Polymers and Nanotechnology

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1 Polymers and Nanotechnology Grant Willson Department of Chemical Engineering Department of Chemistry The University of Texas Austin, Texas The Texas Tower

2 Grad students 2009

3 Nano, Nano Bizarre television comedy with Robin Williams as Mork from Ork,, who is an alien hatched from an egg, sent to investigate Earth and report back to his superiors. Robin Williams as Mork

What is a nanometer anyhow? Start with a centimeter. Now divide it into 10 equal parts. 1 cm 1 mm A centimeter is about the size of a bean. Each part is a millimeter long. About the size of a flea.

4 What is a nanometer anyhow? Start with a centimeter. Now divide it into 10 equal parts. 1 cm 1 mm A centimeter is about the size of a bean. Each part is a millimeter long. About the size of a flea. Now divide that into 10 equal parts. 100 µm Each part is 100 micrometers long. About the size (width) of a human hair. Now divide that into 100 equal parts. Now divide that into 10 equal parts. 1 µm 100 nm Each part is a micrometer long. About the size of a bacterium. Each part is a 100 nanometers long. About the size of a virus. Finally divide that into 100 equal parts. 1 nm Each part is a nanometer. About the size of a small molecule.

5 Why Make Things so Small? Faster Lighter Cheaper More energy efficient Can get into small spaces Different properties at very small scale

6 Color Depends on Size!?

7 The Lotus Effect Buddha

8 Super Hydrophobic Leaf Surface

9 Self Cleaning Paint

10 There was n the Prof. beginning.. Richard Feynman and on December 29th 1959 in a talk to the APS He did say unto to the people..

Why cannot we write the entire 24 volumes of the Encyclopedia Brittanica on the

11 And so we did ``There is Plenty of Room at the Bottom'' And thereby did he then start the nano movement and he asked the multitudes. Why cannot we write the entire 24 volumes of the Encyclopedia Brittanica on the head of a pin? well, we wrote the Torah instead! Where we is Haifa s Technion-srael nstitute of Technology

12 And so it has been since that time that we have continued to find room at the bottom and then..there was NN and the $500M!

14 and so He was chosen by the people and. He did give unto them $500 million and. He did command the multitudes to. Add 1 trillion $ and 2 million nano jobs to the world economy by 2015! He She

15 !!

Moore s Law # Transistors Speed 8080 8086 386 DX 286 Pentium 486 DX Pentium 4 Pentium Pentium 100,000,000 10,000,000

17 Moore s Law # Transistors Speed DX 286 Pentium 486 DX Pentium 4 Pentium Pentium 100,000,000 10,000,000 1,000, ,000 10, , Time tanium Microprocessor Evolution 1Billion

18 Photolithographic Process Photoresist Substrate Coating hυ Mask Negative Positive Exposure Develop Transfer Strip Photoresist

19 Step and Repeat Exposure Systems R= k λ NA

20 Minimum Dimension (nm) Minimum Feature Size Reduction in Semiconductor Devices: Moore s Law 10,000 5,000 2,000 1, K / K / 5000 R= k 64 K / nm λ NA Contact Exposure / 436nm 256 K / M / nm 1:1 Projection 4 M / nm 16 M / nm 64 M / nm 5:1 Projection 256 M / G / G / Year 157nm? 16 G /?

21 Some Scale Perspective Å 193nm resist images These 80nm features are less than 600 carbon atoms wide [based on the average length of a carbon-carbon bond] 40nm images 20nm

22 Physicists increase the NA of the Lenses Starlith 500 Lens (Zeiss)

23 A Prophetic Advertisement?? Size Matters????

24 t All Started Here NCÉPHORE NÉPCE

25 A Historical Perspective Printed with Bitumen of Judea 1826 Point de vue du Gras by Nicephore Niepce

26 Contact Printing in Bitumen of Judeav A Contact Photogravure of Cardinal d Amboise by Niepce (1826)

27 Dicromated Gelatin Protein + K 2 Cr 2 O 7 High Sensitivity Poor Shelf Life William Henry Fox Talbot Photographed in 1864

28 The First Synthetic Photopolymer Louis Minsk Eastman Kodak O n O C CH CH hν O H H O C n H H C O O Poly(vinyl cinnamate) n Adhesion Problems

29 Hans Wegner Co-inventor of Kodak s KTFR O N 3 N 3 hν O N N Swelling Problems

32 Swelling, Snakes, Ugh!!

33 Novolac/DNQ Photoresists O OH CH 3 SO 3 R N 2 nhibited Novolac () UV O OH OH CH 3 SO 3 R Photoproduct (P) Substrate UV Coat LogR Novolac Add DNQ P 365-nm exposure Substrate Substrate P P P P P P Expose Develop

34 DNQ Novolac Resists

36 Power at the wafer plane - Perkin Elmer 500

37 UV Spectrum of Resist Components

38 mpact of Photoresist Absorbance on Developed mage Profile Exposure Step Final Profile Moderate absorbance High absorbance

0 175 ArF 193 nm Polyacrylates (aliphatic) Hiroshi to KrF 248 nm 200 225 250 275 300 325 350 375 400

39 Chemist enable reducing λ mprovement requires higher photosensitivity Absorption coefficient [1/µm] 2.8 Poly-(4-hydroxystyrene) and greatly improved transparency 2.4 Meta-cresol novolak ArF 193 nm Polyacrylates (aliphatic) Hiroshi to KrF 248 nm Wavelength [nm] i-line 365 nm Jean Fréchet Source: R.D. Allen et al., BM J. Res. Develop. 41 (1/2), (1997)

40 Chemical Amplification nsoluble hν Φ < 1 Soluble nsoluble Generator hν Φ < 1 Catalyst Soluble + Catalyst

42 Optical Micrographs of self-developed mages in Polyphthalaldehyde

43 Chemically Amplified Resists for 248nm Photoacid Generation S +- SbF 6 hν H +- SbF 6 Mass with acid without acid Acid-Catalyzed Deprotection Temperature ( C) CH 2 protecting group CH O O n H + O CH 2 + H + CH OH n + CO 2 + CH 2 =C CH 3 CH 3

45 First Commercial mplementation of Deep UV Photolithography ROX level of 1M DRAM BM

46 enjoyed working with you! Please study hard for the final Rework midterm problems Look over homework and correct errors Review vocabulary Review the quantitative work we did Kinetics Characterization Moments of the molecular weight Viscosity Etc. Let us help you

Section 2: Lithography. Jaeger Chapter 2 Litho Reader. The lithographic process

Section 2: Lithography. Jaeger Chapter 2 Litho Reader. The lithographic process Section 2: Lithography Jaeger Chapter 2 Litho Reader The lithographic process Photolithographic Process (a) (b) (c) (d) (e) (f) (g) Substrate covered with silicon dioxide barrier layer Positive photoresist