# Presentation: 447614

## Materials Science at Argonne

*George Crabtree*
*Director, Materials Science Division*

*Postdoc Lunch*
*May 25, 2007*

## Mission

***Mission***

**Create and Deliver World-Class Science **
**to the International Community**

## Materials Science at Argonne

***Materials Science at Argonne***

- Outstanding staff
- Eight ISI Highly Cited Researchers: seven in materials
- Alexei Abrikosov: Nobel laureate in Physics 2003 for superconducting vortices
- MRS medalist for ultrananocrystalline diamond:  Dieter Gruen
- Amanda Petford-Long, FREng, UK 2005
- Sam Bader, David Adler Lectureship 2007
-                                                . . .

- Forefront research areas
- Synthesis: bulk, film, and nanostructured arrays
- Emergent behavior: order, disorder, multiscale, functionality
- In-situ characterization: watch dynamics in real time
- New materials
***	****biocomposites, spin-charge, correlated electron, oxides ...*
*	**nanoscale materials- hybrids, confinement, interfaces, plasmonics ...*

## Critical Mass of People, Ideas, and Techniques

## Strategic Perspective

- What are the biggest opportunities?

- science and materials for energy
-         e.g. catalysis, biological and biomimetic energy conversion,
-               hydrogen, solar

- scattering science with electrons, neutrons and x-rays
- e.g., Transmission Electron Aberration Corrected Microscopy (TEAM),
-        single crystal diffuse scattering,
-        spin echo resolved grazing incidence spectroscopy (SERGIS)

- in situ experiments probing dynamic response
-         e.g. MOCVD epitaxial film growth, oxidation, environmental TEM

- grand challenges of fundamental science
-         e.g. the mechanism of high temperature superconductivity
-               catalysis and control of chemical transformation

- emerging science frontiers
-         e.g. biomolecular materials, quantum computing, plasmonics, spintronics

- applications of MSD basic research
-         e.g. UNCD, hydrogen sensors, artificial retina, HTS wires

## Science Impact

***Science Impact***

- Reviews of Modern Physics       June 2006

## Argonne’s Materials Science User Facilities

***Advanced Photon Source***

***Electron Microscopy ***
***Center***

***Intense Pulsed Neutron Source***

***Center for Nanoscale Materials***
***ramp up to full operation in 07***

## Emphasis: Synthesis

***Emphasis: Synthesis***

- bulk: high pressure new structures, extended doping ranges, exotic oxidation states
- artificial layers: ALD, digital alloys  control stacking with unit precision
- self-assembled nanostructures: colloidal drop-casting, kinetic electrodeposition, bio-scaffold assembly

***exploratory***
- discover new behavior

***strategic***
- high quality targeted materials

- rapid  turnaround
- characterization

***two scientific frontiers***
- novel synthesis techniques
- new materials

## High Pressure Materials Synthesis

- (VO)2P2O7
- 3 GPa

- Ca2-xNaxCuO2Cl2
- 3-5 GPa

- High Pressure Furnaces

*Pressure extends synthesis reach*

- John Mitchell, Dave Hinks, Ken Gray, MSD

***access more phases***
***denser atomic packing***
***higher oxidation states***
***more symmetric structures***

***High Pressure Materials Synthesis***

- pressure (GPa)

- temperature (°C)

- 4

- 6

- 8

- 900

- 1000

- 1100

- 1200

- 1300

- CaCuO2 (II)

- Ca2CuO3
- + CuO

- CaCuO2 (I)

- 1 Atmosphere ~ 0.1 MPa

## Atomic Layer Deposition: Synthesis/Coating

- Mike Pellin, Wang (MSD), John Elam (ES), Peter Stair (CHM, NU), Richard Van Duyne (NU)

- atomic level control of synthesis and sequential coating
- of AAO, aerogel, and mesoporous materials.

***Atomic Layer Deposition: Synthesis/Coating***

- layer by layer deposition

- ZnO on silica aerogel

- Bare Ag
- nanoparticles

- annealed @  300oC

- Al2O3 coated
- annealed  @ 300oC

- create mixed oxides

- flow-thru
- catalysis

- stabilize nano-assemblies

- conformal coating of complex objects

- 10 nm

- 20 nm

**Notes:**
layer by layer deposition without regard for shape, aspect ratio, or line of sight access.
two step chemical process
reactant 1 reacts with surface but not with itself
reactant 2 reacts with reactant 1 but not with itself.
fully coated surfaces, exactly one layer, full chemical control.

## Self-Assembled Nanoparticle Arrays

***Xiao-Min Lin (CNM), Email: xmlin@anl.gov***

***Self-Assembled Nanoparticle Arrays***

- drop casting of colloidal particles
- ordering at liquid-air surface
- perfect hexagonal array
- transport => multijunction tunneling

## Emphasis: Emergent Behavior

***Emphasis: Emergent Behavior***

**Complex oxides**
- spin, charge, lattice interactions
- ferromagnetic, ferroelectric, superconducting, metallic, insulating
- complex disorder
**Electromagnetically self-assembled granular matter **
- competing long/short range interactions
**Biomolecules/nanoparticles in artificial hosts**
**Decoupled spin-charge systems**

**Notes:**
electromagnetically:  fascinating anisotropic patterns, even more fascinating  dynamic behavior on energizing with ac fields, some of which is remarkably similar to collective response of colonies of bacteria.

Bio nano in artificial hosts:  artificial bilipid membranes where nanoparticles or active proteins can assemble to perform functions: harvest light, transmit selected ions, trigger functions through pH, catalyze reactions, synthesize carbohydrates or fuels. . .  These are nanoscale physical and chemical laboratories.

## Electromagnetically Self-Assembled Microstructures

***Electromagnetically Self-Assembled Microstructures***

*Igor Aronson, Alex Snezhko, *
*Wai Kwok, Maksim Sapozhnikov *

***Snezhko, Aranson, Kwok, Phys. Rev. Lett. 93, 108002 (2005)***

***Metallic particles suspended in fluid ***
***Direct or alternating electric and magnetic fields ***

*90 μ Nickel spheres*
*15 Oe magnetic field*

*40-120 μ bronze spheres in toluene-alcohol*

- dynamics of bacteria
- microfluidic devices

***Binary Stars***

***Dancing Chains***

*** ******Pulsating Rings***

- + 1 kV DC

- - 1 kV DC

## Emphasis: In Situ Experiments

***Emphasis: In Situ Experiments***

**explore dynamic mechanisms in real time**
- polarization reversal
- film growth
- oxidation
- chemical catalysis/reaction
**forefront instruments for electron, neutron, x-ray scattering**

- Brian Stephenson, Paul Fuoss,
- Dillon Fong, Jeff Eastman

- Hoydoo You

**Notes:**
science spent a century understanding equilibrium, working very hard to  achieve equilbrium in a  tiny part of the experimental system isolated from external influences.  In situ experiments are  inherently non-equilibrium, focus on the dynamics of change from one state to another. 
can be structural change as films grow, polarization change as domains reverse their electric or magnetic  dipoles,  or chemical change as reactions and catalysis takes place.  This is a formidable experimental and theoretical challenge, to observe and describe dynamics, and ultimately to control it to produce structures and assemblies that are useful. 

crossed field Lorentz magnetic imaging probe for looking at the polarization dynamics of nanomagnetic structures.

## Emphasis: Materials of Increasing Complexity

**multi-component hybrids**
- multi-ferroic, bio/inorganic, soft/hard,
- magnetic/superconducting, core-shell, core-sheath
**nanoscale assemblies**
- lithographic structures, bio-scaffolds,
- colloidal aggregates, kinetic electrodeposition
**nanoporous materials**

- 500 nm

-    Ag
-    Nb

-   AAO

-   a  101 nm
-   dia 45 nm

- 5 nm

- Val Novosad

- Xiao Min Lin

- Zhili Xiao

- Ulrich Welp, Hau Wang

## Emphasis: Behavior at the Nanoscale

**nanoscale surface chemistry**
**confined magnetic/electric polarization**
**laterally patterned charged and polar surfaces**
**short/medium range order**
**	****frustration, complex disorder**

- electrons         diffuse scattering   x-rays, neutrons

- magnetic amplitude

- magnetic orientation

**Notes:**
nanoscale is full of surprizes
chemistry of nanoscale surface islands is very different from bulk, as shown by reslts of our alloy oxidation program
laterally patterned:  FE domains follow terraces in vicinally cut surfaces

## Surface Plasmon Holography

***Surface Plasmon Holography***

- holographic images of SPP launched at 200-nm hole in Au-film

*L. Yin, V. K. Vlasko-Vlasov, U. Welp, S. K. Gray et al, APL ****85****, 467 (2004****)***
*L. Yin  et al,Nanoletters ****5****, 1399 (2005)*

- propagate light along surface
- sub-wavelength lateral confinement of light
*nano-holes convert incident light to SPP*
***SP** = ****inc** {(****m** + ****d **)** **/****m****d**)}**1/2*

- holographic mapping
- amplitude, phase, wavelength

- focusing single nano-hole-fields
- building blocks for photonic chip design

- 200-nm holes
- circle of R=5μm
- focus to sub-μ spot

- NSOM

- SEM

*Ulrich Welp, Vitalii Vlasko-Vlasov, Wai Kwok *

## Next Generation Lorentz Microscopy

**Monochromator**

**Condenser**

**C****s**** corrector**

**LIS Objective**

**Specimen + Stage, **
**             ****10 mm gap**

**LIS Objective**

**C****s**** and C****c**** corrector**

**Projectors**

**Energy filter**

**Fast CCD-system**

**Schottky FEG**

- components
-  JEOL column
-  spherical aberration correction: commercial
-  novel Lorentz image reconstruction
-  chromatic aberration correction: TEAM spin-off

- Amanda Petford-Long, Bernd Kabius, Nestor Zaluzec, Dean Miller

**world-class imaging of magnetic/electric **
**structure with sub-nm resolution**

**Notes:**

design for column based on a new objective lens that allows lots of space for the sample and in situ experimental cells, and dramatically improves spatial resolution.  We already have an implementation plan involving a JEOL column, spherical aberration correction, novel Lorentz image reconstruction, and chromatic aberration based on TEAM spin-off.  This system is well within reach and the top three elements could be operational within a year.  This will be the major research activity of Amanda Petford-Long in collaboration with .  We hope to be sending a white paper to you soon.

## Ferroelectrics Sliced Thin

***Ferroelectrics Sliced Thin***

*** ******Ferroelectricity in Ultrathin Perovskite Films***
- Dillon D. Fong, G. Brian Stephenson, Stephen K. Streiffer, Jeffrey A. Eastman, Orlando Auciello, Paul H. Fuoss, and Carol Thompson, MSD
*Science 11 June 2004: 1650-1653*

- Perspectives in Materials Science:
***Fundamental Size Limits in Ferroelectricity***
- Nicola A. Spaldin
*Science 11 June 2004: 1606-1607*

*Minimum size for ferroelectricity?*
- Basic nanoscience: ferroelectric confinement - 10 nm?
- Applications: memory, transducers, capacitors

*Science/facility synergy*
*• * in situ synthesis of PbTiO3 by MOCVD
- •  characterize ferroelectricity structurally
- •  high intensity x-ray diffraction at APS* *

*3 unit cells = 1.2 nm supports ferroelectricty*

*Dillon Fong, Brian Stephenson, Jeff Eastman, Orlando Auciello, Paul Fuoss (MSD), Stephen Streiffer (CNM), Carol Thompson (NIU)*

## Molecular Machines Based Upon Biofunctionalized Ferroelectrics

***Molecular Machines Based Upon Biofunctionalized Ferroelectrics***

*Fluorescence Micrograph*

- Photoresist

- Electrodes

- E-beam fabricated PZT Channels

**“****Top-Down”** – Lithographically Fabricated BioMEMS

**“****Bottom-up”** - virus produces peptides that link to PZT

- Virus

- peptide

- Millie Firestone, Orlando Auciello (MSD), Leo Ocola (APS/CNM)

- Switching polarization state of patterned ferroelectrics
- controls conformation/orientation of biomolecules

*Cross-section schematic of device*

## Further Information

- Ferroelectric
-  domains measured
- by AFM

*search by*
- research direction
- author
- technique
- material

- http://www.msd.anl.gov/highlights/index.html