EU: NANOMOL-CANEL. Bottom-up opportunities - the promise of molecular electronics. Thomas Bjørnholm, Nano-Science Center, University of Copenhagen

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1 Bottom-up opportunities - the promise of molecular electronics Thomas Bjørnholm, Nano-cience Center, University of Copenhagen EU: NANOMOL-CANEL INGLE ELECTRON TRANITOR OF A INGLE CONJUGATED MOLECULE WITH ACCE TO EVERAL REDOX TATE ergey Kubatkin, Andrey Danilov, Mattias Hjort, Jérôme Cornil, Jean-Luc Brédas, Nicolai tuhr-hansen, Per Hedegård, and Thomas Bjørnholm Nature, (2003). Kasper Nørgård, Thomas Bjørnholm Chem. Commun. Feature 1793 (2005) Artist view

2 Background: Two-terminal devices (diodes) H - H TM BrJ H π H Gold electrode Aviram & Ratner: ingle molecule diode (in theory)

3 Background: Three-terminal devices (field effect transistors) R (ΓG 0 ) -1 V sd V g R ource Q R Drain Q D D D Q Q Energy Gate R GΩ, Q = ne equential electron transfer R kω, Q 0 Tunneling V sd current V sd no current current no current V g Current V g

4 Background: Three-terminal devices (field effect transistors) R Q R V sd Q1 Q1 ource Drain V g Gate V sd 3 nm V g Classical Coulomb charging dominates large nanostructures

5 Organic molecules are great. We are made of them! (1) Easy to tailor make all alike; (2) flexible (responsive); (3) easy to process from solution; (4) self-organize; (stability (auto repair)) H n N 1 nm N N Co 2+/3+ n n n N N N H n

6 ynthesis of efficient building blocks for self-assembling electronics CHO R OHC R 1) CH 3 COCl/ BBr 3 /CH 2 Cl 2 2) I 2 /Toluene O R O all trans OPV5 Nicolai tuhr Hansen J. Org. Chem. 68, (2003).

7 Fabrication of the ET 3.2 nm 2 nm CVD T = 4 K ergey Kubatkin Nature, (2003).

8 ingle molecule single electron transistor 2 nm Nature, (2003).

9 ingle molecule single electron transistor R GΩ, Q = ne equential electron transfer V sd current no current no current V g current V sd 300 mev V g

10 EC: J. Heinze, K. Müllen, et al, J. Chem. oc. Chem. Commun Ι(n n+1) = μ OPV (n+1, 0) μ OPV (n, 0) = (C g /(C s +C d +C g ) )e ( V g (n) - V g (n+1)) Redox chemistry in the ET R 5 GΩ

11 ummary of ET results HOMO - LUMO GAP

12 -1 Al 2 O mev mev mev mev

13 Molecule and device are not separable due to strong image charge effects δ(α) = 27.2 evå/(4 Å * ε r ) 4eV E (ev) Per Hedegaard Hubbard model: t = 3.92 ev, U = 4.27 ev, aε r = 4.7 Å Chem. Phys. in press (2005), Cond. Mat. 2005

14

15 tructure model of the ET of OPV5

16 Zoom on image charge

17 Prediction for chemisorbed OPV

18 ynthesis of efficient building blocks for self-assembling electronics CHO R OHC R 1) CH 3 COCl/ BBr 3 /CH 2 Cl 2 2) I 2 /Toluene O R O all trans OPV5 Nicolai tuhr Hansen J. Org. Chem. 68, (2003).

19 TEM of electromigration QuickTime and a Cinepak decompressor are needed to see this picture. QuickTime and a Cinepak decompressor are needed to see this picture. H.B. Heersche, G. Lientschnig, H.W. Zandbergen and H.J. van der Zant (to be published).

20 Breaking process with and without molecules Molecules self assemble on the gold electrodes prior to breaking bare gold OPV3 I (na) boomerang I (na) CB I (na) tunnel I (na) steps Vb (mv) Vb (mv) Vb (mv) Vb (mv)

21 Controls with solvent only 20 T =4.2 K 10 I (na) Vb (mv) 0.20 Large Kondo temperatures and in general very little gate dependence! diff. cond. (μ) T k = 500 K Vb (mv)

22 Molecular junction with OPV-3: Kondo I (na) peak height (μ) 10 5 T k 20 K peak height (e 2 /h) T (K) Vb (mv) weak gate dependence diff. conductance (μ) diff. conductance (e 2 /h) V bias (mv) Vb (mv) Herre van der Zant unpub. V gate (V)

23 Another molecular junction with OPV-3: Kondo? V bias (mv) QuickTime and a TIFF (LZW) decompressor are needed to see this picture. B = 0 NDR spin blockade? B = 7T Diff. Cond. (n) K 2.7K 3K 3.5K 4K 4.5K 5K 5.5K 6K 6.5K T-dependence T k 12 K x Vb (mv) 5.2x x x x x10-3 Diff. Cond. (e 2 /h) V gate (V) Diff. Cond. (n) Herre van der Zant unpub. g = 3.4 V gate (V) B-dependence Vb (mv) Diff. Cond. (e 2 /h)

24 Relation between molecular properties and charge transport H π H H π H R/Ω H H H H I (na) Vb (mv) na pa

25 MEMPHY LOGO, Tegning af O. B. ørensen Proof of concept

26 Nature (2000)

27 AFM topgraphy of DPPC + Au-nanoparticles b + 25 μm 50 μm Adv. Mat. 14, (2002).

28 TEM 3 nm Tue Hassenkam/Kasper Nørgård Adv. Mat. 14, (2002).

29 LIPID Nano Letters 4, (2004)

30 LIPID Nano Letters 4, (2004).

31 Nano Letters 4, (2004).

32 QuickTime and a TIFF (LZW) decompressor are needed to see this picture. QuickTime and a TIFF (LZW) decompressor are needed to see this picture. QuickTime and a TIFF (LZW) decompressor are needed to see this picture. 3 nm Adv. Mat. 14, (2002).

33

34 Molecular memory devices of Langmuir films of Rotaxanes (Collaboration with Fraser toddart et al) -2e - + 2e - ++ olution: Yes olid state (film):?

35

36

37

38 Nano-imaging

39

40 QuickTime and a TIFF (LZW) decompressor are needed to see this picture.

41 Rotaxane status -2e - + 2e - ++? Der kræves QuickTime og et TIFF (LZW)-komprimeringsværktøj, for at man kan se dette billede.

42 Acknowledgements Herre van der Zant, Delft INGLE ELECTRON TRANPORT THROUGH A INGLE CONJUGATED MOLECULE ergey Kubatkin, Andrey Danilov, Mattias Hjort, Jérôme Cornil, Jean-Luc Brédas, Nicolai tuhr-hansen, Per Hedegård, Thomas Bjørnholm Nature, (2003). ELF-AEMBLY AND CONDUCTIVE PROPERTIE OF MOLECULARLY LINKED GOLD NANOWIRE Tue Hassenkam, Kasper Moth-Poulsen, Nicolai tuhr-hansen, Kasper Nørgaard, M.. Kabir, Thomas Bjørnholm Nano. Lett (2004) FABRICATION OF 2D GOLD NANOWIRE BY ELF-AEMBLY OF GOLD NANOPARTICLE ON WATER URFACE IN THE PREENCE OF URFACTANT. Tue Hassenkam, Kasper Nørgaard, Lars Iversen, Chris Kiely, Mathias Brust,Thomas Bjørnholm Adv. Mat. 14, (2002). WITCHING ROTAXANE IN LANGMUIR FILM. AN X-RAY REFLECTIVITY TUDY Kasper Nørgaard, Jan O. Jeppesen, Bo W. Lauersen, Jens Bæk imonsen, Fraser toddart, and Thomas Bjørnholm J. Phys. Chem. B in press. WATER IN CONTACT WITH EXTENDED HYDROPHOBIC URFACE. DIRECT EVIDENCE OF DEWETTING Torben R Jensen, Kristian Kjær, Morten Ø. Jensen, Günther Peters, Thomas Bjørnholm Phys. Rev. Lett. 90, (2003); P. Ball, News & Views, Nature 423, (2003). FLUCTUATION CAUGHT IN THE ACT Lars K. Nielsen, Thomas Bjørnholm, Ole G. Mouritsen, Nature 404, 352 (2000). NOVEL YNTHEI OF PROTECTED THIOL END-CAPPED TILBENE AND OLIGO(PHENYLENEVINYLENE) (OPV). Nicolai tuhr-hansen, Jørn B. Christensen, Niels Harrit, Thomas Bjørnholm J. Org. Chem. 68, (2003). ADAPTIVE CHEMITRY OF BIFUNCTIONAL GOLD NANOPARTICLE AT THE AIR/WATER INTERFACE. A YNCHROTRON X-RAY TUDY OF GIANT AMPHIPHILE. Kasper Nørgaard, Marcus Weygand, Kristian Kjaer,Mathias Brust,Thomas Bjørnholm. Faraday Discussions 125, (2004). Funding:Danish Research Counsil, EU

43 Acknowledgements Herre van der Zant, Delft INGLE ELECTRON TRANPORT THROUGH A INGLE CONJUGATED MOLECULE ergey Kubatkin, Andrey Danilov, Mattias Hjort, Jérôme Cornil, Jean-Luc Brédas, Nicolai tuhr-hansen, Per Hedegård, Thomas Bjørnholm Nature, (2003). ELF-AEMBLY AND CONDUCTIVE PROPERTIE OF MOLECULARLY LINKED GOLD NANOWIRE Tue Hassenkam, Kasper Moth-Poulsen, Nicolai tuhr-hansen, Kasper Nørgaard, M.. Kabir, Thomas Bjørnholm Nano. Lett (2004) FABRICATION OF 2D GOLD NANOWIRE BY ELF-AEMBLY OF GOLD NANOPARTICLE ON WATER URFACE IN THE PREENCE OF URFACTANT. Tue Hassenkam, Kasper Nørgaard, Lars Iversen, Chris Kiely, Mathias Brust,Thomas Bjørnholm Adv. Mat. 14, (2002). WITCHING ROTAXANE IN LANGMUIR FILM. AN X-RAY REFLECTIVITY TUDY Kasper Nørgaard, Jan O. Jeppesen, Bo W. Lauersen, Jens Bæk imonsen, Fraser toddart, and Thomas Bjørnholm J. Phys. Chem. B in press. WATER IN CONTACT WITH EXTENDED HYDROPHOBIC URFACE. DIRECT EVIDENCE OF DEWETTING Torben R Jensen, Kristian Kjær, Morten Ø. Jensen, Günther Peters, Thomas Bjørnholm Phys. Rev. Lett. 90, (2003); P. Ball, News & Views, Nature 423, (2003). FLUCTUATION CAUGHT IN THE ACT Lars K. Nielsen, Thomas Bjørnholm, Ole G. Mouritsen, Nature 404, 352 (2000). NOVEL YNTHEI OF PROTECTED THIOL END-CAPPED TILBENE AND OLIGO(PHENYLENEVINYLENE) (OPV). Nicolai tuhr-hansen, Jørn B. Christensen, Niels Harrit, Thomas Bjørnholm J. Org. Chem. 68, (2003). ADAPTIVE CHEMITRY OF BIFUNCTIONAL GOLD NANOPARTICLE AT THE AIR/WATER INTERFACE. A YNCHROTRON X-RAY TUDY OF GIANT AMPHIPHILE. Kasper Nørgaard, Marcus Weygand, Kristian Kjaer,Mathias Brust,Thomas Bjørnholm. Faraday Discussions 125, (2004). Funding:Danish Research Counsil, EU

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