Ganguli Future Of Material Science

Advanced Materials High Tc Superconductors GMR materials Negative thermal expansion Supercapacitors Thermoelectrics Porous materials Solid oxide Fuel cell (SOFC) Organic-inorganic hybrid materials Fullerenes Nano Materials Advanced or Smart Biomaterials Biodegradable Advanced Materials Self-assembled Materials Future of Material Science :

Nanostructured materials for technologies in 2015 and beyond Professor A K Ganguli Department of Chemistry Indian Institute of Technology Delhi New Delhi 110016 [email_address] March 9, Bangalore, EmTech India 2010

E.U USA Japan China Rest of world Global Government Funding 12000 million dollars 2600 million dollars N A N O T E C H N O L O G Y

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 core Ganguli et al , Chem Soc Rev ( 2010)

Variety of nanomaterials NaNbO 3 Electroceramics Catalysts magnetics, catalysts Photocatalysts Toxin traps Batteries BaTiO 3 MnC 2 O 4 MnO, Mn 2 O 3 Mn 3 O 4 CdS @ TiO 2 [email_address] 2 Co Ba 2 TiO 4 FeC 2 O 4 Fe 2 O 3 , Fe 3 O 4 CdS @ SiO 2 Cu SrTiO 3 CoC 2 O 4 CoO, Co 3 O 4 NiS @ TiO 2 Ni Sr 2 TiO 4 NiC 2 O 4 NiO NiS @ SiO 2 Cu-Ni PbTiO 3 CuC 2 O 4 CuO [email_address] 2 Co-Ni BaZrO 3 ZnC 2 O 4 ZnO [email_address] 2 Co-Cu SrZrO 3 CdC 2 O 4 SnO 2 GMR materials Magnetic recording Mn-Ni PbZrO 3 Ce 2 (C 2 O 4 ) 3 ZrO 2 LaMnO 3 Hard coatings Fe 2 (C 2 H 4 C 2 O 4 ) 3 CeO 2 La .67 Sr .33 MnO 3 LaB 6 NaTaO 3 CoC 2 H 4 C 2 O 4 La .67 Ca .33 MnO 3 NbB 2 SrTa 2 O 6 CuC 2 H 4 C 2 O 4 CrB 2

Hollow TiO 2 via Ostwald Ripening J. Phys. Chem. B , 2004, 108, 3492 Digestive Ripening Controlling size and shape Journal of Nanoparticle Research 2000, 2, 157–164 2. J. Am. Chem. Soc. , 2002, 124, 2305-2311

Controlling shape CTAB/1-butanol/Isooctane TX-100/1-hexanol/cyclohexane Tergitol/1-octanol/cyclohexane NiC 2 O 4 .2H 2 O Ganguli et al, J. Phys. Chem. C 2008, 112, 12610–12615. NiO 20 nm 10 nm 25 nm

Silica nanoparticles on copper succinate nanorods silica nanoparticles coated with aminoacid. By reverse micelles Commercially available NANO - SiO 2 SiO 2 Aparna Ganguly et al IITD 100nm 100 nm

Silica particles (40 nm) : Aparna et al, Journal of ClusterScience (2009) 50 nm Porous silica (200 nm) Pores : 5 nm 550 m 2 /g 120 m 2 /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. Mallouk Penn. State Univ. SH-DNA Au Complementary DNA strands on 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

CNT Applications 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 variable cost 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. Ni-TNT 300 C 400 C 500 C 600 C 700 C 800 C 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 components to separate two reactive components to 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 Zeta potential

Biodegradable nanocapsules for the entrapment of drugs Example 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 Methyl Orange Toxin Traps Ganguli et al (2009) SiO 2 Metal oxide Hollow shell Hollow shells 002 200 Ag crystalline TiO 2 amorphous 5 nm

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 10 6 • Higher transmission frequencies and more efficient utilization of optical spectrum to provide higher bandwidth • Small mass storage devices: multi-tera bit levels

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 grains Heat (Sinter) Schematic Microstructure Lower M. Pt. Electroceramics : Nanocomposites “ ( n µ) - Composites” Barium titanium oxide Enhancing the dielectric properties using nano-dopants

n μ -composite of BaTiO 3 Sintered disk 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) At ~25 o C Bulk BaTiO 3 1 wt% BaTiO 3

Nanomaterials in Medical applications

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 Non – toxic Technology transferred to American Pharmaceutical company Anti – Cancer drug (Taxol) No selectivity … toxic for cancer and normal cells 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 Ca 2+ complexes with DNA Enters cell Nucleus Polymeric micelle nanoparticles Encapsulate Taxol

• 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 fuel efficiency 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 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 Substrate Immobilized RDX analog Anti-RDX antibody Free RDX Luminescent QD

Materials of Major Interest Carbon nanotubes(CNT) ( electronics, sensors, high strength fibres) Si Nanowires (biosensors) Metal powders ( Al, B) ( space, defence) BaTiO 3 (electroceramics) TiO 2 , GaN, ZnO, CdS (photovoltaics, energy) Metal oxides (catalysts) Fe 2 O 3 , SiO 2 , Au ( biomedical applications) Biodegradable polymers (Food & Drug industry) Precise control of size and shape Large scale synthesis Self-assembly

GRAPHENE realized 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 spintronics light-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

Cost of some nanomaterials 3360 50g 15 nm 99.5 Silica 3696 50g 10 nm 99.5 Silica 2399 25g 99.5 Rutile 4982 50g 5 nm 99.7 Anatase 2620 25g 25-70 nm 99.9 Mixture of Anatase and rutile 13860 250 mg 1.3-2.0 nm * 50 μ m 50 (CVD) CNT (doublewalled) 13860 250 mg 1.1 nm * 0.5-100 μ m 50 (CVD) CNT (single walled) 5290 250 mg 1.2-1.5 nm * 2-5 μ m 50 (Arc method) CNT (single walled) 6540 25g 10-20 nm 99.7 CaZrO 3 5395 25g 60-100 nm 99.9 CaTiO 3 3638 25g 30-50 nm 99+ BaTiO 3 Cost (Rs) Quantity Avg size % purity Compund

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

Self-propelled nanorotors Prepared from Au-Ni nanorods (alumina membrane as the template ) The rotor is propelled by H 2 O 2 . The angular velocity can be varied by H 2 O 2 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 method 400 Si nanowires A Molecular switch tunnel junction (1 bit) 10 11 per sq.cm rotaxane molecules between the electrodes 33 nm pitch achieved Size of One WBC 13 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 mechanics optimized 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 H 2 , Couple with O 2 in a Fuel Cell Energy ( 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 ??? H 2 O + CO 2 H 2 + O 2 + carbohydrates catalyst

c 111 Rod shaped copper particles cube shaped copper particles spherical shaped copper particles Hydrogen evolution reaction Ganguli et al 2010 Shape-dependent Copper nanostructures as electrocatalysts 20 nm

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 harmless enrich 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 India Nanomission, Physical Chemistry & ( IITD-EPFL) projects Ministry of Human Res. & Dev., Govt. of India Council of Scientific & Industrial Research, Govt. of India

Ganguli Future Of Material Science

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