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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Charge ordering and multiferroicity in Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} oxyborates

The comparison of Fe{sub 3}BO{sub 5} and Fe{sub 2}MnBO{sub 5} reveals that the 2Fe{sup 2+}: Fe{sup 3+} charge ordering of the former is suppressed in the latter. Spin dynamics probed by ac susceptibility are strongly affected by the substitution, inducing superparamagnetism at low temperature in Fe{sub 2}MnBO{sub 5}. Interestingly, for both oxyborates, glassiness is observed in the dielectric properties at low temperature, but only Fe{sub 3}BO{sub 5} shows a magnetodielectric effect close to its lower magnetic transition. A change in the electrical polarization, measured by pyroelectric current integration, is observed in Fe{sub 3}BO{sub 5} and is even more pronounced in Fe{sub 2}MnBO{sub 5}. Such results suggest that these oxyborates behave like antiferromagnetic relaxor ferroelectrics. These features are proposed to be related to the distribution of the species (Fe{sup 3+}, Fe{sup 2+} and Mn{sup 2+}) over the four transition metal sites forming the ludwigite structure. - Graphical abstract: 90 K [010] electron diffraction patterns of Fe{sub 3}BO{sub 5}. The yellow arrows in the pattern indicate the extra-spots corresponding to the superstructure induced by the charge ordering. - Highlights: • The TEM (ED) study of the Fe{sub 3}BO{sub 5} oxyborate at 90 K reveals a superstructure related to a Fe{sup 2+}/Fe{sup 3+} ordering. • The Fe{sub 2}MnBO{sub 5}, Mn-substituted counterpart, does not show such ordering. • Our magnetic and electric measurements demonstrate that these magnetic ferrites exhibit glassiness in their charges (relaxor-type) with additional superparamagnetism at low T for Fe{sub 2}MnBO{sub 5} and magnetodielectric coupling near T{sub N2}=72 K in Fe{sub 3}BO{sub 5}. • The pyroelectric measurements confirm the existence of a ferroelectric behavior in these antiferromagnets. Accordingly, our results open the route to the study of other large class of the M{sub 2}{sup 2+}M’{sup 3+}BO{sub 5} ludwigites and to their complex magnetism and its relationship to relaxor ferroelectricity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Microstructure and Texture Evolutions in AISI 1050 Steel by Flow Forming

Hot rolled and annealed AISI 1050 steel cylindrical coupons were flow formed at different levels of deformation (66% and 90% wall thickness reduction). TEM studies revealed development of ultra fine (sub) grain cell structure due to severe plastic deformation. The transverse subgrain size changed from 10 m (beginning) to 300nm (66% deformation) to 40nm (90% deformation). EBSD study revealed decreased recrystallization fraction at 90% deformation compared with 66% deformation due to orientation pinning from preferred orientation along {002} planes. No evidence of dislocation pinning or cracking was observed on any samples. The aim of the present work is to study the deformation behaviour and microstructural evolution during conventional flow forming process. The study also sheds light on the strengthening behaviour and structural changes during severe straining.

Dynamic Recrystallization↗
DOE OSTI2022

Microwave catalytic conversion of acetylene for co-production of hydrogen and carbon nanotubes

Natural gas conversion to hydrogen and solid carbon can drastically reduce the carbon footprint. Microwave plasma pyrolysis is an emerging process for chemical industries to directly convert methane (CH 4 ), the major component of natural gas, to hydrogen and carbon, which offers benefits such as fast process dynamics, flexibility, and high product yield. However, the formation of unwanted by-products, like acetylene (C 2 H 2 ), will require extra cost for gas separation. Plasma pyrolysis of CH 4 produces large amount of acetylene at downstream, which is currently used mainly for welding. Here, to avoid gas separation and upgrade acetylene from the downstream of methane plasma reactor, a novel approach toward its transformation to carbon nanotubes (CNT) and pure hydrogen (H 2 ) over Ni-based bimetallic catalyst driven by microwave irradiation has been reported in this work. The dominant gas product was hydrogen. Low concentrations of methane, ethane, and ethylene were observed in the product stream. Catalytic acetylene decomposition was carried out at 400 °C over Al 2 O 3 supported Ni catalyst. The results showed that, at 400 °C, acetylene was dehydrogenated to CNT and hydrogen was the dominant gas in product stream over 10Ni-1Pd-Al 2 O 3 catalyst. Characterizations of spent catalysts was conducted using Raman spectroscopy and transmission electron microscopy (TEM) to investigate the properties of carbon deposited over the catalyst during the catalytic acetylene decomposition. The results highlight that methane can be efficiently converted to hydrogen and CNT through 2-step process, microwave plasma and microwave catalytic conversion of intermediate acetylene, operated in a single reactor system driven by microwave.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A new paradigm in electron microscopy: Automated microstructure analysis utilizing a dynamic segmentation convolutional neutral network

Over the past half century, the transmission electron microscope enabled insight into the fundamental arrangements and structures of materials. State-of-the-art electron microscopes can acquire large image datasets across multiple imaging modalities. However, the manual annotation process for feature or defect quantification may not be feasible with the modern microscope. Convolutional neural networks emerged to characterize individual microstructural features from an image in a cost-effective, consistent manner. However, many of these neural network approaches rely on thousands to hundreds of thousands of manual annotations of each feature type across hundreds of images to train the network for adequate performance. This work focused on the development and application of a pixel-wise defect detection machine-learning dynamic segmentation convolutional neural network with associated automated acquisition and postprocessing to identify microstructural features rapidly and quantitatively from a small initial dataset incorporating multiple imaging modes. The approach was demonstrated for characterization of superalloy 718 from both single image acquisition on multiple detectors to in-situ evolution captured with a single detector on a standard desktop computer to demonstrate the low barrier to entry required for widespread adoption. Pixel-by-pixel class identification was excellent with strong identification of chemically distinct phases, structurally distinct phases, and defect structures, thus demonstrating the new paradigm of machine learning-assisted characterization.

36 MATERIALS SCIENCE↗
DOE OSTI2016

A Closed-Loop Proportional-Integral (PI) Control Software for Fully Mechanically Controlled Automated Electron Microscopic Tomography

A closed-loop proportional-integral (PI) control software is provided for fully mechanically controlled automated electron microscopic tomography. The software is developed based on Gatan DigitalMicrograph, and is compatible with Zeiss LIBRA 120 transmission electron microscope. However, it can be expanded to other TEM instrument with modification. The software consists of a graphical user interface, a digital PI controller, an image analyzing unit, and other drive units (i.e.: image acquire unit and goniometer drive unit). During a tomography data collection process, the image analyzing unit analyzes both the accumulated shift and defocus value of the latest acquired image, and provides the results to the digital PI controller. The digital PI control compares the results with the preset values and determines the optimum adjustments of the goniometer. The goniometer drive unit adjusts the spatial position of the specimen according to the instructions given by the digital PI controller for the next tilt angle and image acquisition. The goniometer drive unit achieves high precision positioning by using a backlash elimination method. The major benefits of the software are: 1) the goniometer drive unit keeps pre-aligned/optimized beam conditions unchanged and achieves position tracking solely through mechanical control; 2) the image analyzing unit relies on only historical data and therefore does not require additional images/exposures; 3) the PI controller enables the system to dynamically track the imaging target with extremely low system error.

Ren, Gang↗
DOE OSTI2014

Dynamic Void Growth and Shrinkage in Mg under Electron Irradiation

We report in-situ atomic-scale investigation of void evolution, including growth, coalescence and shrinkage, under electron irradiation. With increasing irradiation dose, the total volume of voids increased linearly, while nucleation rate of new voids decreased slightly, and the total number of voids decreased. Some voids continued to grow while others shrank to disappear, depending on the nature of their interactions with nearby self-interstitial loops. For the first time, surface diffusion of adatoms was observed largely responsible for the void coalescence and thickening. These findings provide fundamental understanding to help with the design and modeling of irradiation-resistant materials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dynamic observation of dual-beam irradiated Fe and Fe-10Cr alloys at 435 °C

The attractive mechanical properties and superior resistance to void-swelling make ferritic/martensitic alloys a promising structural material for advanced nuclear reactors. However, one anomaly that has intrigued researchers for more than 50 years is the proportion of two types of dislocation loops in Fe and Fe-Cr alloys with Burger vectors b=½<111> and b=<100>. Although the possible mechanisms responsible for the presence of <100> loops continue to be the subject of intense modeling studies, there remains incomplete experimental understanding of fundamental irradiation processes in Fe(Cr) alloys. Here, the dose dependence of the irradiation-induced microstructural evolution was examined from 0 to 20 displacement per atom (dpa) in high purity Fe and Fe-10Cr during simultaneous dual-beam (1 MeV Kr + 10 appm He/dpa) irradiation at 435 °C. We experimentally revealed that the mechanism for the formation of <100> loops may not follow the conventional simple dislocation reaction between two 1½<111> loops. Real-time dynamic formation and evolution of defects including black dot loops, loop coarsening, loop decoration, network dislocations, and cavities were demonstrated. Several results indicated that the addition of Cr and He could impede dislocation loop motion. The evolution of the defect size/density and relative fraction of ½<111> vs <100> loops were quantitatively summarized. With increasing dose, ½<111> loops became the dominant type of loop in both materials. Notably, <100> loops were predominantly observed near grain boundaries only for pure Fe, while arrays of nanoscale black dot defects composing the <100> loop strings were observed in plenty in Fe-10Cr.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Polymer‐Based Ruthenium(II) Polypyridyl Chromophores on TiO 2 for Solar Energy Conversion

Abstract A polychromophoric light‐harvesting assembly featuring a polystyrene (PS) backbone with ionic carboxylate‐functionalized Ru II polypyridyl complexes as pendant groups (PS‐Ru‐A) was synthesized and successfully anchored onto mesoporous structured TiO 2 films (TiO 2 //PS‐Ru‐A). Studies of the resulting TiO 2 //PS‐Ru‐A films carried out by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM) confirmed that the ionic carboxylated Ru II complexes from PS‐Ru‐A led to the surface immobilization on the TiO 2 film. Monochromatic light photocurrent spectroscopy (IPCE) and white light (AM1.5G) current–voltage studies of dye‐sensitized solar cells using the TiO 2 //PS‐Ru‐A photoanode give rise to modest photocurrent and white light efficiency (24 % peak IPCE and 0.33 % PCE, respectively). The photostability of surface‐bound TiO 2 //PS‐Ru‐A films was tested and compared to a monomeric Ru II complex (TiO 2 //Ru‐A), showing an enhancement of ∼14 % in the photostability of PS‐Ru‐A. Transient absorption measurements reveal that electron injection from surface‐bound pendants occurs on the picosecond time scale, similar to TiO 2 //Ru‐A, while time‐resolved emission measurements reveal delayed electron injection occurring in TiO 2 //PS‐Ru‐A on the nanosecond time scale, underscoring energy transport from unbound to surface‐bound complexes. Additionally, charge recombination is delayed in PS‐Ru‐A, pointing towards intra‐assembly hole transport to complexes away from the surface. Molecular dynamics simulations of PS‐Ru‐A in fluid solution indicate that a majority of the pendant Ru II complexes lie within 10–20 Å of each other, facilitating efficient energy‐ and charge transport among the pendant complexes.

Leem, Gyu↗
DOE OSTI2025

Bistable random momentum transfer in a linear on-chip resonator

Optical switches and bifurcation rely on the nonlinear response of materials. Here, we demonstrate linear temporal bifurcation responses in a passive multimode microresonator, with strongly coupled chaotic and whispering gallery modes (WGMs). In microdisks, the chaotic modes exhibit broadband transfer within the deformed cavities, but their transient response is less explored and yields a random output of the analog signal distributed uniformly from “0” to “1.” Here, we build chaotic states by perturbing the multimode microring resonators with densely packed silicon nanocrystals on the waveguide surface. In vivo measurements reveal random and “digitized” output that ONLY populates around 0 and 1 intensity levels. The bus waveguide mode couples first to chaotic modes, then either dissipates or tunnels into stable WGMs. This binary pathway generates high-contrast, digitized outputs. In conclusion, the fully passive device enables real-time conversion of periodic clock signals into binary outputs with contrasts exceeding 12.3 dB, data rates of up to 10 7 · bits per second, and 20 dB dynamic range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Buta-1,3-diyne-Based π-Conjugated Polymers for Organic Transistors and Solar Cells

We report the synthesis and characterization of new alkyl-substituted 1,4-di(thiophen-2-yl)buta-1,3-diyne (R-DTB) donor building blocks, based on the -C≡C-C≡C- conjugative pathway, and their incorporation with thienyl-diketopyrrolopyrrole (R'-TDPP) acceptor units into π-conjugated PTDPP-DTB polymers (P1-P4). The solubility of the new polymers strongly depends on the DTB and DPP solubilizing (R and R', respectively) substituents. Thus, solution processable and high molecular weight PDPP-DTB polymers are achieved for P3 (R = n-C12H25, R' = 2- butyloctyl) and P4 (R = 2-ethylhexyl, R' = 2-butyloctyl). Systematic studies of P3 and P4 physicochemical properties are carried using optical spectroscopy, cyclic voltammetry, and thermal analysis, revealing characteristic features of the dialkynyl motif. For the first time, optoelectronic devices (OFETs, OPVs) are fabricated with 1,3-butadiyne containing organic semiconductors. OFET hole mobilities and record OPV power conversion efficiencies for acetylenic organic materials approach 0.1 cm2/(V s) and 4%, respectively, which can be understood from detailed thin-film morphology and microstructural characterization using AFM, TEM, XRD, and GIWAXS methodologies. Importantly, DTB-based polymers (P3 and P4) exhibit, in addition to stabilization of frontier molecular orbitals and to -C≡C-C≡C- relief of steric torsions, discrete morphological pliability through thermal annealing and processing additives. The advantageous materials properties and preliminary device performance reported here demonstrate the promise of 1,3-butadiyne-based semiconducting polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Enhancement of electron energy during vacuum laser acceleration in an inhomogeneous magnetic field

In this paper, the effect of a stationary inhomogeneous magnetic field on the electron acceleration by a high intensity Gaussian laser pulse is investigated. A focused TEM (0,0) laser mode with linear polarization in the transverse x-direction that propagates along the z-axis is considered. The magnetic field is assumed to be stationary in time, but varies longitudinally in space. A linear spatial profile for the magnetic field is adopted. In other words, the axial magnetic field increases linearly in the z-direction up to an optimum point z{sub m} and then becomes constant with magnitude equal to that at z{sub m}. Three-dimensional single-particle simulations are performed to find the energy and trajectory of the electron. The electron rotates around and stays near the z-axis. It is shown that with a proper choice of the magnetic field parameters, the electron will be trapped at the focus of the laser pulse. Because of the cyclotron resonance, the electron receives enough energy from the laser fields to be accelerated to relativistic energies. Using numerical simulations, the criteria for optimum regime of the acceleration mechanism is found. With the optimized parameters, an electron initially at rest located at the origin achieves final energy of γ=802. The dynamics of a distribution of off-axis electrons are also investigated in which shows that high energy electrons with small energy and spatial spread can be obtained.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Kinetics of Magnetic Skyrmion Crystal Formation from the Conical Phase

The particle-like magnetic skyrmion or skyrmion lattice (SkX) formation has promoted strong application and fundamental science interests. Despite extensive research, the kinetic of the SkX development is much less understood because of the ultrafast spin rotation and high sensitivity to external perturbations. In this work, using in situ Lorentz transmission electron microscopy, we successfully measured the dynamics of SkX formation from the conical phase with precise control of both the temperature and the magnetic field. We discovered that the Avrami equation can accurately describe the transition process with an initial Avrami constant around 1, suggesting that the rate-limiting step for the quasiparticle lattice formation is one-dimensional heterogeneous nucleation of individual skyrmions. A modified Arrhenius rate law is established, with an energy barrier that has a square-root dependence on temperature and a quadratic dependence on the magnetic field. This study paves the way toward precise and predictable manipulation of topological spin structures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Atomic Origin of the Autocatalytic Reduction of Monoclinic CuO in a Hydrogen Atmosphere

Reducibility is key for the use of bulk metal oxides in chemical transformation involving redox reactions but probing microscopic processes of oxide reduction is challenging. This is because the insulating nature of bulk oxides restricts ion and electron spectroscopic measurements of oxide surfaces. Herein, using a combination of environmental transmission electron microscopy and atomistic modeling, we report direct in-situ atomic-scale observations of the surface and subsurface dynamics and show that the hydrogen induced CuO reduction occurs via the surface decay of Cu-O/Cu bilayer atomic steps, formation of partially reduced CuO superstructure by the self-ordering of O vacancies in the subsurface, and collapse of Cu-O layers in the bulk. In this work, all these substeps can be traced back to the progressively increased concentration and activity of O vacancies in the surface and subsurface of the oxide, thereby leading to the self-accelerated oxide reduction. These results demonstrate the microscopic details that may have broader applicability in modulating various redox processes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mapping 1D Confined Electromagnetic Edge States in 2D Monolayer Semiconducting MoS 2 Using 4D-STEM

Here, four-dimensional (4D) scanning transmission electron microscopy is used to study the electric fields at the edges of 2D semiconducting monolayer MoS2. Sub-nanometer 1D features in the 2D electric field maps are observed at the outermost region along zigzag edges and also along nanowire MoS-terminated MoS 2 edges. Atomic-scale oscillations are detected in the magnitude of the 1D electromagnetic edge state, with spatial variations that depend on the specific periodic edge reconstructions. Electric field reconstructions, along with integrated differential phase contrast reconstructions, reveal the presence of low Z number atoms terminating many of the uniform edges, which are difficult to detect by annular dark field scanning transmission electron microscopy due to its limited dynamic range. Density functional theory calculations support the formation of periodic 1D edge states and also show that enhancement of the electric field magnitude can occur for some edge terminations. The experimentally observed electric fields at the edges are attributed to the absence of an opposing electric field from a nearest neighbor atom when the electron beam propagates through the 2D monolayer and interacts. These results show the potential of 4D-STEM to map the atomic scale structure and fluctuations of electric fields around edge atoms with different bonding states than bulk atoms in 2D materials, beyond conventional imaging.

2D materials↗
DOE OSTI2015

Observing the Growth of Metal-Organic Frameworks by In-Situ Liquid Cell Transmission Electron Microscopy

Liquid Cell Transmission Electron Microscopy (LCTEM) can provide direct observations of solution phase nanoscale materials, and holds great promise as a tool for monitoring dynamic self assembly processes. Control over particle behavior within the liquid cell, and under electron beam irradiation, is of paramount importance for this technique to contribute to our understanding of chemistry and materials science at the nanoscale. However, this type of control has not been demonstrated for complex, organic macromolecular materials, which form the basis for all biological systems, all of polymer science, and encompass important classes of advanced porous materials. Here we show that by controlling the liquid cell surface chemistry and electron beam effects, the dynamics and self-assembly of metal-organic frameworks (MOFs) can be observed. Our results demonstrate that hybrid organic/inorganic beam sensitive materials can be analyzed with LCTEM and at least in the case of Zif-8 dynamics, the results correlate with observations from bulk growth or other standard synthetic conditions. We anticipate that direct, nanoscale imaging by LCTEM of MOF nucleation and growth mechanisms, may provide insight into controlled MOF crystal morphology, domain composition, and processes influencing defect formation.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2024

In Situ Liquid Electron Microscope Cells Strongly Attenuate Electrochemical Behavior

In situ electrochemical Scanning Transmission Electron Microscopy (ec-S/TEM) probes the dynamics of electrochemical processes in real time and at high spatial resolution. This method utilizes microfabricated electrochemical cells, with enclosed dimensions of 800 μm wide, 800 μm long, and 1–2 μm tall, with electron-transparent silicon nitride windows. Working, counter, and reference electrodes in the configuration studied are deposited Pt with a planar surface area of about 1 μm 2 and a height of 50 nm. The cell confines the electrolyte within a 1 μm tall channel, and the microfabricated electrodes have a non-standard geometry, are coplanar, and are not front-facing. As such, standard assumptions of electrochemical experiments do not apply. COMSOL modeling was used to compare and contrast differences in electrochemical behavior between conventional experimental setups and the in situ ec-S/TEM cells. Cell height strongly affected voltammogram measurements: peak magnitudes and shifts correlate directly to cell height. Reactant concentration above the electrode quickly decreases during deposition, leading to a planar diffusion-dominated regime. The concentration gradient prioritizes particle growth along the thin edges of the electrode and not on the planar part of the electrode. Experiments done in the ec-S/TEM ex situ of a TEM verify the model’s accuracy.

Wittman, Reed M. [Oak Ridge National Laboratory (O↗
DOE OSTI2016

Applications of Transient Grating Spectroscopy to Radiation Materials Science

Radiation damage is an inherently multi-scale phenomenon, with much of the key material evolution occurring at the mesoscale. Current techniques for the direct interrogation of material property changes due to irradiation either function with very small volumes, such as in-situ TEM, cannot cover the full range of defect populations produced, such as in positron annihilation spectroscopy, or requires destruction of the test material, such as in standard or micromechanical testing. In addition, the ultimate quantities of interest to radiation materials scientists are the changes in key material properties with irradiation. These include stiffness, ductility, and thermal conductivity for structural materials, and optical properties such as index of refraction or changes in transmittance spectra for optically active materials. The latter of these are often correlated directly to stress- or thermally-induced changes, themselves a function of the specific defect populations responsible for their change. The rapid study of such a mesoscale phenomenon requires an inherently mesoscale technique, where multiple quantities of interest can be accurately measured in very short times. Determining the sensitivity of any technique with known certainly is of critical importance to qualifying a new technique to measure in-situ material property changes during irradiation. In this paper, we present the new applicability of an existing technique, known as transient grating (TG) spectroscopy, to rapidly and accurately study key problems in radiation materials science. Results quantifying the absolute sensitivity of the technique are presented, alongside molecular dynamics (MD) simulations of the TG spectroscopy process to gauge direct agreement between theory, simulation, and experiment. An example problem of interest is demonstrated as an illustration of what is possible, showing elastic and thermal changes in irradiated silicon carbide (SiC) films. Finally, future work to quantify the effects of experimentally-simulated radiation defects is proposed, in support of building a database to use TG spectroscopy to deconvolve irradiated material property changes in-situ in terms of the defect populations responsible for their evolution. The application of the TG spectroscopy technique to in-situ radiation materials science has the potential to answer long-standing questions in the field, relating to ion beam rastering, the onset of void swelling, and direct measurement of radiation-created point defect concentrations. Before it can do so, the technique must carefully be analyzed and tuned to increase its sensitivity, the certainty of its results, and the ability to predict radiation-induced changes by simulations must be developed. Making such measurements in-situ with the aid of predictive MD simulations has the potential to elucidate mechanisms of radiation damage accumulation, as well as more rapidly qualify radiation-resistant alloys for service in nuclear systems. Work is underway to build this database of experimentally-simulated radiation-produced defects, which will be combined and compared with actual irradiated materials for eventual in-situ deconvolution of the TG signal into the defect populations responsible for irradiation-induced microstructural change. (authors)

36 MATERIALS SCIENCE↗
DOE OSTI2015

Charge Recombination, Transport Dynamics, and Interfacial Effects in Organic Solar Cells

The need for renewable sources of energy is well known. Conversion of sunlight to electricity using solar cells is one of the most important opportunities for creating renewable energy sources. The research carried out under DE-FG02-08ER46535 focused on the science and technology of “Plastic” solar cells comprised of organic (i.e. carbon based) semiconductors. The Bulk Heterojunction concept involves a phase separated blend of two organic semiconductors each with dimensions in the nano-meter length scale --- one a material that functions as a donor for electrons and the other a material that functions as an acceptor for electrons. The nano-scale inter-penetrating network concept for “Plastic” solar cells was created at UC Santa Barbara. A simple measure of the impact of this concept can be obtained from a Google search which gives 244,000 “hits” for the Bulk Heterojunction solar cell. Research funded through this program focused on four major areas: 1. Interfacial effects in organic photovoltaics, 2. Charge transfer and photogeneration of mobile charge carriers in organic photovoltaics, 3. Transport and recombination of the photogenerated charge carriers in organic photovoltaics, 4. Synthesis of novel organic semiconducting polymers and semiconducting small molecules, including conjugated polyelectrolytes. Following the discovery of ultrafast charge transfer at UC Santa Barbara in 1992, the nano-organic (Bulk Heterojunction) concept was formulated. The need for a morphology comprising two interpenetrating bicontinuous networks was clear: one network to carry the photogenerated electrons (negative charge) to the cathode and one network to carry the photo-generated holes (positive charge) to the anode. This remarkable self-assembled network morphology has now been established using Transmission electron Microscopy (TEM) either in the Phase Contrast mode or via TEM-Tomography. The steps involved in delivering power from a solar cell to an external circuit are the following: • Photo-excitation of the donor (or the acceptor). • Charge transfer with holes in the donor domain and electrons in the acceptor domain. • Sweep-out to electrodes prior to recombination by the internal electric field. • Energy delivered to the external circuit. Each of these four steps was studied in detail using a wide variety of organic semiconductors with different molecular structures. This UC Santa Barbara group was the first to clarify the origin and the mechanism involved in the ultrafast charge transfer process. The ultrafast charge transfer (time scale approximately 100 times faster than the first step in the photo-synthesis of green plants) is the fundamental reason for the potential for high power conversion efficiency of sunlight to electricity from plastic solar cells. The UCSB group was the first to emphasize, clarify and demonstrate the need for sweep-out to electrodes prior to recombination by the internal electric field. The UCSB group was the first to synthesize small molecule organic semiconductors capable of high power conversion efficiencies. The results of this research were published in high impact peer-reviewed journals. Our published papers (40 in number) provide answers to fundamental questions that have been heavily discussed and debated in the field of Bulk Heterojunction Solar Cells; scientific questions that must be resolved before this technology can be ready for commercialization in large scale for production of renewable energy. Of the forty publications listed, nineteen were co-authored by two or more of the PIs, consistent with the multi-investigator approach described in the original proposal. The specific advantages of this “plastic” solar cell technology are the following: a. Manufacturing by low-cost printing technology using soluble organic semiconductors; this approach can be implemented in large scale by roll-to-roll printing on plastic substrates. b. Low energy cost in manufacturing; all steps carried out at room temperature (approx. a factor of ten less than the use of Silicon which requires high temperature processing). c. Low carbon footprint d. Lightweight, flexible and rugged Because of the resolution of many scientific issues, a significant fraction of which were addressed in the research results of DE-FG02-08ER46535, the power conversion efficiencies are improving at an ever increasing rate. During the funding period of DE-FG02-08ER46535, the power conversion efficiencies of plastic solar cells improved from just a few per cent to values greater than 11% with contributions from our group and from researchers all over the world.

14 SOLAR ENERGY↗