Introduction to nanoscience and nanotechnology

Nanoscience & Nanotechnology

1. Introduction to Nanoscience and Nanotechnology Dr. Bharat Parekh School of Technology Pandit Deendayal Petroleum University Gandhinagar-382007 Gujarat, India Pandit Deendayal Petroleum University

2. Plan of the Talk Nanoscience-Definition Background Lesson from Nature Building nano structures Synthesis of nanomaterials ( CdTe ) Applications in different field Nano Industry Summary

3. A biological system can be exceedingly small . Many of the cells are very tiny, but they are very active; they manufacture various substances ; they walk around; they wiggle; and they do all kinds of marvelous things—all on a very small scale . Also, they store information. Consider the possibility that we too can make a thing very small that does what we want—that we can manufacture an object that maneuvers at that level. ( From the talk “There’s Plenty of Room at the Bottom ,” delivered by Richard P. Feynman at the annual meeting of the American Physical Society at the California institute of Technology, Pasadena , CA , on December 29, 1959.) Introduction

4. What is Nanoscience? When people talk about Nanoscience, many start by describing things Physicists and Material Scientists point to things like new nanocarbon materials: They effuse about nanocarbon’s strength and electrical properties Graphene Carbon Nanotube C60 Buckminster Fullerene "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience

5. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience Biologists counter that nanocarbon is a recent discovery THEY’VE been studying DNA and RNA for much longer (And are already using it to transform our world)

6. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience And Chemists note THEY’VE synthesized molecules for over a century <= First OLED material: tris 8-hydroxyquinoline aluminum (OLED = organic light emitting diode) Commercial OLED material: Polypyrrole Most heavily investigated molecular electronic switch: Nitro oligo phenylene ethynylene

7. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience All of these things ARE very small Indeed, they are all about the size of a nanometer: Nano = 10 -9 = 1/ 1,000,000,000 = 1 / Billion A nanometer is about the size of ten atoms in a row This leads to ONE commonly used definition of nanoscience : Nanoscience is study of nanometer size things (?) Why the question mark? Because what is so special about a nanometer? A micrometer is ALSO awfully small: Micro = 10 -6 - 1/1,000,000 = 1 / Million A micrometer (or "micron") is ~ size of light's wavelength

8. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience And micro technology has been rolling along for half a century! Microelectronics = Integrated circuits, PC's, iPods, iPhones . . . Intel 4004: The original "computer on a chip" - 1971 (Source: UVA Virtual Lab) Also = MEMS (Micro-electro-mechanical-systems): Air bag accelerometers, micro-mirror TVs & projectors . . . (Source: Texas Instruments DLP demo - www.dlp.com/tech/what.aspx)

9. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience Indeed, microtechnology has gotten smaller EVERY year MOORE'S LAW: The (then almost whimsical) 1965 observation by Intel co- founder Gordon Moore that the transistor count for integrated circuits seemed to be doubling every 18-24 months He was really sticking his neck out: IC's had only been invented 7 years before! (by Moore, his Fairchild/Intel colleagues, and Texas Instrument's Jack Kilby ) But his "law" has since been followed for forty five years: (Source: www.intel.com/technology/mooreslaw/index.htm)

10. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience So is Nanoscience/technology really new & unique? Micro is also VERY small Micro has been around for a long time Micro has steadily shrunk to the point that it is now almost NANO anyway ! Leading to a LOT of confusion about the distinction between Micro & Nano Even among scientists!! And likelihood that Nanotechnology will be built UPON Microtechnology Either by using certain Microfabrication techniques Or, literally, by being assembled ATOP Microstructures

11. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience Meaning that the NANO "revolution" is just a lot of hype? Just about making things incrementally smaller? Just about a simple shift in the most convenient unit of measure? I DO see something very unique about Nano : Nano is about boundaries where BEHAVIOR radically changes: When the BEHAVIOR OF THE OBJECTS SUDDENLY CHANGES Or when OUR BEHAVIOR MUST CHANGE to make those things

12. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience Boundary : ELECTRON WAVES Separate NanoSCIENCE from MicroSCIENCE The discovery that electrons = waves led to QUANTUM MECHANICS A weird, new, counter intuitive, non-Newtonian way of looking at the nano world With a particular impact upon our understanding of electrons: Electrons => Waves How do you figure out an electron’s wavelength?  electron = h / p “De Broglie’s Relationship” (  = electron wavelength, h = Planck’s Constant, p = electron’s momentum) This relationship was based on series of experiments late 1800’s / early 1900’s To put the size of an electron’s wavelength in perspective:

13. Nanometer Scale - Unknown Behavior “Magical Point on Length Scale, for this is the point where the smallest man-made devices meet atoms and molecules of the natural world.” Eugene Wong, Knight Rider Newspapers, Kansas City Star, Monday Nov. 8 th , 1999 Just wait, the next century is going to be incredible. We are about to be able to build things that work at the smallest possible length scales, atom by atom . These little nanothings will revolutionize our industries and our lives.” R. Smalley, Congressional Hearings, Summer 1999.

14. "We're not in Kansas Anymore!" - A Hands-on Introduction to Nanoscience Size of Things Millimeters Microns Nanometers Ball of a ball point pen 0.5 Thickness of paper 0.1 100 Human hair 0.02 - 0.2 20 – 200 Talcum Powder 40 Fiberglass fibers 10 Carbon fiber 5 Human red blood cell 4 – 6 E-coli bacterium 1 Size of a modern transistor 0.25 250 Size of Smallpox virus 0.2 – 0.3 200 – 300 Electron wavelength: ~10 nm or less Diameter of Carbon Nanotube 3 Diameter of DNA spiral 2 Diameter of C60 Buckyball 0.7 Diameter of Benzene ring 0.28 Size of one Atom ~0.1

15. Consider a human hand How Big is a Nanometer? white blood cell skin DNA atoms nanoscale Source: http://www.materialsworld.net/nclt/docs/Introduction%20to%20Nano%201-18-05.pdf

16. History of Nanomaterials 1974 The word Nanotechnology first coined by Nario Taniguchi, Univ. of Tokyo --- production technology to get ultra fine accuracy and precision – 1nm 1981 IBM invented STM scanning tunneling microscope which can move single atoms around 1985 new form of carbon discovered --- C60 buckminister fullerene 60 carbon atoms arranged in a sphere made of 12 pentagons and 20 hexagons

17. Lycurgus chalice 4 th Century A.D. Appears green in reflected light and red if light is directed through it (70 nm particles of silver and gold in the glass) Lycrugus cup with diffused light Lycrugus cup with focused light History of Nanomaterials

18. 1991 carbon nanotubes discovered “graphitic carbon needles ranging from 4 nm – 30 nm and up to 1 micron in length” ( Sumino Iijima ) 1993 First high quality quantum dots prepared --- very small particles with controlled diameters of CdS , CdSe , CdTe History of Nanomaterials

19. 2000 First DNA motor made similar to motorized tweezers may make computers 1000 more powerful. Nature 406 (6796) 2000, 605-608. DNA motors can be attached to electrically conducting molecules – act as basic switches History of Nanomaterials

20. 2001 prototype fuel cell made with nanotubes 2002 Nanomaterials make stain repellant trousers Nano -care khakis have nanowhiskers (10-100 nm in length) History of Nanomaterials

21. Nano airborne particles (100 -1000 nm) cause water to condense and form raindrops or snowflakes Plankton – varies in sizes from (1- 100 nm) Marine bacteria and viruses Lesson from Nature

22. Glucose and Glucose oxidase All cells require glucose (0.6 nm) as a fuel for metabolism. Energy is released from glucose when it is precisely positioned relative to the glucose oxidase enzyme ( 5 nm) Lock and key mechanism common in biology

23. Actin and Myosin Actin and myosin molecules form the system responsible for muscle contraction. The system operates by a series of steps where the head of myosin molecule pulls the actin past itself by 10–28 nm each step.

24. NATURE - Gecko Power Gecko foot hairs typically have diameters of 200 – 500 nm. Weak chemical interaction between each hair and surface (each foot has over 1 million of these hairs) provides a force of10 N/cm 2 . This allows Gecko’s to walk upside down across glass ceilings.

25. Bucky Balls (C60) were discovered in soot! Nanoparticles in Smoke from Fires

26. Ferrofluids Coated Iron oxide nanoparticles (wikipedia) Great demo Buy ferrofluid, use Synthesize ferrofluid

27. Nanoscience Is Everywhere in Nature Living cells have been using their own nanoscale devices to create structures one atom or molecule at a time for millions of years. To be specific, DNA is copied, proteins are formed, and complex hormones are manufactured by cellular devices far more complex than the most advanced manufacturing processes we have today. http://dallas.bizjournals.com/dallas/stories/2001/09/10/focus2.html?page=3

28. So How Did We Get Here? New Tools! As tools change, what we can see and do changes

29. Light microscope (magnification up to 1000x) to see red blood cells (400x) Sources: http://www.cambridge.edu.au/education/PracticeITBook2/Microscope.jpg http://news.bbc.co.uk/olmedia/760000/images/_764022_red_blood_cells300.jpg Using Light to See The naked eye can see to about 20 microns A human hair is about 50-100 microns thick Light microscopes let us see to about 1 micron Bounce light off of surfaces to create images

30. Greater resolution to see things like blood cells in greater detail (4000x) Sources: http://www.biotech.iastate.edu/facilities/BMF/images/SEMFaye1.jpg http://cgee.hamline.edu/see/questions/dp_cycles/cycles_bloodcells_bw.jpg Using Electrons to See Scanning electron microscopes (SEMs), invented in the 1930s, let us see objects as small as 10 nanometers Bounce electrons off of surfaces to create images Higher resolution due to small size of electrons

31. This is about how big atoms are compared with the tip of the microscope Source: Scientific American, Sept. 2001 Touching the Surface Scanning probe microscopes, developed in the 1980s, give us a new way to “see” at the nanoscale We can now see really small things, like atoms, and move them too!

32. Scanning Probe Microscopes Atomic Force Microscope (AFM) A tiny tip moves up and down in response to the electromagnetic forces between the atoms of the surface and the tip The motion is recorded and used to create an image of the atomic surface Scanning Tunneling Microscope (STM) A flow of electrical current occurs between the tip and the surface The strength of this current is used to create an image of the atomic surface

33. Source: http://www.uwgb.edu/dutchs/GRAPHIC0/GEOMORPH/SurfaceVol0.gif Is Gold Always “Gold”? Cutting down a cube of gold If you have a cube of pure gold and cut it, what color would the pieces be? Now you cut those pieces. What color will each of the pieces be? If you keep doing this - cutting each block in half - will the pieces of gold always look “gold”?

34. Source: http://www.nano.uts.edu.au/pics/au_atoms.jpg Nanogold Well… strange things happen at the small scale If you keep cutting until the gold pieces are in the nanoscale range, they don’t look gold anymore… They look RED ! In fact, depending on size, they can turn red, blue, yellow, and other colors Why? Different thicknesses of materials reflect and absorb light differently 12 nm gold particles look red Other sizes are other colors

35. Nanostructures What kind of nanostructures can we make? What kind of nanostructures exist in nature?

36. Source: http://www.library.utoronto.ca/engineering-computer-science/news_bulletin/images/nanotube.jpeg Model of a carbon nanotube Carbon Nanotubes Using new techniques, we’ve created amazing structures like carbon nanotubes 100 time stronger than steel and very flexible If added to materials like car bumpers, increases strength and flexibility

37. Model of Buckminsterfullerene Source: http://digilander.libero.it/geodesic/buckyball-2Layer1.jpg Carbon Buckyballs (C60) Incredible strength due to their bond structure and “soccer ball” shape Could be useful “shells” for drug delivery Can penetrate cell walls Are nonreactive (move safely through blood stream)

38. Source: http://faculty.abe.ufl.edu/~chyn/age2062/lect/lect_06/lect_06.htm http://www.zephyr.dti.ne.jp/~john8tam/main/Library/influenza_site/influenza_virus.jpg Biological Nanomachines in Nature Life begins at the nanoscale Ion pumps move potassium ions into and sodium ions out of a cell Ribosomes translate RNA sequences into proteins Viruses infect cells in biological organisms and reproduce in the host cell Influenza virus

39. Building Nanostructures How do you build things that are so small?

40. Fabrication Methods Atom-by-atom assembly Like bricklaying, move atoms into place one at a time using tools like the AFM and STM Chisel away atoms Like a sculptor, chisel out material from a surface until the desired structure emerges Self assembly Set up an environment so atoms assemble automatically. Nature uses self assembly (e.g., cell membranes) IBM logo assembled from individual xenon atoms Polystyrene spheres self-assembling Source: http://www.phys.uri.edu/~sps/STM/stm10.jpg; http://www.nanoptek.com/digitalptm.html

41. Example: Self Assembly By Crystal Growth Grow nanotubes like trees Put iron nanopowder crystals on a silicon surface Put in a chamber Add natural gas with carbon (vapor deposition) Carbon reacts with iron and forms a precipitate of carbon that grows up and out Growing a forest of nanotubes ! Because of the large number of structures you can create quickly, self-assembly is the most important fabrication technique Source: http://www.chemistry.nmsu.edu/~etrnsfer/nanowires/

42. Arrested Precipitation: General Approach

43. Aqueous reduction of metal salts (Ag, Au) in the presence of citrate ions – Chemisorption of organic ligands for handling – Distribution varies > 10% II-VI ME nanocrystals (NCs) (M = Zn, Cd , Hg; X = S, Se, Te) – Metal alkyls + organophosphine chalcogenides – Phosphine binding to M controlled by temperature – Ostwald ripening allows for size- selective aliquots; growth time for 1-2 nm NCs in minutes

44. Synthesis of Nanomaterials • CdSe nanocrystals

45. CdO + oleic acid + octadecene • Heat to 250° C to dissolve the CdO Selenium + octadecene + tributylphosphine • Heat to 150° C to dissolve the selenium Transfer Se solution to the Cd solution • Take aliquots

46. 47 Materials Stain-resistant clothes Health Care Chemical and biological sensors, drugs and delivery devices Potential Impacts of Nanotechnology Thin layers of gold are used in tiny medical devices Carbon nanotubes can be used for H fuel storage Possible entry point for nanomedical device Technology Better data storage and computation Environment Clean energy, clean air

47. 48 Materials: Stain Resistant Clothes Nanofibers create cushion of air around fabric 10 nm carbon whiskers bond with cotton Acts like peach fuzz; many liquids roll off Sources: http://www.sciencentral.com/articles/view.php3?article_id=218391840&cat=3_5 http://mrsec.wisc.edu/Edetc/IPSE/educators/activities/nanoTex.html Nano pants that refuse to stain; Liquids bead up and roll off Nano-Care fabrics with water, cranberry juice, vegetable oil, and mustard after 30 minutes (left) and wiped off with wet paper towel (right)

48. 49 Materials: Paint That Doesn’t Chip Protective nanopaint for cars Water and dirt repellent Resistant to chipping and scratches Brighter colors, enhanced gloss In the future, could change color and self-repair? Mercedes covered with tougher, shinier nanopaint Sources: http://www.supanet.com/motoring/testdrives/news/40923/

49. 50 Environment: Paint That Cleans Air Nanopaint on buildings could reduce pollution When exposed to ultraviolet light, titanium dioxide (TiO2) nanoparticles in paint break down organic and inorganic pollutants that wash off in the rain Decompose air pollution particles like formaldehyde Buildings as air purifiers? Sources: http://english.eastday.com/eastday/englishedition/metro/userobject1ai710823.html

50. 51 Environment: Nano Solar Cells Nano solar cells mixed in plastic could be painted on buses, roofs, clothing Solar becomes a cheap energy alternative! Source: http://www.berkeley.edu/news/media/releases/2002/03/28_solar.html Nano solar cell: Inorganic nanorods embedded in semiconducting polymer, sandwiched between two electrodes ] 200 nm

51. 52 Technology: A DVD That Could Hold a Million Movies Current CD and DVD media have storage scale in micrometers New nanomedia (made when gold self-assembles into strips on silicon) has a storage scale in nanometers That is 1,000 times more storage along each dimension (length, width)… Source: Images adapted from http://uw.physics.wisc.edu/~himpsel/nano.html …or 1,000,000 times greater storage density in total!

52. 53 Technology: Building Smaller Devices and Chips Nanolithography to create tiny patterns Lay down “ink” atom by atom Mona Lisa, 8 microns tall, created by AFM nanolithography Sources: http://www.ntmdt.ru/SPM-Techniques/Principles/Lithographies/AFM_Oxidation_Lithography_mode37.html http://www.chem.northwestern.edu/~mkngrp/dpn.htm Transporting molecules to a surface by dip-pen nanolithography

53. 54 Health Care: Nerve Tissue Talking to Computers Neuro -electronic networks interface nerve cells with semiconductors Possible applications in brain research, neurocomputation , prosthetics, biosensors Snail neuron grown on a chip that records the neuron’s activity Source: http://www.biochem.mpg.de/mnphys/publications/05voefro/abstract.html

54. 55 Health Care: Detecting Diseases Earlier Quantum dots glow in UV light Injected in mice, collect in tumors Could locate as few as 10 to 100 cancer cells Sources: http://vortex.tn.tudelft.nl/grkouwen/qdotsite.html http://www.whitaker.org/news/nie2.html Early tumor detection, studied in mice Quantum Dots: Nanometer-sized crystals that contain free electrons and emit photons when submitted to UV light

55. 56 Health Care: Growing Tissue to Repair Hearts Nanofibers help heart muscle grow in the lab Filaments ‘instruct’ muscle to grow in orderly way Before that, fibers grew in random directions Source: http://www.washington.edu/admin/finmgmt/annrpt/mcdevitt.htm Cardiac tissue grown with the help of nanofiber filaments

56. 57 Health Care: Preventing Viruses from Infecting Us Nanocoatings over proteins on viruses Could stop viruses from binding to cells Never get another cold or flu? Sources: http://www.zephyr.dti.ne.jp/~john8tam/main/Library/influenza_site/influenza_virus.jpg http://pubs.acs.org/cen/topstory/8005/8005notw2.html Influenza virus: Note proteins on outside that bind to cells Gold tethered to the protein shell of a virus

57. 58 Health Care: Making Repairs to the Body Nanorobots are imaginary, but nanosized delivery systems could… Break apart kidney stones, clear plaque from blood vessels, ferry drugs to tumor cells Source: http://www.genomenewsnetwork.org/articles/2004/08/19/nanorobots.php

58. FNI 1A 59 The Nano Industry Equipment suppliers Imago Instruments – Atom probe microscope Hysitron Inc Thermo electron Advanced materials 3M Cima Nanotech Electronics – A natural progression Intel HP Motorola IBM Biotechnology Platypus Bioforce Nanoscience Ace Ethanol Healthcare Medtronic Boston Scientific Energy Nanodynamics – Fuel cells Konarka – Flexible solar panels Cymbet Defense and security Detecting explosives and bio agents MIT Institute of Soldier Nanotechnologies

59. FNI 1A 60 NNI http://www.nano.gov/ NNIN http://www.nnin.org/ MRSEC http://www.mrsec.wisc.edu/Edetc/ NanoHUB http://www.nanohub.org/ Conferences: NSTI, UMN, http://www.nsti.org/ http://www.nano.umn.edu/conference2008/ Nanorite Center http://www.nanorite.org/ Nano in the News The Nano Industry

60. FNI 1A 61 Future of Nanotechnology “Nanotechnology products worldwide will be $2.6 Trillion or 15% of global manufacturing output.” Investing in Nanotechnology -- Jack Uldrich Enablers and tools: Hysitron , Imago Nanomaterials : Carbon Nanotechnologies, Aspen Aerogels Fortune 500 Companies: 3M, Affymetrix , Cabot, Dow, Dupont , Kodak, Texaco, AMD, GE, HP, IBM, Intel, Motorola, NEC Disrupters: Bioforce Nanoscience, Nanosolar

61. 62 Potential Risks of Nanotechnology Health issues Nanoparticles could be inhaled, swallowed, absorbed through skin, or deliberately injected Could they trigger inflammation and weaken the immune system? Could they interfere with regulatory mechanisms of enzymes and proteins? Environmental issues Nanoparticles could accumulate in soil, water, plants; traditional filters are too big to catch them New risk assessment methods are needed National and international agencies are beginning to study the risk; results will lead to new regulations

62. 63 Summary: Science at the Nanoscale An emerging, interdisciplinary science Integrates chemistry, physics, biology, materials engineering, earth science, and computer science The power to collect data and manipulate particles at such a tiny scale will lead to New areas of research and technology design Better understanding of matter and interactions New ways to tackle important problems in healthcare, energy, the environment, and technology A few practical applications now, but most are years or decades away

63. Mother Nature Mankind has always found inspiration in Mother Nature. Today developing technologies allow us to probe and better understand the nanoscience of Mother Nature.

64. FNI 1A 65 1. Intro to Nano Nano Industry Ch 1, 2,16 2. The Nano Debate Smalley vs Drexler Ch 15 3. History of Nano Future of Nano Ch 15 4. Scale of Things Nano Ch 1 5. Nanochemistry Ch 3 6. The Atom Game Ch 3 7. Quantum mechanics (Ch 6) Unit 1Test 8. Waves – Slinkys, Light and Orbitals Ch 3 9. Tools of Nano Ch 3 10. Microscopy 1 Optical and Electron Ch 3 11. Electron microscopy Ch 3 12. Microscopy 2 Electron beam specimen interactions 13. Scanning probe microscopy Ch 3 14. Microscopy 3 Scanning Probe Ch 3 15. Other Tools Ch 3 Test 2 16. UWEC Field Trip 17. X-Ray Analysis Ch 3 18. X-Ray Diffraction 19. Carbon Nanotubes Ch 4 22. Carbon Nanotubes 21. Nanomaterials Ch 5, 12 20. Gold Nanoparticles 23. Synthesis/self assembly/Test 3 24. Magnetic Nanoparticles 25. Special Topics Energy Ch 9 26. Alternative energy applications of Nano 27. Special Topics Biomedical Ch 10-11 28. Lab on a Chip 29. Student Presentations 30. Student Presentations 31. Final Exam 32. Last Day Introduction to Nanoscience