Advanced Materials

High Tc SuperconductorsGMR materialsNegative thermal expansion SupercapacitorsThermoelectricsPorous materialsSolid oxide Fuel cell (SOFC)Organic-inorganic hybrid materialsFullerenesNano Materials

Advanced or Smart BiomaterialsBiodegradable Advanced MaterialsSelf-assembled Materials

Future of Material Science :

Nanostructured materials for technologies in 2015 and beyond

Professor A K GanguliDepartment of Chemistry

Indian Institute of Technology Delhi New Delhi 110016

ashok@chemistry.iitd.ac.in

March 9, Bangalore, EmTech India 2010

E.U

USA

Japan

China Rest of world

Global Government Funding

12000 million dollars

2600 million dollars

NANOTECHNOLOGY

Large industry currently supports about half of the R&D in U.S_ $2 billion per yr.

CHINA

Russia<1% to 23%

2004 2009

3% to 10%

INDIA less than 1 %

J. Nanoparticle Res. (2010)

Global Nanotech Funds

• Materials : Controlled Synthesis

• Scale up

• Patterning large scale nanostructures

• contacts, system design

• self- assembly

Organized colloidal aggregates

Reverse - micelles as Nano - reactor

• Monodispersed water droplets• Inhibits the growth and aggregation of grains• Easy control of size and shape of the aqueous coreGanguli et al , Chem Soc Rev ( 2010)

Electroceramics Catalysts magnetics, catalysts

Photocatalysts

Toxin traps

Batteries

BaTiO3 MnC2O4 MnO, Mn2O3

Mn3O4

CdS @ TiO2

Ag@TiO2

Co

Ba2TiO4 FeC2O4 Fe2O3 , Fe3O4 CdS @ SiO2 Cu

SrTiO3 CoC2O4 CoO, Co3O4 NiS @ TiO2 Ni

Sr2TiO4 NiC2O4 NiO NiS @ SiO2 Cu-Ni

PbTiO3 CuC2O4 CuO NiOx@TiO2 Co-Ni

BaZrO3 ZnC2O4 ZnO NiOx@SiO2 Co-Cu

SrZrO3 CdC2O4 SnO2 GMR materials

Magnetic recording

Mn-Ni

PbZrO3 Ce2(C2O4)3 ZrO2 LaMnO3 Hard coatings

Fe2(C2H4C2O

4)3

CeO2 La.67Sr.33MnO3 LaB6

NaTaO3 CoC2H4C2O4 La.67Ca.33MnO3 NbB2

SrTa2O6 CuC2H4C2O4 CrB2

Variety of nanomaterials

NaNbO3

Hollow TiO2 via Ostwald Ripening

J. Phys. Chem. B, 2004, 108, 3492

Digestive Ripening

1. Journal of Nanoparticle Research 2000, 2, 157–1642. J. Am. Chem. Soc., 2002, 124, 2305-2311

Controlling size and shape

Controlling shape

CTAB/1-butanol/Isooctane TX-100/1-hexanol/cyclohexane Tergitol/1-octanol/cyclohexane

NiC2O4.2H2O

Ganguli et al, J. Phys. Chem. C 2008, 112, 12610–12615.

NiO

20 nm 10 nm

25 nm

100nm

Silica nanoparticles on copper succinate nanorods100 nm

silica nanoparticles coated with aminoacid.

By reverse micellesCommercially available NANO -

SiO2

SiO2

Aparna Ganguly et al

IITD

Silica particles (40 nm) :

Aparna et al, Journal of ClusterScience (2009)

50 nm

Porous silica (200 nm)Pores : 5 nm

550 m2/g

120 m2/g

Nanowires and Nanotubes Lateral dimension: 1 – 100 nm Nanowires & nanotubes exhibit novel physical, electronic and

optical properties due to – Two dimensional quantum confinement– Structural one dimensionality– High surface to volume ratio

Potential application in wide range of nanodevices & systems– Nanoscale sensors and actuators– Photovoltaic devices – solar cells– Transistors, diodes and LASERs Nanowire Solar Cell: The nanowires

create a surface that is able to absorb more sunlight than a flat surface

Anisotropic NanoMaterials

Synthetic nanomaterials utilized in biomedical applications Polymers, porous silicon, carbon nanotubes

Bone cell on porous silicon

Human cell on PSi

Porous silicon (PSi)

Formation and shape evolution of nano-heterostructures ( metal – carbon)

Chem. Mater., 2007, 19 (26), 6376-6378

Nanowire welding using DNA

T. MalloukPenn. State Univ.SH-DNA

Au

Complementary DNA strandson two wires

Quantum Dot Solar Cells

Complex functionalized Nanostructures

Carbon Nanotubes, (S. Iijima, 1991 )

Single nanotube ..transistor (1998, IBM) may replace silicon

Field effect transistors produced (Stanford/Cornell/Purdue)

Improved Carbon –based FET, IBM,2002 outperforms Si-based transistors,

twice current carrying capacity

World’s smallest computer logic circuit , IBM 2001

Sensors, Bio, NEMS

•

Electronics

• Challenges Challenges

• Control of diameter, chirality• Doping, contacts• Novel architectures (not CMOS based!)• Development of inexpensive Manufacturing processes

• Controlled growth• Functionalization with

probe molecules, robustness• Integration, signal processing• Fabrication techniques

Cost contributions from each process step (a–c) and fixed and variablecost contributions (d–f) for arc, CVD, and HiPco processes

Needs to be reduced

Needs to be reduced

Cost of synthesis

Cost of Labour

Ni-Titanate NanoTubes

as-prepared TNT Ni-TNT

300 C 400 C

500 C 600 C.

0 1 2 3 4 5

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

(c)

(b)

(e)

(f)

(g)

(d)

(h)

A/A

0

Irradiation time/hr

(a)

(a) Ni-TNT(b) 300 C (c) 400 C (d) 500 C (e) 600 C(f) 700 C (g) 800 C (h) 900 C

Photocatalytic degradation

Qamar et al Nanotechnology(2009)Beyond CNT

Biodegradable nanocomposite films for food packaging

Potato starch (PS), clay (C ) nanoparticles (Montmorillonite), bio-degradable polyester (PE) (Ecoflex SBX 7000)

Avella et.al, Food Chemistry, 93, 467(2005)

low overall migration limit and biodegradability

Nanostructured multiple emulsions in Food technology

Examples; oil-in-water-in-oil (O/W/O) and water-in-oil-in-water (W/O/W) emulsions

Water droplets

Oil droplets

Aqueous continuous phase

system for containing multiple food componentsto separate two reactive componentsto protect and release the component trapped within inner water droplets to a specific sites such as the mouth, stomach and small intestine

Thermal stability of primary, secondary and tertiary emulsions

Ze

ta p

ote

ntia

l

Biodegradable nanocapsules for the entrapment of drugsExample

Poly Lactic Acid (PLA) and Poly Ethyl Glycol (PEG) were used to prepare micellar like nanoparticles by precipitation/solvent evaporation method

Copolymer and the drug (procaine hydrochloride) were dissolved in acetonitrile and was precipitated in aqueous phase for the entrapment of drug into the assembly

T. Riley et al, 16, 147(1999)

(63.8 nm

PLA-PEG assembly can be successfully used as a host molecules for the

preservation of the drugs (as a guest molecules).

Core – shell nanostructures

Core

Shell

002200

Ag crystalline

TiO2

amorphous

5 nm

Methyl Orange

0 10 20 30 40 50 60 70 8070

75

80

85

90

95

100

% f

ree

met

hyl

ora

ng

e

Time (h)

Toxin Traps

Ganguli et al (2009)

SiO2

Metaloxide

Hollow shell

Hollow shells

ZnO @ CdS Core Shell Nanorods

Photocurrent

Assembly of core-shell on a substrate

CdS quantum dot sensitized solar cell based on a mesoporous TiO2 film : 1.24%J. Phys. Chem. C 2009,

IITD (2010)

Nanoelectronics

Smaller size of electronic components resistors, transistors, capacitors,

• Processors with increasing efficiency of computer by 106

• Higher transmission frequencies and more efficient utilization ofoptical spectrum to provide higher bandwidth

• Small mass storage devices: multi-tera bit levels

Dielectric Nanoparticles Dielectric Nanoparticles

Nanosized dielectric oxides (40-50 nm) will allow thin dielectric layers

Less dissipation factor

Need for miniaturization of device components

1990 limit (12 µm)

current feature size (chip) ~ 140 nm; by 2014 ~ 50-70 nm

MLCC ( Multilayer ceramic capacitor)For power line stabilization in the packaging of Si –based IC’s

( Pd /Ag)

+

Micron-sized Nanosized grainsHeat (Sinter)

Schematic Microstructure

Lower M. Pt.

Electroceramics : Nanocomposites

“( nµ) - Composites”

Barium titanium oxide

Enhancing the dielectric properties using nano-dopants

nμ-composite of BaTiO3

0

500

1000

1500

2000

0 5 10 15 20 25 30

wt% (Nano-BaTiO3)

0

0.02

0.04

0.06

0.08

0.1

D

D

At ~25oC

Sintered disk

Bulk BaTiO3 1 wt% BaTiO3

Dielectric constant is maximum at 1 wt

% composition

oscillatory nature

V. Shanker, T. Ahmad, H. Ip and A. K. Ganguli. J. Mater. Res., 21, 816 (2006)

Nanomaterials in Medical applications

Biosensor

DNA biosensor using impedance spectroscopy

• Rapid identification of DNA associated with bacterial contamination of food

• Immobilisation of DNA probes

• Hybridisation with sample DNA

• Impedimetric detection with interdigitated electrodes

D. Berdat, A.C. Martin-Rodriguez, F. Herrera, and M.A.M. Gijs, Lab on a Chip 8, 302-308 (2008); Daniel Berdat, L. Bernau, V. Sauvage, and M.A.M. Gijs, Proceed. Transducers’07 and Eurosensors XXI, Lyon, France, June 10-14, 2007, pp. 951-954.

Materials for applications in Gene therapy

viral vectors (toxic)Non – viral vectors…. Transfection ( Gene expression) is low

Drugs encapsulated in virus

Development of Calcium phosphate nanoparticles as a non-viral vector

Ca2+ complexes with DNA Enters cell Nucleus

Non – toxic

Technology transferred to American Pharmaceutical company

Anti – Cancer drug (Taxol)

No selectivity … toxic for cancer and normal cells

Polymeric micelle nanoparticles Encapsulate Taxol

Inject into body ( intravenous) The micelle develops perforations in the cancerous cells only Taxol is released Death of cancer cells

Technology transferred to Dabur, India

Prof A. N. Maitra, Delhi University

• More efficient catalytic converters

• Thermal barrier and wear resistant coatings

• Battery, fuel cell technology

• Improved displays

• Wear-resistant tires

• High temperature sensors for ‘under the hood’; novel sensors for “all-electric” vehicles

• High strength, light weight composites for increasing fuelefficiency

Scope of Nanomaterials for transportation

Carbon –based fibres, polymer-metal nanocomposites

• Improved collection, transmission, protection of information

• Very high sensitivity, low power sensors for detecting chem/bio/nuclear threats

• Light weight military platforms, without sacrificing functionality, safety and soldier security

- Reduce fuel needs and logistical requirements

• Reduce carry-on weight of soldier gear - Increased functionality per unit weight

•Miniature micro-machined silicon cantilever coated with sensitive polymer that detect vapors given off by explosives

Security

polymers

Detection of Explosives (RDX) in Seawater using Biosensors

Substrate

ImmobilizedRDX analog

Anti-RDXantibody

FreeRDX

Luminescent QD

Competition Assay

• QDs conjugated with anti-RDX antibodies

• Variation of PL of QD-bioconjugates bound to a surface prepared with RDX analogs

• Free RDX competes for bioconjugate and reduces PL signal

Materials of Major Interest Carbon nanotubes(CNT) ( electronics, sensors, high strength fibres)

Si Nanowires (biosensors)

Metal powders ( Al, B) ( space, defence)

BaTiO3 (electroceramics)

TiO2, GaN, ZnO, CdS (photovoltaics, energy)

Metal oxides (catalysts)

Fe2O3 , SiO2, Au ( biomedical applications)

Biodegradable polymers (Food & Drug industry)

Precise control of size and shape

Large scale synthesis

Self-assembly

GRAPHENErealized in 2004

(Novoselov, Science 306, 2004)

Predicted in 1947

Intrinsic graphene is a semi-metal or zero-gap semiconductor

remarkably high electron mobility at room temperature

pure graphene is transparent

ideal material for spintronicslight-emitting diodes (LEDs) , improved solar cells

Material of the Future

Large scale synthesis of pure Graphene : Challenge

Single molecule gas detection

Graphene nanoribbons

Graphene transistors

Integrated circuits

Transparent conducting electrodes

Reference material for characterizing electroconductive and transparent materials

Ultracapacitors

Graphene biodevices

Applications of Graphene

Compund % purity Avg size Quantity Cost (Rs)

BaTiO3 99+ 30-50 nm 25g 3638

CaTiO3 99.9 60-100 nm 25g 5395

CaZrO3 99.7 10-20 nm 25g 6540

CNT (single walled) 50 (Arc method) 1.2-1.5 nm * 2-5 μm 250 mg 5290

CNT (single walled) 50 (CVD) 1.1 nm * 0.5-100 μm 250 mg 13860

CNT (doublewalled) 50 (CVD) 1.3-2.0 nm * 50 μm 250 mg 13860

Mixture of Anatase and rutile 99.9 25-70 nm 25g 2620

Anatase 99.7 5 nm 50g 4982

Rutile 99.5 25g 2399

Silica 99.5 10 nm 50g 3696

Silica 99.5 15 nm 50g 3360

Cost of some nanomaterials

Molecules are important ( Molecular electronics)

30 nm

Bottom –up approach

The future : self assembled circuits with molecular components

Molecular machines

motor proteins

Synthetic molecular motors

Chemically driven rotary molecular motors

first example : Kelly and co-workers in 1999 rotation takes place in five steps

amine group present on the triptycene moiety is converted to an isocyanate group

Light-driven rotary molecular motors

Photochromic molecular switches

Prepared from Au-Ni nanorods (alumina membrane as the template )

The rotor is propelled by H2O2.

The angular velocity can be varied by H2O2 concentration and Ni segment length.

• rotational actuators• switches• valves• power sources

Fourier-Bidoz et.al., Chem. Commun. (2005) (4), 441

Nanodevices

Crossbar memory circuit (160 KB)

• Green , Heath et. al. Nature, 445, 414 (2007)

400 Ti n.wires covered by 400 Pt nanowires

By SNAP method400 Si nanowires

A Molecular switch tunnel junction (1 bit)

1011 per sq.cm

rotaxane molecules between the electrodes

33 nm pitch achieved

Size of One WBC13 microns

Predicted for 2020 by normal techniques

bistable [2]rotaxane used as

storage unit in the crossbar memory (molecular switch)

Green et. Al. Nature, (2007)

circumrotation

translation

Si nanowire

Pt/Ti nanowire

TTF TTF+

Balzani et al , J. Org Chem (2000)

Molecular shuttle

passive nano items developed : sunscreens, tennis rackets, stain/water-resistant clothing, and other high-tech products.

cars that automatically repair scratches wiper-less windshield cleaners

nanofoods such as fat-free donuts, cholesterol-lowering cheeseburgers, and “smart” grocery packaging materials that prevent food from spoiling.

2000-2005

2005-2010

products that change states during use

Development of Nanotechnology based products

To have transformable devices (easy to carry and use) leads the way from foldable, sliding, and bendable devices towards more wearable electronics.

In the near Future

protect the core electronics and achieve good reliability, i.e., “washable electronics”.

paper or fabric in ink infused with nanoparticles: lightweight paper batteries

stretchable, conductive textiles - capable of storing energy eTextiles

Nokia Morph ( joint venture between Nokia and Cambridge University )

Nanostructure-based smart device for sensing, communication, time, mobile, user friendly, self charging and self cleaning

• http://www.youtube.com/watch?v=IX-gTobCJHs

effective integration of electronics to device mechanicsoptimized design with multifunctional materials

challenges

With electricity : sizeable voltage is needed and the process is not very efficient

catalysts : a smaller voltage

Production of oxygen and hydrogen gas powered by solar photovoltaic cells

Mimic a green Leaf : A Photoelectrochemical cell can help to split water

Mostly with UV light

low conversion efficiencies and relatively high cost.

.

No material capable of catalyzing reaction with visible light and a QE larger than 10%

Store H2 , Couple with O2 in a Fuel CellEnergy ( in absence of Light)

Energy from water

• Cobalt-based Phosphate (Photocatalyst)

• 30kWh from one bottle of water (4h of sun)

• Daniel Nocera ( MIT) ARPA – Energy meeting, USA

March 2, 2010

How expensive is the catalyst ??? Turnover Number ???

H2O + CO2 H2 + O2 + carbohydrates catalyst

c

111

Rod shaped copper particles

20 nm

cube shaped copper particles

-0.001

-0.0005

0

0.0005

0.001

0 50 100 150 200

Cu-cube shapedCu-rod ShapedCu-Speherical Shaped

Time (sec)spherical shaped copper particles

Hydrogen evolution reaction

Ganguli et al 2010

Shape-dependent Copper nanostructures as electrocatalysts

proteins or viruses that build small batteries

nanostructures that create a lattice on which bone or other tissues can grow

“smart” dust strewn over an area that sense the presence of humans and communicates their location

devices that find and destroy cancer cells without harming neighboring tissues.

Nanotechnology: incredible products predicted for the future

2010-2015

Nanomaterials that self-assemble to achieve a final goal

Beyond 2030

humanity to transcend its biological limitations _interface directly with supercomputers and their stored intelligence

2015-2020

nanobots

computers will be able to sense and respond to human thoughts

render hazardous materials harmlessenrich farmlands by placing correct amounts of oxygen and nutrients into the soil, and roam through bodies analyzing vital conditions and displaying health

information directly on the skin (like a temporary tattoo). tissues and organs will be grown inside the body using stem cell and genetic

engineering techniques

2020 to 2030

tiny computerized nanobots that maintain perfect health in every cell

organic memory devices which would capture memories directly from our brain

Most complex molecules are synthesized atom by atom chemically

Self-organization leads to complex supramolecular entities

Brain -----Most Complex computer , made of molecules , run by molecules/ions

Life is possible because of chemical information processing

Influenced by some lectures of Jean Marie Pierre Lehn , N. L. in Chemistry, 1987

Some Thoughts

The Key is to use chemistry ( solution – based processes) together with the knowledge of biologically relevant molecules and processes

Ultimate Challenge

• Utilizing self-assembly and molecular recognition, different molecular scale “building blocks” may be combined together to tailor active, smart materials to mimic cells, organs and living beings

Department of Science & Technolgy, Govt. of IndiaNanomission, Physical Chemistry & ( IITD-EPFL) projectsMinistry of Human Res. & Dev., Govt. of India Council of Scientific & Industrial Research, Govt. of India