1.A/Prof Jeffrey Funk Division of Engineering and Technology Management National University of Singapore When Will NanoTechnology-Based Products Become Economically Feasible for Specific Applications? For information on other technologies, see http://www.slideshare.net/Funk98/presen

2. Session Technology 1 Objectives and overview of course 2 Two types of improvements: 1) Creating materials that better exploit physical phenomena; 2) Geometrical scaling 4 Semiconductors, ICs, electronic systems 5 MEMS and Bio-electronic ICs 6 Nanotechnology and DNA sequencing 7 Superconductivity and solar cells 8 Lighting and Displays 9 Human-computer interfaces (also roll-to roll printing) 10 Telecommunications and Internet 11 3D printing and energy storage This is Part of the Sixth Session of MT5009 3. Objectives What are the important dimensions of performance for nanotechnologies and their higher level systems? What are the rates of improvement? What drives these rapid rates of improvement? Will these improvements continue? What kinds of new systems will likely emerge from the improvements in nanotechnology? What does this tell us about the future? 4. As Noted in Previous Session, Two main mechanisms for improvements Creating materials (and their associated processes) that better exploit physical phenomenon Geometrical scaling Increases in scale Reductions in scale Some technologies directly experience improvements while others indirectly experience them through improvements in components A summary of these ideas can be found in 1) What Drives Exponential Improvements? California Management Review, Spring 2013 2) Technology Change and the Rise of New Industries, Stanford University Press, 2013 3) Exponential Change: what drives it? What does it tell us about the future? 5. Both are Relevant to Nanotechnology Creating materials (and their associated processes) that better exploit physical phenomenon Creating materials such as carbon nanotubes that better exploit small dimensions Geometrical scaling Increases in scale: larger production equipment Reductions in scale: exploiting phenomena at small dimensions; ability to create smaller dimensions enables more phenomena to be exploited. Some people argue that thin film is part of every important technology Some technologies directly experience improvements while others indirectly experience them through improvements in components Better nanotechnology-based products lead to better electronic systems 6. Both Relevant to Nanotechnology (cont) Rapid improvements in integrated circuits (ICs), magnetic storage, other electronic technologies over last 50 years Moores Law Areal recording density of hard disk platters These improvements have enabled many new forms of electronic products and improvements in them Computers, Mobile Phones, Internet Is there a similar or greater potential for nanotechnology? Are there indications of this potential in a 7. Outline What is nanotechnology? Fullerene, Graphene and Carbon Nanotubes Quantum Dots Nanoparticles Nanofibers Common issues 8. What is NanoTechnology? (1) Things on the nano-meter (10-9) level: 1-100 nm ICs, MEMS, and bio-electronics can be considered nano-technology But, nano-technology should take us to smaller scale, molecular or even atomic level like ICs, these technologies should benefit from the reductions in scale that these nano-dimensions represent involve self-assembly (like with snowflakes and biological reproduction) so that the costs of making them are low Have progress that is measurable and identifiable 9. http://www.nanostart.de/index.php/en/nanotechnology/tiny-structures-with-a- big-future (Currently, mostly semiconductors and pharmaceuticals) Too Much Hype!!!! http://www.nanowerk. com/spotlight/spotid =1792.php 10. What is NanoTechnology? (2) One-dimensional nanoproducts thin film devices, coatings (antireflection, corrosion), graphene and quantum wells (stacked thin film layers) found in semiconductor, metallic, and dielectric films Two-dimensional (2-D) nanoproducts single or multiwall nanotubes nanowires, nanorods Three-dimensional (3-D) nanoproducts fullerenes, dendrimers nanoparticles polymeric dispersions 11. Why do we care? From Large to Small A number of physical phenomena become pronounced as the size of the system decreases increase in surface area to volume ratio altering mechanical, thermal and catalytic properties statistical and quantum mechanical effects at less than 100 nanometers hydrogen bonding, molecular forces, van der waals forces Different properties appear at the nano-scale, enabling unique applications opaque substances become transparent (copper) stable materials turn combustible (aluminum) insoluble materials become soluble (gold) high thermal and electrical conductivities and strength (carbon) 12. As the size of a particle becomes smaller, van der walls (vdw) forces (i.e., electro- magnetic forces between neutral atoms) become much more important than gravitational forces (earth-particle and particle-particle) Source: Treavor A. Kendall, 13. Once we have Small Things, How can we Make Big Things? Top-down approaches are too expensive Micro-machining Photolithography Electron-beam lithography Focused ion beams Bottom-up, or so-called self assembly is needed Modern synthetic chemistry enables synthesis of chemicals from molecules New methods are needed 14. Manufacturing Processes are Critical Processes determine costs and performance of nano- products Needed characteristics of processes High purity: often need 99.9999999% High material yields: low yields are common in many processes such as molecular beam epitaxy (3-10%) or metal organic CVD (theoretical limit is 50%) Small number of process steps Low temperature and vacuum requirements as these raise costs Benefits from increases in scale of equipment, such as those that exist in chemical plants and production of liquid 15. Outline What is nanotechnology? Fullerene, Graphene and Carbon Nanotubes Quantum Dots Nanoparticles Nanofibers Common issues 16. Fullerenes, Graphene, and Carbon Nanotubes Fullerenes specific number of carbon atoms arranged as sphere 20 is the smallest, many other stable numbers Graphene flat sheet of carbon atoms Carbon Nanotubes flat sheet is rolled so that sides are connected, thus 17. Fullerenes As size of fullerenes increases, energy gap between highest and lowest orbital also decreases where this gap is analogous to the band gap in semiconductors One can also dope fullerenes by inserting atoms inside of them Thus, one can design fullerenes with specific electronic properties as with semiconductors Depending on purity, price of fullerenes is more than $100 per gram 18. Graphene A single layer of carbon atoms Very low electrical resistance, high thermal conductivity (4,000 W/m-K), and high mobility (about 200,000 cm2/Vs at room temperature, compared to 1,400 in silicon and 77,000 in indium antimonide) One of strongest materials, but yet flexible Unusual optical behavior: equally transparent to ultraviolet, visible and infrared light Two current markets (composites for strength and electrodes for conductivity) but also displays, computer chips, and solar cells http://www.youtube.com/watch?v=XDJRlBSXsow Source: Segal, Michael (2009). "Selling graphene by the ton". Nature Nanotechnology 4 (10): 6124 Nature 483, S29 (15 March 2012). Also http://www.azom.com/news.aspx?newsID=11679 19. One Measure of Improvement Diameter of the sheets that can be fabricated According to Prof..Tomas Palacios of MIT, the size of graphene sheets has been increased from a few microns to about 30 inches in the last few years. Further increases will open up new applications as will cost reductions. http://edition.cnn.com/2013/04/29/tech/graphene- miracle-material/index.html?hpt=hp_c3 20. 300 square centimeter graphene film from Graphene frontiers Graphene Frontiers claims it will have a roll-to-roll machine prototype ready within a few years. The three big applications will be desalinization and filtration, biosensing and electronics. 21. http://www.azonano.com/article.aspx?ArticleID=3185 22. But lots of controversy!!!! Many argue these large sheets do not have consisten performance (including flatness) across the sheets 23. Another Measure of Improvement is Price (Euros/cm2) http://www.graphenea.com/pages/graphene- price#.Ut8YMRAZ6Uk 24. What About Graphene Composites? Alternate layers of graphene with other materials grow single layer of graphene on a metallic deposited substrate using chemical vapor deposition, then add another metal layer repeat the steps, resulting in multilayer metal-graphene composite of 0.00004% in weight of graphene The graphene makes copper 500 times and nickel 180 times stronger Big application for aircraft? Another material, a nanocoating, reduced fuel consumption by 2 percent and enabled one airline to save $22 million per year http://spectrum.ieee.org/nanoclast/semiconductors/nanotechnology/for-first-time-graphene-and-metal- make-strong-composite 25. Not Just Graphene, i.e., Carbon As of April 2013, >10 materials found that are one or a few atoms thick Transition metal dichalcogenides for solar cells http://gizmodo.com/super-thin-graphene-solar-panels-could-pave-the-way-for-489111383 Boron nitride (insulator) has been fabricated in one- atom sheet as has Molybdenum Sulfide Molybdenum Sulfide is semiconductor, Boron Nitride is insulator, Graphene is for interconnect Together one atom thick flash memory devices have been constructed (http://www.thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based- on-2d-materials-a-single-atom-thick/) More complex devices can be constructed by doping one of the layers http://thessdreview.com/daily-news/latest-buzz/flash-memory-to-be-based-on-2d-materials-a-single-atom- thick/ April 29, 2013. http://edition.cnn.com/2013/04/29/tech/graphene-miracle-material/index.html?hpt=hp_c3 26. Other Materials have Similar Hexagonal Lattice Structures to Graphene Source: Nature, Vol 497, 23 May 2013 27. Returning to Graphene, Why Might it Get Dramatically Cheaper? Material costs are obviously low 28. How much Cheaper will Graphene or other Ultra-thin materials become? Will new processes be found? Will increases in scale help? The large number of possible processes and composites makes people optimistic What applications will become possible as the cost of graphene falls? Source: http://www.multibriefs.com/briefs/spe/Graphene-based%20nanocomposites.pdf 29. http://iopscience.iop.org/1402-4896/2012/T146/014024/article Methods of Making Graphene Film 30. http://iopscience.iop.org/1402-4896/2012/T146/014024/article CVD-Based Graphene Growth on Ni, Cu, 31. Growing Graphene on Cu Films http://iopscience.iop.org/1402-4896/2012/T146/014024/article 32. Different Methods of Synthesis, Different Application 33. What about applications? And Market Growth? 34. A likely early application: Flexible Transparent Electrodes Replace indium tin oxide in solar cells, light- emitting diodes (LEDs), organic light-emitting diodes (OLEDs), touch screens, smart windows LCD displays Different levels of sheet resistance are needed for each Composites have highest levels of conductance and transmittance (FeCl3-FLG [few layer graphene]) Problems with indium tin oxide High deposition temperature, brittle and fragile http://iopscience.iop.org/1402-4896/2012/T146/014024/article 35. http://onlinelibrary.wiley.com/doi/10.1002/adma.201200489/abstract;jsessionid=2450 8C91658C71CB5F94C7AED94D5BC8.d03t01 36. http://iopscience.iop.org/1402-4896/2012/T146/014024/article Transparent Electrodes, continued 37. Looking Further to the Future: Graphene Aircraft? What about making aircraft from grapheme? Why would we want to do this? How might we estimate the cost of making aircraft from grapheme? 38. Looking Further to the Future: Graphene Aircraft? If graphene is 0.1 Euro/cm2(Graphenas estimate for 2020) would Airbus or Boeing use graphene as the material for fuselage or wings? How would you do a rough calculation? Roughly speaking, since a Boeing 777s fuselage and wings have a surface area of about 3000 square meters, it would cost about 3 million Euros for a single layer of Graphene to be used on their fuselage and wings or about 1/100 the current price of a Boeing 777. The fuselage of Boeing 777 has a length of about 80 meters and a diameter of about 6 meters 39. One Possible Future All structures and products are made from single atom thick materials Would lead to much lower material usage And thus less energy needed to make materials? Steel and other materials require lots of energy Lower energy usage by transportation equipment Lighter equipment leads to lower energy usage More interesting structures Taller structures More interesting shapes that are not constrained by weight Carbon fiber has been moving us in these directions for many years, but single atom thick materials can 40. Will Graphene Make these Highways Economically 41. http://nextgenlog.blogspot.sg/2012/07/materials-graphene-rising-to-1- billion.html Back to Reality, the market is still small.How fast will it grow? 42. Replacement of existing component in an existing product. Replace: carbon black, carbon fibre, graphite, carbon nanotubes, silver nanowires, Indium Tin Oxide, silver flakes, copper nanoparticles, aluminium, silicon, GaAs, ZnO, etc. The strength of graphene's value proposition is different for each target market. http://www.printedelectronicsworld.com/articles/idtechex-forecasts-a-100-million-graphene-market-in- 2018-00004721.asp?sessionid=1 IDTechEx forecasts $100 million Graphene market in 2018 (on 12 September 2012) 43. Outline What is nanotechnology? Fullerene, Graphene and Carbon Nanotubes Quantum Dots Nanoparticles Nanofibers Common issues 44. Single (SWNT) and Multi-Walled Nano Tube (MWTB) Carbon nanotubes can be made with single or multiple walls, in different diameters, and with different axes Like fullerenes, only certain diameters exist and each design has different properties 45. Carbon Nanotubes (1) Diameters and axes impact on levels of conduction and thus whether the carbon nanotube is a conductor, semiconductor, or an insulator Conducting nanotubes 1000 times higher conductivities than copper 100 times higher current densities than superconductors but only if there is one continuous piece of nanotube (which is quite difficult) Easier to make long superconductors (but even this is difficult) than long nanotubes Thus, carbon nanotubes will probably be used for short distances, for example for IC or board level interconnect 46. Carbon Nanotubes (2) Carbon nanotubes are the strongest materials known in terms of tension However, lack of consistency means that these strengths may not be maintained at the macroscopic level with many nanotubes One application is cutting thin slices of biologic material (