Quanta to the Continuum: Opportunities for Mesoscale Science 1 meso2012.com John Sarrao George Crabtree BESAC, July 2012

The BESAC Charge on Mesoscale Science Excerpts from Dr. Brinkman’s charge letter of February 14, 2011: Report due early Fall 2012 A central theme of these reports is the importance of atomic and molecular scale understanding of how nature works and how this relates to advancing the frontiers of science and innovation. I would now like BESAC to extend this work by addressing the research agenda for mesoscale science, the regime where classical, microscale science and nanoscale science meet. I see two parts to this new study: 1. Identify mesoscale science directions that are most promising for advancing the Department’s energy mission. 2. Identify how current and future BES facilities can impact mesoscale science. This study could prompt a national discussion of mesoscale science at the level heard during the initial formulation of the National Nanotechnology Initiative a decade ago. 2

The BESAC Meso Subcommittee John Hemminger, Irvine, BESAC chair William Barletta, MIT, BESAC Gordon Brown, Stanford, BESAC Roger French, CWRU, BESAC Laura Greene, UIUC, BESAC Bruce Kay, PNNL, BESAC Mark Ratner, Northwestern, BESAC John Spence, Arizona, BESAC Doug Tobias, Irvine, BESAC John Tranquada, Brookhaven, BESAC Paul Alivisatos, LBNL Frank Bates, Minnesota Marc Kastner, MIT Jennifer Lewis, UIUC Tony Rollett, CMU Gary Rubloff, Maryland John Sarrao, LANL, co-chair George Crabtree, ANL & UIC, BESAC, co-chair 3

Plan for this Meeting 4 Now: Articulate the message that is embodied in the report Later this afternoon: Discuss report in detail and gather your feedback* *we acknowledge some gaps exist now in the report Tomorrow morning: React to your input and propose a path forward Goal: Achieve BESAC approval of report, assuming successful completion of the proposed plan

Venues for Community Input: Town Halls and Website APS Boston Wed Feb 29 Marc Kastner and William Barletta (MIT), hosts ACS San Diego Tues Mar 27 John Hemminger, Douglas Tobias (UCI), hosts MRS San Francisco Mon Apr 9 Cynthia Friend, Gordon Brown (Stanford/SLAC) Don DePaolo, Paul Alivisatos (Berkeley/LBNL), hosts ACS Webinar Thu April 12 John Hemminger, Douglas Tobias (UCI), hosts Chicago Mon May 14 George Crabtree (ANL & UIC), host Website Meso2012.com 5

6 Of the ~ 1000 people that participated in town halls, webinars, and other outreach activities, more than 100 submitted quad charts to meso2012.com Opportunity Meso Challenge Approach Impact Electro-magnetic phenomena can be modeled exactly, with no approximations apart from the discretization  “numerical experiments” are thus enabled, dramatically speeding-up the scientific progress. Numerous large-scale, cheap meso-fabrication techniques have emerged recently, including: nano-imprint, interference lithography, self-assembly. Meso-scales are exactly compatible with the natural length-scale of the light that is relevant for energy applications: visible and infra-red wavelengths. Tailoring the meso-structure, one can tailor the laws of physics (as far as light is concerned) almost at will. Exploring plasmonics, one can “shrink” length-scales of light to even smaller scales, closer to natural length-scales of electronics, thus bridging the gap in the scales between electronics and photonics. To enable massive adoption in the energy sector, one needs to have the ability to control meso-structure in macro-scopic objects: novel cheap and reliable mass-fabrication methods are needed. Novel gain materials are needed, compatible with meso- fabrication methods. Plasmonic losses are large: novel plasmonic materials/approaches are needed. We create the laws of physics  large opportunities to explore novel physics emerge: imagination is the limit. 92% of all primary energy sources are converted into electrical and mechanical energy via thermal processes  ability to tailor thermal radiation and/or absorption has numerous applications in the energy sector. Solar energy is perhaps the most promising clean-energy source: at the heart of its exploration lies the need to control the behavior of light  meso-photonics promises a wide range of applications: more efficient photo-voltaics, solar-pumped lasers, solar-thermal systems… ~25% of US electricity consumption is due to lighting: meso- photonics could enable dramaticaly more efficient lighting, in terms of: better LEDs, incadescent sources... Meso-photonics for energy applications

7  Why: the need for innovation, as articulated in Science for Energy Technology  Why now: the insights and tools we’ve gained (and are still gaining) from nanoscience, as articulated in New Science for a Secure and Sustainable Energy Future  What: build on basic science challenges, as articulated in Directing Matter and Energy: Five Challenges for Science and the Imagination Meso: Background

Meso: Beyond atomic, molecular, and nano quantum classical isolated interacting collective simple perfect homogeneous complex imperfect heterogeneous meso 8

9 bulk Sequential catalyzed reactions atomic Meso integrates structure, dynamics, and function 9 H2OH2O O2O2 H2OH2O H2H2 H+H+ Groundwater dynamics Carbon sequestration Shale oil and gas Mesoscale assembly Solar water splitting

Multiple degrees of freedom interact constructively Complexity enables new phenomena and functionality Consilience of systems and architectures Biological complexity with inorganic materials Multiple spatial, temporal and energy scales meet Quantum meets classical Functional defects and heterogeneous interfaces Multi-scale dynamics essential for functionality At the meso scale, new organizing principles are needed Meso embraces emergent as well as reductionist science What laws unify top-down and bottom-up assembly? Meso is an Opportunity Space 10

Meso exploits interacting degrees of freedom: Light & Matter Photonic crystals Mesoscale structure Controls light : direction, frequency, phase, coherence and intensity Impacting energy technologies : Solar electric, solar fuel, light emitting diodes, chemical energy conversion A broad new horizon as rich as the laser revolution 11 1 µ 5 µ Surface plasmons 1µ Metamaterials 50 nm

Defects and interfaces are functional at the mesoscale 12 Decorated functional mesopores Superconducting pinning landscape Catalytic reactive surface

13 atoms Molecules energy transduction Lattices 1D - 3D polymers membranes solutions vortices structural defects superconductors colloids Electronics insulators - metals mechanics phonons cells chemistry, life electron-phonon resistivity defect aggregation fracture cracks work hardening zero resistivity magnetics domains, hysteresis locomotion photosynthesis mean free path Cooper pairs finite resistivity sedimentary rocks fossil fuels The hierarchy of architectures, phenomena and functionalities plastics 20 th century Reductionist science top down to nano/atomic/molecular 21 st century Constructionist science bottom up nano to meso New architectures, phenomena, functionality and technology

Six priority research directions (PRDs) for mesoscale science have emerged from our study Mastering Defect Mesostructure and its Evolution Regulating Coupled Reactions and Pathway-Dependent Chemical Processes Optimizing Transport and Response Properties by Design and Control of Mesoscale Structure Elucidating Non-equilibrium and Many-Body Physics of Electrons Harnessing Fluctuations, Dynamics and Degradation for Control of Metastable Mesoscale Systems Directing Assembly of Hierarchical Functional Materials 14

Mastering Defect Mesostructure and its Evolution Deformation Crack Initiation Crack Propagation Failure 3D Coherent Imaging x-ray tomography New probes enable imaging of damage initiation and evolution at the mesoscale 15

Regulating Coupled Reactions and Pathway-Dependent Chemical Processes electrons Li + ions solid-electrolyte-interface cathode electrolyte anode Li ion battery 16 CO 2 sequestration Aqueous solution surface Interfaces control reactivity in the natural and synthetic worlds

Optimizing Transport and Response Properties by Design and Control of Mesoscale Structure Phenomena Ionization Ion insertion/extraction Electronic / ionic conduction Volume expansion/contraction Degrees of freedom Electronic Ionic Chemical Mechanical Meso Functionality Energy storage Energy delivery Reversibility on demand 17

Elucidating Non-equilibrium and Many-Body Physics of Electrons ~1µ Making “contact” with many-body electron states… and intrinsic inhomogeneity …to be controlled for electronic functionality reveals dynamic localization 18

Harnessing Fluctuations, Dynamics and Degradation for Control of Metastable Mesoscale Systems Metastability at the mesoscale  control of fluctuation spectra impacts lifetime and aging The opportunity is to emulate nature: smart and self-healing materials for advanced energy technologies 19

20 many interacting degrees of freedom Elements of Assembly compositional structural functional unit architectural connecting functional units temporal connecting sequential steps Directing Assembly of Hierarchical Functional Materials Integration of disparate materials classes by “top down” and “bottom up” approaches is the underpinning focus of directed mesoscale assembly

Realizing the meso opportunity requires advances in our ability to observe, characterize, simulate and ultimately control matter. Synthesis Characterization Theory Simulation Mesoscale Physics, Materials and Chemistry 21 Mastering mesoscale materials and phenomena requires the seamless integration of theory, modeling and simulation with synthesis & characterization

22 Opportunities for Mesoscale Tools and Instruments Synthesis / Assembly -Directed synthesis of complex inorganic materials -Multi-step, multi- component assembly processes -Computational synthesis / assembly Characterization -In situ, real time dynamic measurements: 4D materials science -Multi-modal experiments, e.g. structure + excitation + energy transfer -Multi-scale energy, time and space Theory / Simulation -Far from equilibrium behavior -Heterogeneous/disordered systems -Dynamic functionality of composite systems Cross-cutting Challenges Co-design/integration of Synthesis  Characterization  Theory/Simulation Directed Multi-step, multi-component assembly processes that scale Multi-modal simultaneous and sequential measurements spanning energy, length & time scales Predictive theories and simulation of dynamic functionality 22

23 Creating the materials, structures, and architectures that access the benefits of mesoscale phenomena is a key challenge Computational tools for functionality by design In situ observation and control of synthesis processes Directed synthesis to create complex materials and controlled interfaces Assembly processes and pattering strategies

24 3D Coherent Imaging x-ray tomography New methods to watch multi-d defect evolution & tracking In situ, in operando measurements Long duration measurements Exciting new sources (e.g., LCLS, NSLS-II, SNS) are available, but need to advance optics, detectors, environments, and data handling Notional 3d, in situ, multi-modal measurement Simultaneous diffraction, Imaging and spectroscopy Time-correlated probes of local structure, composition, excitation Data mining strategies

Computational materials challenges includes experimental validation Theory and simulation need to connect models across scales AND incorporate emergent phenomena to realize functionality by design Well-documented and curated community codes is a key gap nm µmmm m length scale time scale fs ps ns µs ms sec days years atomic molecular nano meso macro DFT MD, MC, DMFT Lattice Boltzmann TDGL, DDFT, Mori-Tanaka, Halpin-Tsai, Lattice Spring, Finite Element 25

26 We lack the needed workforce to fully tap the meso opportunity New modalities of research necessitate a new generation of mesoscale scientists Frontier is interdisciplinary, requiring researchers who move across boundaries and interfaces Need for integrated teams to address large, complex challenges Foster and grow science of mesoscale synthesis Complex, multi-modal measurements  enhanced partnering with instrument scientists and large scale facility Seamless integration of theory and simulation with synthesis and characterization AND translation to common codes Future mesoscale scientists will fuel broader manufacturing and innovation workforce

The ability to manufacture at the mesoscale … to yield faster, cheaper, higher performing, and longer lasting products. The realization of biologically inspired complexity and functionality … to transform energy conversion, transmission, and storage. The transformation from top-down design … to bottom-up design … producing next-generation technological innovation. Perspective Meso is an opportunity space: mesoscale phenomena, architectures, and interfaces New capabilities are needed to discover principles and enable solutions: directed assembly, in situ dynamics, and multi-modal function Success will be transformational: Meso2012.com “It is both the magnitude of the challenge in bridging quanta to the continuum and the potential dividend in controlling the mesoscale that have energized the research community and motivated this report.” 27