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Materials Research in the 21Materials Research in the 21stst CenturyCenturyUK Polymer Showcase, Sept. 12, 2006UK Polymer Showcase, Sept. 12, 2006

Anthony K. CheethamInternational Center for Materials Research

University of California at Santa Barbara

icmricmr Materials Research in the 21Materials Research in the 21stst CenturyCentury

• What was science like in 1906?

• How does it look in 2006?

• Major technical trends in the early 21st century

• Future developments in materials research

• Changes in how materials research is being done

• Global scientific issues

• Science and the developing world

• Preparing scientists/engineers for global challenges

• Conclusions

icmricmr SCIENCE IN 1906

• What had recently been discovered?– The periodic table (Mendeleev, 1869)– The electron (1897), X-rays (1895)– Radioactivity (1896), Noble gases (1895-8)

• What was about to be discovered?– The structure of the nucleus (1911)– Isotopes (1913), mass spectrometry (1918)– X-ray diffraction (1912), chemical bond (1918)– Bohr atom (1913), wave mechanics (1923)

• What was still many years away?– Antibiotics, structure of sugars, proteins, DNA– Nylon, polythene, perspex, trans-U actinides…

icmricmr SCIENCE IN 2006

• What has recently been discovered?– First principles computation (1960s on)– Dendrimers (1980s)– Molecular electronics (1981)– Quantum dots (1982)– The buckyball, C60 (1985)– High Tc superconductivity (1986)– Giant magnetoresistance/spintronics (1988)– Wide band gap (In/Ga)N LEDs (1993)– High throughput materials discovery

(1995)• What is about to be discovered and

what is still many years away?

AKC with Alan HeegerOctober 2000

Harry Kroto with Ram Rao

icmricmr Major Scientific Trends in the early Twenty-first Century

• Ramifications of the genomics/proteomics revolution– More powerful tools for drug discovery and targeting– Development of personalized consumer products and functional foods

solutions• Nanotechnology and nanomaterials

– The development of a vast array of nanomaterials– The applications of such materials in devices

• High throughput experimentation– Now being applied in a wide range of areas, beyond drug and materials

discovery, e.g. rapid screening and characterization• Computational methods

– There are dramatic advances in our ability to model chemical behavior• Energy and the environment

– Trends in batteries, solar energy (PV), lighting, emission control

Nanoparticles

icmricmr C60: Buckminsterfullerene

The diameter isone billionthof a meter indiameter, i.e.10-9 meters, orone nanometer

Kroto, Heath, O’Brien, Curl and Smalley, 1985

icmricmr Carbon Nanotubes

Carbon Nanotubeimages -Sumio IijimaNature 1991;Note the multiple walls, which are more common than single ones

Carbon nanotubeshave ten times the tensile strength of steel!

icmricmr Potential Applications ofBuckyballs and Carbon Nanotubes

• Structural materials, as in carbon nanotubereinforced composites (Hyperion)

• Sensors (Nanomix)• Displays using Field Emission (Applied Nanotech)• Carbon nanotube transistors for molecular

computers (IBM)• Data storage (IBM)• Hydrogen storage in carbon nanotubes for fuel

cells and related applications (Nanomix)• Photovoltaic cells (Konarka)• Scanning probe tips for AFMs (Seiko/Daiken) • Water purification (Seldon)

icmricmr Inorganic Nanotubes

Onions and nanotubes form with other inorganic systems that adopt layered structuresTenne, Weizmann Institute, Israel

Molybdenum Disulfide

icmricmrNanocrystals and nanorods of

metals and semiconductors (1999)

Cadmiumselenide

nanorod; morphology

can be controlled by

surface Chemistryin solutionCadmium selenide

nanocrystal (15K atoms)

This is the tip of the iceberg…

icmricmr Other Inorganic Nanomaterials

• Metal nanoparticlese.g. Au, Ag, Al, Si, Fe, Pd, Pt….

• Oxide nanoparticlese.g. TiO2, SiO2, CeO2, Fe2O3, Fe3O4….

• Ceramicse.g. BN, Al2O3, SiC, Al4C3….

• Semiconductorse.g. GaN, ZnO, CdSe….

• Mineralse.g. clays, zeolites, hydroxyapatite, talc, spinels

• Various other functional inorganicse.g. BaCO3, LnPO4, MS2 (M=Mo,W,Nb etc)

icmricmr Nanowires of Ceramics

Most nanomaterials can be made in a number of different morphologies. For example, many oxides and other ceramics can bemade not only in regular particulate form, but also as nanowires etc. Examples of nanowires of Al2O3 and ZnO are shown below. In this case we use a different synthetic approach: carbothermal synthesis.

Rao, Gundiah, Deepak, Govindaraj and Cheetham J. Mater. Chem. 14, 440-450 (2004)

icmricmr Nanomaterials - Properties

• Many of the properties of nanomaterials are fundamentally different from those of their macroscopic analogues

• Smaller size (1-100 nm) results in:– Changed solubility (high surface/bulk ratio)– Changed biological properties (increased activity)– Changed physical properties

(eg color, transparency, magnetism, quantum effects)– But unchanged chemical properties, other than surface

properties which can radically affect catalysis• Morphologies and aspect ratios also affect properties

icmricmr Qdots of CdSe give intense fluorescencewhen excited in the UV

The color can be controlled by controling the particle size

Reproduced From http://www.qdots.com/new/technology/what.html

icmricmr Applications of Inorganic Nanoparticles

• Nanocrystals of gold functionalized with DNA for biorecognition • Platinum group metal nanorods for security barcodes• Nanocrystals of aluminum for rocket propellants etc• Magnetic nanoparticles of iron for drug delivery• Purification filters based on Al2O3 nanowires• Porous nanoparticles of silica for delivery of functional molecules• Nanocrystals of ZnO or TiO2 for UV absorption• Nanocrystals of zeolites and other oxides for catalysis• MoS2 onions for lubrication • Nanocrystals of CdSe, Si and TiO2 for solar cells• Nanocrystals of SiC for ceramic applications• Calcium phosphate nanoparticles for bone applications• Nanoparticles of rare-earth phosphors for security tagging and solid state

lighting• Nanoparticles of minerals for composites

icmricmr Organic Nanomaterials

There is a wide range of organic and polymer nanoparticles that are finding applications indrug delivery, cosmetics, foods, catalysis, etc:

• Micelles• Liposomes• Dendrimers• Nanoemulsions• Calixarenes• Cyclodextrins

icmricmr Dendrimers

The monomers (dendrons) are linked to form globular shapes, 2-10 nm

D.A. TomaliaF. VögtleJean Fréchet

icmricmr Synthetic Liposomes & Micelles

Above the critical micell concentration (CMC) amphiphilic lipids tend to adopt specific aggregates in aqueous solution in order to avoid contact between theirhydrophobic alkyl chains and the aqueous environment. Such lipids can form monomolecular layers at the air-water boundary and bimolecular layers betweentwo aqueous compartments. Micelles are spherically closed monolayers, whereasliposomes are closed bimolecular vesicles possessing a bilayer structure.

icmricmr Calixarenes –Molecular Nanoparticles

The proposed structureof Zinke and Ziegler,1944

Calixarenes and cyclodextrins provide excellent hosts for small molecules and can be used as delivery systems (e.g. Insert Therapeutics). They can also be functionalized, e.g. with lipids that self assemble to form liposomes (A. Hirsch)

Nanostructured Materials

icmricmr Nanoporous Inorganics

• Aluminosilicate zeolites• Aluminum phosphates (AlPO4s)• Transition metal and other phosphates• Metal sulfates• Metal oxides• Metal chalcogenides• Metal halides• Metal nitrides

Many inorganics form open-framework polymorphs, but not all can be rendered nanoporous!

Nanoporous Nickel Phosphate

icmricmr Hybrid Inorganic-Organic Materials

Coordination polymers are an important new class of hybrid materials. They form some of the lowest density materials ever synthesized O’Keeffe & Yaghi, Nature, 402 276 (1999)

•Zn4O(1,4 benzenedicarboxylate):–Synthesized using room temperature solvent routes.–Structure may be modified by varying the carboxylic acids–Extremely Low densities (~0.1 g/ml)

icmricmr Hybrid Nanoporous Solids II

Metal oxide type structures can also be made in the form of inorganic-organic hybrids, e.g. nickel succinate, left Cheetham & Forster, Angew. Chem., 41, 457 (2002)

Lanthanum iminodiacetate,right Neeraj, Keller & Cheetham, 2005

icmricmr Nanoscale Morphology Control of Block Copolymers

Linked homopolymer blocks.

B

A

AAHolden & Legge(Shell – Kraton Polymers)

ABA Triblock Thermoplastic Elastomer

f

icmricmr Nanocomposite Materials

SEM image of an abalone shell nanocomposite; the tablets of calcite are about 1 micron thick (Morse & Stucky, UCSB) Silica diatom

icmricmr SWNT Nanocomposites

Stress-Straincurves

Single walled carbon nanotubes have a marked influence on the mechanical properties of polyelectrolyte thin films A. Hirsch in Nature Materials, 2002

icmricmr Two Classes of LEDs for SSL

• Inorganic GaN and In/GaN Materials- Blue light was the missing color needed for full-

color displays and white solid-state lighting- New options with near UV LEDs - Ideal for point source illumination- Recent LED efficiency improvements

• Organic LEDs (OLEDs)- All colors now available- Ideal for area illumination- Cheaper to manufacture- But poorer stability than inorganic LEDs

(20 k hours versus 100 k hours that is needed)

icmricmr SSL Statistics

• Lighting consumes about 30% of the USA’s electricity• Solid state lighting has the potential to reduce energy

consumption from lighting by ~30% by 2025• That equates to ~9% of the USA’s electricity consumption• It would eliminate the need to build ~40 1000 MW power

plants• Most of the cost savings are in the Commercial sector,

followed by Residential• Savings should begin in ~2010• The cost savings are approx. $25 billion per year by 2025• The SSL market revenues are ~$10 billion per year by 2025• R&D investment (excluding OLED) in the USA in 2005 was

$171 million; Japan- $166 mill. and Europe $62 mill.

icmricmr LED Traffic Lights

• 85 - 90 % Electricity Savings

• 5 + Year Life

• Maintenance Savings

• Tort Savings

Philadelphia Replaced 14,000 Red Traffic Signals

Projected 5 Year Savings = $4.8 million

• Full color projection displays• Backlighting for LCDs and cellphones• Automotive• Streetlighting

New Applicationsof Solid State Lighting

Off-Grid Lighting for Developing Countries by the Light Up The World Foundation (www.lutw.org)

Two Modular 1Watt Luxeon WLED lamps

12 Volt 7 Ah Sealed Lead Acid Battery – Rechargeable maintenance free battery

5 Watt Kyocera Solar Panel

100,000 hour lifetime

icmricmr Lighting Efficiency

A key goal is to save energy by achieving greater efficiency:

150Solid State Lighting – DOE target for 2010

120High Pressure sodium lamps

120Metal halide lamps

70Fluorescent lamps

20Halogen incandescent lamps

15Incandescent lamps

1.4 lm/WEdison’s first lamp

icmricmr How do we obtain white lightfrom LEDs ?

Blue LED

RGPhosphor

White light White light

RGB LEDs

Mixing Optics

1st generation

Blue LED

OGPhosphor

White light White light

UV/Purple LED

RGB Phosphors

2nd generation 3rd generation

icmricmr Current Versions use a Blue InGaNLED combined with a YAG Phosphor

Yellow phosphorBlue LED

The yellow phosphor is based upon Ce3+-YAG

icmricmr Patterns in Innovation in the 21Patterns in Innovation in the 21stst CenturyCentury

• Innovation is still being driven by academia, national laboratories and major corporations

• But an increasing fraction is being done in start-up companies

• Good news – others (angel investors, venture capitalists etc) are carrying part of the risk

• Bad news – major corporations do not have the same degree of control over such developments!

• Emerging nations, especially India and China, are becoming major sources of innovation

icmricmr R&D Investment in ChinaR&D Investment in China

An Incomplete List of Multinational Companies Setting up R&D in China

ABB, Accenture, Ajinomoto, Amway, Alcatel, AVL List GmbH, BASF, BEA Systems, Bearingpoint Inc, Calsonic Kansei, Cisco, Coca-cole, Danone, Degussa, Dell, Delphi Corp, Dow International, DuPont, eBay, Ericsson, Firmenich, France Telecom, GE, GlaxoSmithKline, Hitachi, Honda, Honeywell, HP, Hyundai, IBM, Intel, Kao, Keihin Corporation, Kodak, LG, L’Oreal, Lucent, Matsushita, Microsoft, Motorola, NEC, Nestle, Nifco Inc, Nissan Motor, Nissin Kogyo,Nokia, Nortel Networks, Novo Nordisk, Novozymes, Oracle, Panasonic, Pepsi, Philips, Procter & Gamble, Roche, Rohm and Haas, Samsung, SAP, Schindler, Shell, Siemens, Sony, Synopsys, Teling Manufacturing, Tetrapak, Toray, Toyo Ink, Trelleborg AB, Unilever, Valeo Group, Volkswagen

GE - A global lab of 2,000 FTEs opened in ShanghaiPhilips - A global R&D Campus planned in Shanghai

icmricmr Trends in Technology inTrends in Technology inEmerging NationsEmerging Nations

• China and India graduate 500,000 PhD scientists and engineers per year, compared with 60,000 in the USA

• They now boast some of the most innovative laboratories in the world

• The number of life scientists in India and China will grow by 35% to 1.6 million by 2008 (USA will fall by 11% to 760,000)

• From 1980 to 2001, US share of high tech exports fell from 35 to 18%. S.E. Asia increased from 7 to 25%

• But, intellectual property remains a major issue!

www.futureofinnovation.org

icmricmr Global Trends in Materials InnovationGlobal Trends in Materials Innovation

• Innovation is no longer the prerogative of the developed world

• Developing countries such as India and China are not limited to low cost manufacturing, but can often deliver innovation faster, cheaper and better than their competitors in the USA and Europe

• The pharmaceutical industry is perhaps most vulnerable because the present cost structure is becoming unsustainable in the developed world

• American/European companies (and universities!) need more than protectionism to address these challenges

icmricmr Is There Any Good News?Is There Any Good News?

• The USA still has the strongest tradition of bringing innovationto the marketplace through start-up companies, with a culture of entrepreneurship, angels, venture capital

Scientific training should include more opportunities to study technology management, in and out of the classroom

• One of the strengths of US institutions is that they still attract outstanding talent from around the world. This is a source of great strength and cannot be found in most other countries

This needs to be recognized at government level (e.g. INS)• Our young scientists need to gain the experience and outlook they will need to function productively in a very competitive international research and business environment

The International Center for Materials Research at UCSB has been created to meet this challenge

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The NGEN Enabling TechnologiesVenture Capital Fund

www.ngenpartners.com

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History of NGEN• NGEN was conceived at the height of the dot.com bubble in 1999 by Tony Cheetham and Peter Grubstein.

• The aim was to provide venture capital funding for materials science related start-up companies

• The first close for NGEN-I was on March 31, 2001, with four corporate investors: Air Products, BASF, Bayer, and Boeing ($25 million under management, incl. two private investors)

• By the final close in late 2002, the additional corporate Limited Partners were DSM, Henkel, Schott, Du Pont, Unilever, BHP-Billiton, Canon and Honda

• Total funds under management in NGEN-I: $70.5 million

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NGEN-1 Focus Areas• Polymers and Organics

• Active organic coatings, molecular recognition, gene chips, etc.• Infrastructure and Telecommunications

• Photonics• Computer Simulation, high throughput experimentation, informatics, processing, manufacturing systems, etc.

• Ceramics, displays, and electronics• Electrical, optical, magnetic, mechanical• Luminescent materials, dielectrics, etc

• Energy and Environmental• Catalysts, sensors, fuel cells, batteries etc.

• Nanotechnology• Molecular Electronics, drug delivery, coatings and cosmetics

• Biomaterials and biomimetics• Diagnostics, sensors, implants, imaging

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NGEN-I Portfolio – some examples• Catalytic Solutions

• Catalysts for the automotive, diesel and co-gen markets. • Pionetics

• Water purification system for developed and developing countries• Sensicore

• Portable multi-functional water sensor• Konarka

• Photovoltaics • Nanosphere

• Disease detection and diagnosis/ DNA and protein detection• Artificial Muscle

• Polymer-based signal transduction for pumps, drives etc• Powerspan

• Power plant emission remediation technology• Sol Focus

• Concentrator technology for high performance photovoltaic cells

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NGEN-II• First close in spring 2005 with $50 million

• Most of the original corporate LPs joined

• New Corporate LPs include Siemens and Asahi Glass

• Financial investors include CalPERS and CalSTERS

• Emphasis on CleanTech and Biomaterials

• Final close in summer 2006 with ~$150 million total

• Some investments to date:• Rennaissance Lighting

• White lighting based upon Red, Green and Blue LEDs• Cerox

• Mixed waste remediation (nuclear & organic)

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icmricmr What about Europe?What about Europe?Trends in PublicationsTrends in Publications

icmricmr Phys Rev E Publications1993-2006

icmricmr Macromolecules

icmricmr Global Trends in EnergyGlobal Trends in Energyand the Environmentand the Environment

• Global energy consumption is expected to more than double between now and 2040, partly by increasing population (up ~40%) and partly by increasing demand from the developing world.

• At the same time, global warming, anthropogenic and otherwise, will lead to changing in our climate and environment.

• Science and engineering will be called upon to help address these issues.

• The twenty-first century will turn out to the century of materials science rather than life sciences and medicine!

icmricmr Global Materials Issues andSustainable Development

• Alternative forms of energy must be harnessed in order to reduce dependence on fossil fuels. Inexpensive photovoltaic cells will be important (e.g. role-to-role manufacture of Graetzel cells), especially for off-grid applications in the DCs

• Pollution must be reduced by the development of new abatement chemistries and new processes

• Emissions from combustion must be reduced to combat global warming. Carbon dioxide sequestration and utilization must be pursued

• Methods to achieve inexpensivewater purification must be be developed, as must methods to minimize water utilization.

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THANK YOU!THANK YOU!