akgun 2 Sushil K. Satija 2 Yimei Zhu 3 Miriam H. Rafailovich 1
1Stony Brook University Stony Brook USA2National Institute of Standards and Technology Gaithersburg USA3Brookhaven National Laboratory Upton USAShow Abstract
In recent years, organic photovoltaic, especially the polymer-fullerene bulk heterojunction solar cells, exhibit many promising features, such as intrinsic flexibility, low cost, and ease-fabrication. Because of the phase separation between two components, the disordered structure in the active layer is the critical problem limiting the power conversion efficiency (PCE) of BHJ solar cell. Therefore, an ordered inner structure is one possible solution to enhance the efficiency of the BHJ solar cells. Our research demonstrated a method to build up self-assembled vertical columns of the photoactive polymer, poly (3-hexylthiophene) (P3HT), within the active layer of BHJ solar cells via the spontaneous phase segregation in the polymer blends of P3HT, a non-active but well characterized polymer PMMA or PS and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM) confined at the interface between PMMA/PS and P3HT. After selectively removed the PMMA or PS by solvent soaking, we obtained the highly ordered columns as P3HT template. This template was further utilized to fabricate real devices by filling a second photovoltaic polymer into the template. The as prepared devices were promising for exhibiting higher power conversion efficiency due to the shorter carrier transportation pathway and larger interface area between donor and acceptor. The columnar structured template is investigated under atomic force microscopy (AFM) and transmission electron microscopy (TEM). Neutron reflectometry was used to demonstrate the confinement of PCBM at the interface between P3HT and PMMA/PS in the active layer.
9:00 AM - GG3.20
Proton Transport Characteristics in Structurally Oriented Polyimide Thin Films for Fuel Cells
Karthik Krishnan 1 Masaki Noro 1 Hiroko Iwatsuki 2 Mitsuo Hara 2 Shusaku Nagano 2 Yuki Nagao 1
1Japan Advanced Institute of Science and Technology Ishikawa Japan2Nagoya University Nagoya JapanShow Abstract
Polymer electrolytes are regarded as an essential component in proton exchange membrane fuel cells (PEMFC) because of its high ionic transport, permeability to fuels, stability against corrosive environment and high electrical resistance, etc,. Of particular interest, thin polymer electrolytes have been attracted widely due to its distinct physical properties by the interfacial confinement, free surface effects and specific interactions between the active surface and polymer chains. A study of proton transport on nanoscaled thin polymer electrolytes disclose the clear scenario between the structure and property relations in confined systems. Indeed, the proton conductivity, structural orientation and water uptake capability in confined polymeric systems are influenced by varying the nature of substrate surface, origin of interfacial effects, morphology of thin films, and characteristics of domain spacing, etc,.
To understand the correlation between proton transport and structural orientation in polyelectrolytes, we have prepared the nanostructured polyimide thin films. Spin-coating was used to prepare the polyimide thin films and the desired thickness has been achieved by controlling the polymer to solvent composition. Thus, the 40 nm thin and 250 nm thick films have obtained on the quartz substrate. Both the relative humidity (RH) and temperature dependent proton conductivities were measured on these nanostructured polyimide thin films. A 40 nm thin polyimide film showed a slight enhancement of proton conductivity and the obtained maximum conductivity is 4.5 Chi; 10-2 S cm-1 at 298 K and 95% RH. Based on the orientation kinetics of polymer chains, the proton transport property have investigated. It is expected that the polymer chains are highly oriented in the in-plane direction, when the polyimide system is confined into thin film. Furthermore, confinement to thicknesses at nanoscale can lead to the anisotropies in internal morphology of the films, which is favorable for higher proton transport. From the Arrhenius plot, the activation energies were estimated and the obtained values are 0.24 and 0.20 eV respectively for 40 nm and 250 nm polyimide thin films. Employing the infrared (IR) p-polarized multiple-angle incidence resolution spectrometry (p-MAIRS) technique, polymer orientation was investigated in both the in-plane and out-of-plane direction.
9:00 AM - GG3.21
Aluminum Oxide Passivation Layer for Crystalline Silicon Solar Cells Deposited by Non-Vacuum Mist CVD
Toshiyuki Kawaharamura 1 Takayuki Uchida 2 Kenji Shibayama 2 Shizuo Fujita 2 Takahiro Hiramatsu 3 Hiroyuki Orita 3
1Institute for Nanotechnology Kami Japan2Kyoto University Kyoto Japan3Toshiba Mitsubishi-Electric Industrial Systems-Corpration Kobe JapanShow Abstract
There is much demand for back side passivation films of crystal silicon (Si) based solar cells, with slimming down Si wafer. Thermal silicon oxide, which is fabricated by an annealing at high temperature, is generally used as a passivation film of Si based solar cells. However, high temperature process gives Si a damage with deterioration of crystallinity. Hence passivation films fabricated by low temperature process are greatly requested. Aluminum oxide (AlOx) thin film which has a large amount of negative fixed charge at the AlOx/c-Si interface is expected as a most suitable one .
Several vacuum-based deposition processes, such as atomic layer deposition (ALD) and plasma enhanced chemical vapor deposition (PECVD), have been employed for AlOx thin films fabrication. In this study, AlOx thin films were grown by non-vacuum mist CVD, which is a suitable technique for fabricating metal and oxide alloy thin films with simple configuration and environmental friendliness .
AlOx thin films were deposited on both sides of p-type Si wafers under several conditions, namely samp.1-6. The carrier lifetime was measured and calculated by the microwave photo conductivity decay (mu;-PCD) method. The carrier lifetime of samp.4 was longest in those samples and was longer than that of sample treated with chemical passivation. The result suggests that the high quality AlOx passivation layer grown by mist CVD as same as that grown by vacuum process is obtained.
In the conference, the information of mist CVD and the passivation performance of AlOx thin film including fixed charge density and interface state density calculated from capacitance-voltage measurements will be reported and discussed in detail.
 J. Schmidt, et all., Prog. Photovolt: Res. Appl., Vol.16, Iss.6, (2008) pp.461-466
 T. Kawaharamura, T. Uchida, et all., AIP Advances, Vol.3, Iss.3, (2013) pp.032135
9:00 AM - GG3.23
Synthesized, Characterization and Multilayer Deposition of Oligothiophenes:From Fundamental Studies to Interfacial Modification for OSCs
Hsinhan Tsai 1 Cheng-Yu Kuo 1 Wanyi Nie 2 Aditya Mohite 2 Sergei Tretiak 3 Gautam Gupta 2 Leeyih Wang 4 Dmitry Yarotski 3 Hsing-Lin Wang 1
1Los Alamos National Lab Los Alamos USA2Los Alamos National Lab Los Alamos USA3Los Alamos National Lab Los Alamos USA4National Taiwan Univeristy Taipei City TaiwanShow Abstract
Oligothiophenes and their derivatives have attracted lots of attentions as they can be used to fabricate opto-electronic devices including OLEDs, OFETs and OPVs. The ability to functionalize oligothiophene backbone allows for the fine-tuning of the electronic properties1. These conjugated oligomers can be synthesized via Suzuki coupling and Grignard reaction, which have proven to be particularly advantageous in the large-scale production of oligothiophenes. Here we demonstrate synthesis and characterization of a series of conjugated oligothiolphene derivatives; terthiophene, tetrathiophen and pentathiophene, and their self-assemblies organized on the air-water interface. Our results suggest conjugation length-dependent properties (UV-Vis and Photoluminescence). Furthermore, we can control the thickness of oligothiophene multilayer and the molecular orientation in a self-assembled multilayered thin films by using Langmuir-Blodgett technique.2 This method has advantages of experimental simplicity, time-efficiency and low cost, and it also plays a crucial role in device fabriacation. Notably, the lambda;max and PL spectra of the LB films exhibit a blue shift with increasing conjugation length, contradicts the trend that we observed for solution spectra of the oligothiophenes. The structure of these self-assemblies and the impacts toward devices performance will also be discussed.
9:00 AM - GG3.24
Corrosion and Wear Resistant Ceramic Coatings for Bearings in Wind Power Systems
Sung-Yong Chun 1
1Mokpo National University Jeonnam Republic of KoreaShow Abstract
Wind carrying large amounts of sand and water droplets can erode the leading edge of a turbine blade and increase surface roughness. Superior hard and corrosion-resistant coatings of chromium nitride (CrN) have been prepared in reactive bipolar pulsed sputtering system. CrN coatings have also been prepared using dc generator in the same sputtering system under identical deposition conditions. The properties of these coatings are compared with the pulsed sputtered coatings. FE-SEM, AFM, potentiostat and nanoindentation tester have been used to characterize the coatings. We present in detail coatings (e.g., growth rate, morphology, surface roughness, corrosion resistance and nanohardness). The columnar growth of the deposited films could be suppressed by using the pulsed plasma without increasing the deposition temperature. Our studies show that CrN coatings with superior properties can be prepared using a bipolar pulsed sputtering.
Following are results of a study on the "Leades INdustry-university Cooperation" Project, supported by the Ministry of Education, Science & Technology (MEST)
9:00 AM - GG3.25
Graphene Nanosheets and Platinum Nanoparticles Composite Layer-by-Layer Films Applied to Methanol Oxidation Aiming DMFC Application
Celina Massumi Miyazaki 1 2 Marystela Ferreira 2 Antonio Riul 3
1POSMAT/UNESP - Universidade Estadual Paulista Sorocaba Brazil2UFSCar Sorocaba Brazil3UNICAMP - IFGW Campinas BrazilShow Abstract
Direct Methanol Fuel Cells (DMFCs) are promising candidates to produce more clear and efficient power supplies due its high energy density, low pollution, fast recharge and room temperature operation. Therefore, Platinum is the best catalyst for methanol oxidation in DMFCs and due to its high cost, different Pt-based composite materials have been tested in the last couple of years for use as methanol oxidation reaction catalysts for replacing Pt. More recently, graphene and graphene derivatives appear as promising support materials for heterogeneous catalysts due to the excellent electronic, mechanical and optical properties largely exploited nowadays in numerous technological developments. In this way, we apply the simple and versatile self-assembly Layer-by-Layer (LbL) technique to synergistically combine distinct materials properties and produce highly uniform composite films, aiming the DMFC performance enhancement. Different nanostructured LbL architectures containing graphene and graphene oxide (GO) nanosheets together with platinum nanoparticles were fabricated and tested. GO was synthesized using the Hummers method being further reduced using hydrazine in the presence of poly(sthyrenesulfonate)-PSS, producing stable grapheme nanosheets in aqueous suspension (GPSS), suitable for LbL applications. Platinum nanoparticles (PtNP) were synthesized and applied in different ways: i) reduced and suspended in PSS; ii) anchored to the graphene nanosheets and suspended in PSS; and iii) in situ reduction of Pt salt by sodium borohydride. Materials were analyzed by X-Ray Diffraction and UV-vis spectroscopy, and the electrocatalytic performance of these composite LbL films for methanol oxidation was analyzed by cyclic voltammetry. It was verified long-term stability and the tolerance of the LbL films due to the accumulation of intermediates species into the electrode (electrode poisoning), relating the anodic peak current in the forward (If) and backward (Ib) peak. Some LbL architectures have shown a good methanol oxidation capability and good tolerance to the intermediate contamination. Hereafter, the better LbL structure will be tested in a DMFC.
9:00 AM - GG3.26
The Influence of Anneal Temperature on the Efficiency of Zno/Si Heterojunction Solar Cells Grown by R.F Magnetron Sputtering
Xiaoyan Peng 1 Jin Chu 1 Peter Feng 1
1University of Puerto Rico San Juan USAShow Abstract
ZnO/Si junction solar cells were prepared by r.f magnetron sputtering system. After deposition, the ZnO samples were annealed under different temperature from 400 °C to 1000 °C at air ambient. High conversion efficiencies ranging between 10.5% and 15.5% without using frontal grid contact have been carefully studied and tested for the annealed samples. The photovoltaic properties of solar cells grown under different operating temperature are characterized and analyzed. Furthermore, the stability conditions and reliability of these solar cells have been tested.
9:00 AM - GG3.27
Thermochromic Properties of Vanadium Oxide Based Transition Metal Oxides Thin Films on Quartz Substrate
Adetayo Adedeji 1 Stephanie Worsley 1 Terrence Baker 1
1Elizabeth City State University Elizabeth City USAShow Abstract
The optical and electrical properties of sputtered vanadium oxides and co-sputtered mixed transition metal oxides were studied as a function of temperature. The effect of depositing the metal oxides on very thin layer dielectric (RF sputtered SiO2 and Si) instead of directly on quartz substrate was investigated as well. The atomic composition of the films and the surface morphology were determined with Rutherford Backscattering Spectroscopy (RBS), X-Ray Diffraction (XRD), Energy Dispersive Spectroscopy (EDS), Scanning Electron Micrograph (SEM) and Atomic Force Microscopy (AFM)
9:00 AM - GG3.28
Investigation of the Silicon Solid Electrolyte Interface in Lithium Ion Batteries Using the Technique of Hard X-Ray Photoelectron Spectroscopy
Benjamin Young 1 David Heskett 1 Brett Lucht 2 Joseph C. Woicik 3
1University of Rhode Island Kingston USA2University of Rhode Island Kingston USA3National Institute of Standards and Technology Gaithersburg USAShow Abstract
Formation of a stable Solid Electrolyte Interface (SEI) between the anode and electrolyte material of a lithium ion battery (LIB) is a key factor in the performance of these batteries. Materials combinations which optimize battery performance and stability in demanding applications are the focus of major efforts as researchers attempt to correlate desirable battery properties with the presence of various chemical species in the SEIs after cycling. Often, however, the analysis is limited to the few outermost nanometers of the SEI. The greater photon energies available at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory permit performance of Hard X-ray Photoemission Spectroscopy (HAXPES) at beamline X24A. HAXPES experiments significantly extend the photoemission probing depth to yield important information regarding the growth and composition of the SEI and a better understanding of LIBs.
Silicon is a promising anodic material for use in LIBs because its theoretical energy storage capacity is ten times that of more thoroughly investigated carbonaceous anodes. A recent study by Lucht, et al. has compared the addition of ethylene carbonate (EC) or fluoroethylene carbonate (FEC) solvent to the base electrolyte material in coin cell LIBs. Test cells containing FEC retained capacity better and showed more consistent efficiency for repeated cycling than those using EC. Analysis of the LIB anodes after cycling by TEM, EDX, TOF-SIMS, FT-IR and NMR indicate that the solvents added to each battery&’s electrolyte influence SEI formation and its maturation under cycling.
The present study investigates SEI formation and composition for LIBs using electrolytes containing LiPF6 salt and EC or FEC additives with a binder-free silicon nanoparticle anode in lithium ion coin cells. Utilizing the HAXPES technique, we are able to access information about the SEI composition down to the substrate anodic silicon. Using multiple photon energies up to 6 keV and the concomitant ability to probe more tightly bound core electrons than traditional XPS studies allows us to present depth-dependent characterization of the SEIs in order to display the unique properties of SEI growth and composition for each electrolyte additive.
9:00 AM - GG3.29
Synthesis and Nano-Mechanical Properties Characterization of Conjugated Polymer Thin Films
Nimitt Patel 1 Arvind Sreeram 2 Stephan DeLuca 2 Sitaraman Krishnan 2 Philip A. Yuya 1
1Clarkson University Potsdam USA2Calrkson University Potsdam USAShow Abstract
Conjugated polymers have received considerable attention as organic semiconductors, with applications ranging from solar cells and organic light-emitting diodes (OLEDs) to organic field-effect transistors (OFETs). In addition to desirable opto-electrical properties, thermal and oxidative stability and mechanical toughness (resistance to fracture) are also important in large-scale fabrication of devices using these polymers. In this study, thin films of polyacetylene (PA) and poly(p-phenylenevinylene) (PPV) were prepared using the precursor approach. The precursor films, cast on glass substrates by spin-coating, were converted to the corresponding conjugated polymers by heating at different temperatures. The effect of temperature on the extent of reaction was studied using gravimetric and spectroscopic (infrared) techniques. Nanoindentation was used to measure the mechanical properties of the films at the sub-micron level. Reduced modulus, storage modulus, loss modulus, and loss factor (tan δ) were characterized through quasi-static and dynamic nanoindentation, using a three-faceted diamond Berkovich tip. The reduced modulus of PPV was found to be about 4 GPa with no significant change over the range of annealing temperatures. In contrast, PA showed a considerable decrease in the values of reduced modulus as the annealing temperature was increased. Similar trend was observed in storage modulus, that is, no significant decrease in storage modulus in case of PPV, but a decrease in storage modulus of PA with an increase in the annealing temperature.
9:00 AM - GG3.30
Synthesis and Characterization of Poly(phenylene)-Based Electrolytes Having Alkyl Group
Yusuke Kawano 1 Satoru Obayashi 1 Masahiro Yoshizawa-Fujita 1 Yuko Takeoka 1 Masahiro Rikukawa 1
1Sophia University Tokyo JapanShow Abstract
Sulfonated aromatic polymers such as poly(p-phenylene)s have been widely investigated as polymer electrolyte membrane (PEM) materials for fuel cell applications due to their high thermal stability, high proton conductivity, and low cost. Sulfonated aromatic polymers, however, have low mechanical properties under hydrous conditions. The excess water sorption causes large and undesirable dimensional change of PEMs. Therefore, the control of water uptake for the PEMs based on poly(phenylene) derivatives is one of critical demands for fuel cell applications.
In order to control their water uptake, we synthesized sulfonated poly(phenylene)s having alkyl groups on the side chain. The sulfonated monomer, 2-hexyl-5-(2,5-dichlorobenzoyl)-benzene sulfonic acid 2,2-dimethyl-1-propyl ester, was polymerized via nickel-catalyzed coupling polymerization to obtain the polymer (NS-PHBP). NS-PEtBP, NS-PBuBP, which have ethyl and butyl groups, were also synthesized with the same procedure of NS-PHBP. The weight-average molecular weights of NS-PEtBP, NS-PBuBP, and NS-PHBP, were 126,000, 101,000, and 178,000 g mol-1, respectively. S-PHBP, S-PEtBP, and S-PBuBP, were synthesized by the deprotection of neopentyl groups of corresponding NS-type polymers with diethylamine hydrobromide. The ion exchange capacity (IEC) of S-PHBP was 2.91 meq g-1, while those of S-PEtBP and S-PBuBP were 3.47 meq g-1 and 3.16 meq g-1. The each sulfonation level calculated from the elemental analysis of the polymers was consistent with the theoretical value. The thermal stability of the polymers was investigated by using TG-DTA. The polymers showed no weight loss up to 200 - 210 °C. The water uptake of S-PHBP was 27% under 90%RH at 80 °C, whereas those of S-PEtBP and S-PBuBP were 45% and 31%. The ratio of freezable water molecules in membranes hydrated at 100%RH, determined by DSC measurements, decreased from 29% to 9% by increasing the alkyl side chain length. This suggested that the introduction of alkyl groups suppressed the sorption of free water. The proton conductivity of these polymers increased with increasing relative humidity and was about 10-1 S cm-1 at 90%RH and 80 °C.
9:00 AM - GG3.31
Synthesis and Characterization of Poly(phenylene) with Super Acid Groups for Proton Exchange Membrane Fuel Cells
Tatsuya Oshima 1 Yusuke Sakaki 1 Masahiro Yoshizawa-Fujita 1 Akihiro Ohira 2 Yuko Takeoka 1 Masahiro Rikukawa 1
1Sophia University Tokyo Japan2AIST FC-Cubic Tokyo JapanShow Abstract
Perfluorosulfonic acid polymers such as Nafion® are the most promising polymer electrolytes for proton exchange membrane fuel cells (PEMFCs) because of their high proton conductivity and high chemical stability. However, the practical use of such polymers suffers from high cost, relatively low glass transition temperature, and high gas permeability. These issues have stimulated the research to develop alternative polymer electrolyte membranes, especially, acid-functionalized aromatic hydrocarbon polymers over the past decade. Typical aromatic ionomers have aryl or alkyl sulfonic acid groups to induce high proton conductivity. The conductivities of these ionomers at high temperature and low humidity are lower than that of Nafion®, because aryl or alkyl sulfonic acid groups have lower acidity compared to super acidic groups such as perfluoroalkyl sulfonic acid. In this study, we report the synthesis of novel poly(phenylene)-based electrolyte having perfluoroalkyl sulfonic acid groups and investigate the effect of acidity for electrolyte properties by comparing with poly(phenylene)s containing aryl or alkyl sulfonic acid groups.
Three kinds of poly(phenylene)-based polymer electrolytes with perfluoroalkylsulfonic groups (FES-PPBP), benzenesulfonic groups (S-PPBP), and propylsulfonic groups (S-PrPBP) were synthesized via nickel-catalyzed coupling polymerization. The weight-average molecular weights (Mw) of FES-PPBP, S-PPBP, and S-PrPBP were 78.9 kg mol-1, 119 kg mol-1, and 178 kg mol-1, respectively. The ion exchange capacities (IECs) of FES-PPBP, S-PPBP, and S-PrPBP were 2.12, 2.82, and 3.16, respectively. FES-PPBP, S-PPBP, and S-PrPBP exhibited lyotropic nematic liquid crystal behavior in dimethyl sulfoxide. FES-PPBP showed hydration numbers lambda; of 2-9 at 30-90%RH and 80 °C, which were the almost same lambda; values of S-PPBP and higher lambda; values than those of S-PrPBP. We employed the pulsed field gradient nuclear magnetic resonance (PFG-NMR) technique to investigate the self-diffusion coefficient of water in these membranes. The water diffusion coefficient in FES-PPBP membranes was 6.33×10-10 m2 s-1 at 30 °C and 90%RH, which was higher than those of S-PPBP and S-PrPBP. The proton conductivity measured by impedance analyzer at 80 °C, and 30%RH of FES-PPBP was higher than S-PPBP and S-PrPBP, despite of the lower IEC values. These results showed the introduction of perfluoroalkyl sulfonic acid groups induces high proton conductivity without high sulfonation level.
9:00 AM - GG3.32
Synthesis and Evaluation of Poly(phenylene)-Based Ionomers with pi;-Conjugated Unit-Synthesis of Thiophene Derivatives-
Kohei Seto 1 Satoshi Miura 1 Masahiro Yoshizawa-Fujita 1 Yuko Takeoka 1 Masahiro Rikukawa 1
1Sophia University Tokyo JapanShow Abstract
The membrane electrode assemblies (MEAs) are composed of an ionomer, catalyst layer, and diffusion layer. Since there are no suitable hydrocarbon ionomers, which are used for catalytic layers, Nafion solution is used in most cases. If electron conductivity and redox properties can be given by using π-conjugated polymers as the ionomer, the improvement in catalyst activity or durability can be expected. In this study, we synthesized amphiphilic diblock copolymers composed of poly(thiophene) and poly(phenylene) electrolyte and evaluated their properties.
Block copolymers (NSmHTn) with π-conjugated units were synthesized by the polymerization of 1,4-dibromo-2,5-di-[4-(2,2-dimetyl-propoxysulfonyl)phenyl]proxybenzene (NS-DBPrB) and 2,5-dibromo-3-hexylthiophene (DBrHT) via catalyst transfer polycondensation. The m and n mean the polymerization degree of the hydrophilic and hydrophobic units, respectively. The number-average molecular weights and polydispersity indexes of NSmHTn were 10.8 - 18.3 kg mol-1 and 1.10 - 1.25, respectively. SmHTn were synthesized by the deprotection of neopentyl groups of NSmHTn with diethylamine hydrobromide. The ion exchange capacity (IEC) values of SmHTn were determined by back titration to be in the range of 1.13 and 2.39 meq g-1. The optical properties of NSmHTn and SmHTn was investigated by UV-vis-NIR absorption spectroscopy. The absorption bands corresponding to the phenylene and thiophene based bones were observed at around 300 nm and 500 nm, whereas SmHTn showed the absorption bands corresponding to the bipolaron bands at around 800 nm and 2000 nm. This suggested that the P3HT units were doped by the sulfonate groups of phenylene units . The PEFC performance was evaluated using the MEAs fabricated with Nafion® 211 membranes and S8HT82, S9HT29 or S18HT23 ionomers. S9HT29 showed the best performance among three hydrocarbon ionomers. The limiting current density was 2420 mW cm-2, and the maximum power density was 794 mW cm-2 at 80 °C and 80%RH under 0.1 MPaG. The performance of MEAs with SmHTn were better than those of Nafion ionomers at 30%RH and 80 °C. Impedance measurements were carried out by using a impedance analyzer. The charge transfer resistance of the MEAs with Nafion ionomers was lower than those of MEAs with SmHTn ionomers at 80 %RH and 80 °C, while MEAs with SmHTn ionomers showed lower charge transfer resistance value than that of MEAs with Nafion ionomers at 30 %RH and 80 °C. The electrochemically active surface area (ECA) values were derived from cyclic voltammograms. ECA values decreased as relative humidity decreased. The ECA values of MEAs with S8HT82, S9HT29 and S18HT23 were better than that of MEA with Nafion at 30%RH and 80 °C.
9:00 AM - GG3.33
Triboelectric-Based Harvesting of Gas Flow Energy and Detection of Dust Concentration
Majid Taghavi 1 2 Ali Sadeghi 1 Barbara Mazzolai 1 Lucia Beccai 1 Virgilio Mattoli 1
1Istituto Italiano di Tecnologia Pontedera Italy2Scuola Superiore Santamp;#8217;Anna Pontedera ItalyShow Abstract
Lots of efforts have been focused on harvesting the energy of wind or gas flow, mainly based on three commonly used mechanisms for converting mechanical energy to electrical energy: electromagnetic, piezoelectric and electrostatic mechanisms. In this work we propose a different approach that can convert gas flow energy to electric energy by using the triboelectric effect, in a structure integrating at least two conductive parts (i.e. electrodes) and one non-conductive part. The gas flow induces vibration of the cited parts. Therefore, the frequent attaching and releasing between a non-conductive layer with at least one electrode generates electrostatic charges on the surfaces, and then a electron flow between the two electrodes. Blowing natural air or other impure gas flows containing dust increase the generated charges since the friction produced at the interface between dust and other materials will increase the triboelectric charging. This approach allows detecting the concentration of dust in the gas flow without the need of any powering.
We demonstrate our concept by the development of some prototypes. For instance, a rectangular PET sheet with the dimension of 12mm×40mm, which is fixed from one of the shorter sides, serves as a movable part. It is placed, with two 0.25 mm spacers, between two Plexiglass sheets covered by copper tape, which are used as a frame and electrodes, respectively. The sheet is able to oscillate by blowing air through the channel, and then due to both charge transferring and inducing, a LED is continuously lightened up. As mentioned before, the intensity of generated voltage signals differ by flowing gases containing dust.
The polarity and the amount of those generated charges depend on the place of those materials in the triboelectric series as well as roughness, humidity, temperature, etc. Air is listed as the most positive triboelectric material in some triboelectric series . Since pure gas cannot charge any surfaces, then we believe that the contaminated particles are able to charge the surfaces by coming into contact with them. However, depending on the dust types (i.e. material of particles), the electrodes or the non conductive material can be covered by an appropriate layer in order to detect and maximize the amount of generated charges.
1. Adams, Charles K. Nature's electricity. Tab Books, 1987.
9:00 AM - GG3.34
UV and Air Stability of High-Efficiency Photoluminescent Silicon Nanocrystals
Jihua Yang 1 Richard Liptak 2 Steve Campbell 2 Uwe Kortshagen 1 James Casey 3 Jon Hannington 3
1University of Minnesota Minneapolis USA2University of Minnesota Minneapolis USA3Dow Corning Corporation Midland USAShow Abstract
As the primary source material for optoelectronic devices, silicon (Si) has unique advantages of being less toxic and naturally abundant on Earth. These advantages have led to a great deal of attention to nanostructured Si for various applications such as biological labeling, light emitting devices, transistors, and solar cells. The nonthermal plasma technique provides an effective method for synthesis of well-crystallized Si nanocrystals (Si NCs) with large production yield and excellent size control. Liquid thermal hydrosilylation with alkene ligands enables to form colloids of Si NCs well-dispersed into solvents with high-efficiency PL by utilizing. The NC size can be tuned such that one can obtain short-wavelength absorption and photoluminescence (PL) which spans across the visible-to-infrared region of the solar spectrum. This prompts an alternative potential use of Si NCs as a luminescent concentrator, which can improve absorption of solar cells by absorbing UV light and down-shifting it to a lower energy light via photoluminescence. This process can enhance the incident light intensity in the main absorption region of a solar cell and therefore increase the amount of the photons to be effectively absorbed. Aiming at UV and air stable photoluminescence of Si NCs, in this work, we investigate the UV and air stability of highly-efficient luminescence of Si NCs synthesized using nonthermal plasma technique and the effects of hydrogen gas-passivation and phosphorous (P) doping on it. After hydrosilylation, the Si NCs can be well dispersed into common solvent such as toluene with high-efficiency photoluminescence quantum yield (PLQY) of 73%. The Si NCs exhibit photobleaching effect within the first 4 hours of 365 nm UV irradiation and retain a PL quantum yield (PLQY) of 52% of the initial value irrespective of further irradiation. PLQY of the UV-irradiated Si NCs can recover with time, similar to the Staebler-Wronski effect. Gas-phase passivation of Si NCs by hydrogen afterglow injection plays a crucial role for improving PLQY and PL stability against UV or air exposure. Furthermore, phosphorous doping of Si NCs improves PLQY and leads to UV-stable Si NCs, as a result of suppression of surface defects and reduction of weak chemical bonds.
9:00 AM - GG3.35
PEDOT:PSS Lbl Modified Nafionreg; 212 Membranes to Reduce the Methanol Permeation
Tiago P. Almeida 1 Valdecir A. Paganin 2 Celina M. Miyazaki 3 Marystela Ferreira 1 Joelma Perez 2 Antonio Riul 4
1Samp;#227;o Carlos Federal University Sorocaba Brazil2University of Samp;#227;o Paulo Samp;#227;o Carlos Brazil3Samp;#227;o Paulo State University Bauru Brazil4UNICAMP Campinas BrazilShow Abstract
Multilayer films of poly(allylamine hydrochloride) (PAH) with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) were assembled onto Nafion® 212 membranes using the layer-by-layer (LbL) technique to check how ultrathin films of PAH/PEDOT:PSS influence the methanol permeability and resistance of Nafion® membranes. The LbL assembly was chosen due to its simplicity and versatility to produce thin films with controllable thickness and morphology, taking the advantages of nanoscale engineering to create tailored nanostructures and functional surfaces with fine control in the film composition. The PEDOT:PSS choice was based on its chemical stability and possibility to increase the proton conduction due to the presence of sulfonic groups in the PSS structure, quite important for proton transfer in Nafion® membranes. Here, UV-vis and impedance spectroscopy were used to investigate the nanostructured PAH/PEDOT films onto a Nafion® 212 membrane, which was also characterized by voltammetric measurements to check the effect of the LbL films in the methanol permeation. Our results indicated good adherence and linear growth of the LbL films onto Nafion® 212, and also good action as a methanol barrier. Therefore, we believe that the LbL assembly requires some important charged groups to water permeation present at the Nafion® surface, consequently affecting the membrane resistance.
9:00 AM - GG3.36
Nanoscale Confinement Induces Reversal of the Direction of Electrochemical Process
Nan Yang 1 2 Sandra Doria 1 Amit Kumar 3 Thomas M. Arruda 3 Antonello Tebano 2 Ilia N. Ivanov 3 Stephen Jesse 3 Arthur P. Baddorf 3 Silvia Licoccia 4 Carmela Arruta 2 Giuseppe Balestrino 2 Jae Hyuck Jang 5 Albina Y. Borisevich 5
1University of Roma amp;#8220;Tor Vergataamp;#8221; Rome Italy2University of Roma amp;#8220;Tor Vergataamp;#8221; Rome Italy3Oak Ridge National Laboratory Oak Ridge USA4University of Roma amp;#8220;Tor Vergataamp;#8221; Rome Italy5Oak Ridge National Laboratory Oak Ridge USAShow Abstract
Electrochemical reactions on solid surfaces directly underpin the functionality of batteries, [1-3] fuel cell, [4-6] sensors, and multiple other electrochemical devices. In many cases, the direction and mechanism of reaction is controlled by the nanoscale details of surface structure, On the nanometer scale, localized electrochemical reactions enable technologies such as scanning probe microscopy (SPM) based nanofabrication,[7-9] data storage, and charge writing in oxide electronic devices.[10,11] However,the basic premise of electrochemistry holds that application of a negative bias induces local reduction and a positive bias induces local oxidation. We demonstrate by SPM that the reverse happens in (001) oriented epitaxial CeO2 thin films i.e. application of positive bias to an SPM probe can induce local reduction, a behavior we refer to as “electrochemical field effect”. Two different regimes are observed: a moderate bias/negligible current regime, where an anomalous redox processes occurs (2CeO2+3H2O --- 2Ce(OH)3+1/2 O2) and a high bias/sizeable current regime, where standard redox processes take place. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizeable transport current flows between the tip and film. The role of water in this process is explored by scanning transmission electron microscopy - electron energy loss spectroscopyanalysis. We believe that this behavior can be universal for electrochemical processes in nanoconfined volumes. Our study gives insight into the mechanism of the tip-induced electrochemical reactions as mediated by electronic currents as well as allows nano-structures and devices to be explored at the surface.
M.Winter, J.O. Besenhard, M.E. Spahr, P. Novak, Adv. Mater. 1998, 10, 725.
A. Kraytsberg, Y. Ein-Eli, J. Power Sources 2011, 196, 886.
D. Aurbach, J. Power Sources, 2000, 89, 206.
E.D. Wachsman, K.T. Lee, Science, 2011, 334, 935.
E.V. Tsipis, V.V. Kharton, J. Solid State Electrochem. 2011,15, 1007.
V.S. Bagotsky, Wiley Press: 2009.
R.Garcia, N.S. Losilla, J. Martinez, R.V. Martinez, F.J. Palomares, Y. Huttel, M. Calvaresi, F. Zerbetto F. Appl. Phys. Lett. 2010, 96, 143110.
M. Tello, R. Garcia, Appl. Phys. Lett. 2001, DOI: 10.1021/nl049544f.
Garcia, R.; Calleja, E.; Perez-Murano, F. Appl. Phys. Lett. 1998, 72, 2295.
Y.W. Xie, C. Bell, T. Yajima, Y. Hikita, H.Y. Hwang, Nano Letters 2010, DOI: 10.1021/nl1012695.
A. Kumar, T.M. Arruda, Y. Kim, I. N. Ivanov, S. Jesse, C. W. Bark, N. C.Bristowe, E. Artacho, P.B. Littlewood, C.B. Eom, S.V. Kalinin, ACS Nano 2012, 6, 3841.
GG1: Organic Photovoltaics
Monday AM, December 02, 2013
Hynes, Level 3, Room 312
9:30 AM - *GG1.01
Energetics of Organic Interfaces: Solutions to Challenging Carrier Injection and Extraction
Antoine Kahn 1
1Princeton University Princeton USAShow Abstract
Significant and steady improvements have been recorded over the past decade in the efficiency of organic light-emitting diodes and solar cells, or in charge carrier mobility in organic field-effect transistors. Interfaces between active organic layers and inorganic electrodes or other organic films or dielectrics control charge injection and collection, charge separation, and charge transport through devices, and a better understanding and control of these interface materials and structures has played a key role in the process. In this talk, we first review the most important mechanisms that control the energetics of organic/electrode interfaces, and show why low barrier contacts to wide band gap, low electron affinity or high ionization energy organic semiconductors are challenging. We then focus on three methods / materials that provide solutions to this challenge. The first involves transition metal oxides (TMO), such as molybdenum and tungsten tri-oxides (MoO3, WO3), which exhibits good n-type conductivity and very high work function (> 6.5 eV) . A detailed analysis of organic/TMO interface energetics and the resulting hole injection process is given. The second involves the realization of efficient electron injection/harvesting electrodes. A “universal” lowering of the work function of many different types of electrodes is implemented via application of an ultra-thin film of the polymer polyethylenimine ethoxylated (PEIE) . Finally, we discuss the role of chemical doping (n- and p-type) in making high conductivity, low energy barrier contacts to organic thin films .
 J. Meyer et al., Adv. Mat. 24, 5408 (2012)
 Y. Zhou et al., Science 336, 327 (2012)
 Y. Qi et al., J. Am. Chem. Soc. 131, 12530 (2009)
10:00 AM - GG1.02
Inducing Metallicity in Organic-Semiconductor Monolayers
Georg Heimel 1 Steffen Duhm 2 Ingo Salzmann 1 Alexander Gerlach 3 Antje Vollmer 4 Frank Schreiber 3 Norbert Koch 1 4
1Humboldt-Universitamp;#228;t zu Berlin Berlin Germany2Soochow University Suzhou China3Universitamp;#22