Molecular Electronics For Fun and Profit(?)

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1 Molecular Electronics For Fun and Profit(?) Prof. Geoffrey Hutchison Department of Chemistry University of Pittsburgh July 22,

2 Moore s Law: Transistor Count Doubles Every 18 Months Gordon Moore: Co-founder of Intel From Intel Corp. circa 2007 Similar trends observed in chip performance, price per peformance, etc.

3 Moore-San s Law Image courtesy M. Ratner

4 Don t Underestimate Silicon... Actually, these are from 1997(!)

5 Current Intel Roadmap 45nm 32nm

6 International Technology Roadmap for Semiconductors (ITRS)

7 Moore s Second Law: Exponential Economics Cost of a building a new fabrication plant doubles every 3-4 years: 6,000,000,000 Cost (US$) 4,800,000,000 3,600,000,000 2,400,000,000 1,200,000, : ~$6 billion! Advances in conventional lithography are quickly becoming cost-prohibitive!

8 Molecular Electronics: Just anoscale? 3D: Bulk Films 2D: Monolayer M 2+ M M M 2+ M 2+ 1D: Chains 0D: Individual Molecules

9 Why Organic Electronics? Relative to Inorganic Materials: Pros Greater tailorability through synthetic chemistry Wet deposition Wide-area Inexpensive Flexible, lightweight Synthesis = 6.02x10 23 Cons Lower electron mobility Slower switching speeds Hard to obtain complementary p/n logic Integration into industry?

10 Broad Applications for Molecular Electronic Materials Light-Emitting Diodes Hole transport layers Flexible anodes Photovoltaic Devices Thin-Film Transistors Flexible circuits Smart Windows Fast color changes Anti-Static Films Device fabrication Photographic film

11 Batteries: ot Just Inorganics... Energy Density for Secondary Batteries Volumetric Energy Density / WhL Smaller Lead i-cd i-mh Li-Ion Polymer Li-Ion Li-Metal Lighter Gravimetric Energy Density / Whkg -1

12 Reaction Mechanism for LIBs : Doped Li + : Li + Anode Current Collector Anode Graphite (Intercalation Layer) Electrolyte Organic Solvent plus Supporting Electrolyte (ex. LiBF4/PC) Cathode Lithium Metal Oxide (ex. LiCoO2) Cathode Current Collector

13 Reaction Mechanism for LIBs e - e - : Doped Li + : Li + Anode Current Collector Anode Graphite (Intercalation Layer) Electrolyte Organic Solvent plus Supporting Electrolyte (ex. LiBF4/PC) Cathode Lithium Metal Oxide (ex. LiCoO2) Cathode Current Collector

14 Ink-Jet Printing of Organic Electronics Ink-Jet Printing Konarka: Ink Jet Printing for Solar Cells Mar. 4, 2008 Transistors GE: Ink Jet Printing for Displays Mar. 11, 2008 Sekitani et al. PAS 2008 p. 4976

15 Organic Field-Effect Transistors Vsd Source Semiconductor Dielectric Gate Electrode Drain Isd ~ 0.0 A Off Applied Gate Potential Vsd Source Semiconductor Dielectric Gate Elecrode Drain Vgate Isd = 10 x A On

16 Organic Field-Effect Transistors Operation of an Organic Field-Effect Transistor Example Organic Semiconductor Materials Source Semiconductor Drain O X O Dielectric Gate Electrode S S S S Applied Gate Potential O X O Source Semiconductor Dielectric Gate Elecrode Drain O S O O S R O n S R S n H H n n

17 Back to the anoscale... 3D: Bulk Films 2D: Monolayer M 2+ M M M 2+ M 2+ 1D: Chains 0D: Individual Molecules

18 Enough Bulk Conductivity: How Do You Wire Up a Molecule? Many, Many Methods... STM tip Crossbars Break Junctions

19 Example: Device Fabrication Sixty 15 mm x 6 mm chips are fabricated on a thin (200 µm) Si wafer. Bonding pads are defined by photolithography. Critical features are defined by e-beam lithography. A timed etch is used to suspend the junctions. Ralph Group, Cornell

20 Electromigration: Making a 1-3nm Gap Current Voltage Ralph Group, Cornell

21 Single Molecule Transistors ote: o Guarantee of 2 Connections Source V (Pt) Ru Ru Gate Oxide (Al2O3) Gate (Al) Vg Ralph Group, Cornell Drain (Pt)

22 Metal / Molecule Interface Coordination One-Site Bridging Three-Site WARIG: PowerPoint Science!

23 Coulomb Blockade Source Drain

24 Coulomb Blockade e - Source Drain

25 Coulomb Blockade e - e - e - Source Drain

26 Coulomb Blockade ee - e - - e - e - Source Source Drain

27 Coulomb Blockade in [Ru2(tppz)3] +4 e - 4K Temp. Single-Molecule Coulomb Blockade Transistor 7.5 Source Drain Vsd Charge passes when source, drain and molecule bridge electronic states are aligned Gate (V) Conductance (ns)

28 Is it Really Single-Molecule? You must do statistics... You must do statistics... Careful controls ( no molecules ) Dilution Experiments Venkataraman, L. et. al. ano Letters 2006 v. 6,

29 Is it Really A Molecule? Is it a nanoparticle? What are molecular signatures? What are control experiments? What are our statistics? WARIG: Be Skeptical! We can do theory... But what s the real experiment?

30 Prospectus Statistics, Statistics, Statistics! Charge Transport Mechanisms More Charge Transport Ensembles & Dynamics Solar Energy: Where things get (more?) complicated

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