Tutorial T5 Will Carbon Replace Silicon? The future of graphitic electronics.

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1 Tutorial T5 Will Carbon Replace Silicon? The future of graphitic electronics. 1:30-2:20 Jim Meindl Nanoelectronics in Retrospect and Prospect 2:20-3:10 Millie Dresselhaus From Graphene to Graphite to Nanotubes to Graphene. 3:10-3:30 Break 3:30-4:20 Phillip Kim The Physics of Graphene 4:20-5:10 Walt de Heer Epitaxial Graphene: Designing a new electronics material from the ground up 5:10-5:30 Panel Discussion

2

3 Outline The problem The carbon solution Why epitaxial graphene Properties Patterning Prototype Devices Chemistry: opening a gap

4 The first transistor (Bell labs 1947) The crystal triode John Bardeen, Walter Brattain and William Shockley

5 The Shockley Building

6 The silicon revolution The end.

7 The carbon solution

8 Carbon electronics Carbon is prominent!

9 Carbon nanotubes: Room temperature ballistic conductors - L (!m) G (2e 2 /h) Nanotube fiber! L V Quantized ballistic conductance T. Ando, T. Nakanishi and R. Saito J. Phys. Soc. Jpn. 67, 2857 (1998) The absence of backward scattering is shown to be ascribed to Berry's phase which corresponds to a sign change of the wave function under a rotation of a neutrino-like particle* in the wave vector space in a two-dimensional graphite *i.e obeying the Dirac-Weyl equation

10 reservoir dissipation in river bed reservoir no dissipation in channel dissipation in reservoir reservoir reservoir Diffusive transport Ballistic transport

11 Carbon nanotube transistors

12 Band structure of graphene: (used for graphite, Wallace 1947, McClure 1957, and for nanotube transport, Ando 1998) H = v F " ˆ # " p E = ±v F p Linear dispersion Symmetry electrons - holes Pseudo spin! ˆ = (! ˆ, ˆ, ˆ x! y! # " x = 0 1 & # % (;" $ 1 0 y = 0 )i & # % (;" ' $ i 0 z = 1 0 & % ( ' $ 0 )1' T. Ando, J. Phys. Soc. Jpn 67 (1998) 2857 z )

13 Graphene ribbons resemble nanotubes gap!1/width metallic bands edge states E F mettalic semiconducting

14 Quantum confinement gap in exfoliated graphene ribbons Exfoliated Graphene flakes Philip Kim Phys. Rev. Lett. 98, (2007) E gap = 0.2 ev /(W-20 nm)

15 Graphene s advantage: cut-a-structure Semiconducting strip Seamless connection between graphene components E F! Quantum dot conduction band Simple ballistic FET valence band Von Voff Quantum interference ring

16 Epitaxial graphene

17 Production of Epitaxial graphene Standard UHV method Charrier et al. STM Typical UHV system Epitaxial graphene

18 Production of Epitaxial graphene Georgia Tech Vacuum Furnace method (2003) Vacuum Furnace STM

19 Epitaxial Graphene Growth UHV Grown Si-Face Furnace Grown Si-Face Furnace Grown C-Face 10X10!m 10X10!m 7.5X7.5!m C-Face termination C Thick graphene films ML SiC SiC Si Thin graphene films 1-5 ML Si-Face termination J.Milan,L U Joanna Hass

20 Epitaxial graphene, C-face AFM LEED: 72.2eV STM 10 Å 20!m

21 Epitaxial graphene pleats

22 Epitaxial graphene, Si-face UHV grown Furnace grown LEED: 78.3eV AFM 20!m AFM 10!m %"""#$!# STM 400 Å G. M. Rutter, et al. Science 317, (2007). %"""#$!#!"#$%$&'$!$ STM!""#$!#

23 Properties

24 Berger, D Xioasong Wu Y Hall bar C-face Magnetotransport: graphene like; non-trivial Berry s phase, Field (T) 1!m x 6.5!m R= 502!/sq!= 9500 cm/vs "R (") R xx ("/sq) Landau level index 1/B (T -1 ) "R/R=4% 100 mk Shubnikov de Haas oscillations Landau level index 1/B (T -1 ) Solid State Com. 2007,Grenoble/GIT collaboration!

25 IR cyclotron resonance spectroscopy: Dirac cone Transition energy (mev) energy E F Field Relative transmission Infrared absorption spectrum in a magnetic field Field dependence of Landau level transitions B(T 1/ 2 )!B dependence of Landau levels v = m/s Dirac cone measured within 10 mev of the Dirac point (B) line Transmission 5-7 layers B=1.5T layers 50 layers Wavenumber (cm) -1 Sadawski, Potemski, Martinez, Berger de Heer. PRL 97, (2006); Gerard Martinez P T 1.5T 1.5T Multi-layer Graphene Graphite ~ 1!m

26 Raman of C-face EG: Graphene-like Faugeras, Nerriere, Potemski, Mahmood, Dujardin, Berger, de Heer APL 2008 Epitaxial multilayer graphene Graphene Monolayer on SiO 2 q~k layers K K Graphite (HOPG) Epitaxial graphene 5-10 layers q~k K K (Graphitic residue) (SiC substrate)

27 STM/XRD: rotational stacking of C-face EG STM : moiré pattern 2 graphene layers rotated 2.2 ; supercell 46.1 Density functional theory graphene AB stack graphene bi-layer R30/R2 stack graphene bi-layer Rotational stacking yields same electronic structure as isolated sheet L. Magaud, F. Varchon, CNRS J. Hass et al. cond-mat/ ! U Joanna Hass

28 Substrate-induced band gap in Si-face EG Zhou, Gweon, Fedorov, First, de Heer, Lee, Guinea,. Castro Neto, Lanzara Nature Materials 6, (2007) n=1 n=2 n=3 n=# Graphene on Si-face: gap is observed; Gap closes as the number of layers increases.

29 Patterning

30 Process

31 e-beam lithography Hall bar FET Quantum Interference loop

32 Devices

33 Confinement and Coherence Berger, D

34 Magneto-transport of a narrow graphene Hall bar T=4,6, 9, 15, 35 and 58 K; -9 T!B!9 T. Landau levels: E n (B)="(2neBv 02 ) Confinement: E n (W)=n#v 0 /W Confined Landau levels: E n (B,W)$ [E n (W) 4 +E n (B) 4 ] 1/4!*=2.7 m 2 /Vs.

35 Anomalous Conductance Transition A reversible, reproducible, drop in the conductivity is observed at 200K.! The resistance is at its theoretical minimum.! Transport is phase coherent over the entire structure (0.5X5 µm).! Resistance is at its theoretical minumum (no boundary scattering!)! Oscillations periodic in the magnetic field are seen.! Temperature (K)

36 Gating Epitaxial Graphene Graphene transistors (Conventional FETs)

37 Side gate structure

38 Top and side gated FETs Si-face Top gate g1 Top gated FET g2 Resistance (k!/sq) x12.5!m s d C-face Top gate 3.5x12.5!m Side gated FET g1 g C-face Side gate d Xuebin Li Q x1!m Gate Voltage (V) The first epitaxial graphene transistors S g2

39 The Dirac point E F! E D # xx (Resistance)(k")$ K! -5 Tesla! Negative Hall (holes) Dirac point Positive Hall (electrons) 5 0!# xy (Hall)(k")$ 1.5!mx12!m Top gated Hall bar, Si face G D S G V g (V) -5

40 Large scale patterned epitaxial graphene FET s Jakub Kedzierski, Craig Keast, Peter Wyatt, Paul Healey, Pei-Lan Hsu MIT Lincoln Labs Mike Spinkle, Claire Berger, Walt de Heer, Georgia institute of Technology

41 Production process SiC blank Hydrogen etch Device Integration Furnace Graphitize Pattern

42 Final Device Geometry SiC Pt Source Al gate (next level) L=10um W=5um Gr Al SiC Pt Drain Al HfO 2 SiC Graphene! Device description and cross section! Nominal device Graphene/SiC active layer (C-side), L = 10um, W = 5 um, ridge parallel, 50nm HfO 2 dielectric, Al gate! Microscope image shown before gate lift-off

43 Set of Identical Devices (Si-face) 1. 4 m % d (1/Ohms) 1. 2 m 1. 0 m ! ! ! G r a p h C W 2 S i T = 40 n m H f O 2 W = 5 µ m, L = 10 µ m!! Minimum conductivity! 130uS to 250uS Field Effect Mobility values! cm 2 /Vs! I on /I off ~ ! V ( V ) g Drain current vs. gate voltage at V d = 0.5V

44 Quantum Interference Device Propagating wave; unit transmission! V=0! Standing wave; (Destructive interference); no transmission!

45 Chemistry: opening a gap

46 graphene oxide Preparation: Hummer s method oxidation Graphite Graphene oxide (GO) Reduction of GO Ruoff et al. Nature 448, 457 (2007)

47 Device made of GO flakes 2!m$2!m AC electrophoresis 2-3 Volts, khz Separation between electrodes: 400 nm, 800 nm, 1400 nm Graphene oxide suspension from N. Kovtyukhva and T. Mallouk, Penn State University Xiaosong Wu, Mike Sprinkle, Xuebin Li, Fan Ming, Claire Berger, Walt de Heer L Mike Sprinkle; L , Fan Ming

48 Typical I-V curve! Asymmetric in bias voltage! Asymmetry correlates with the lengths of the contact edges! There is no systematic dependence on the width of the gap & b Forward Reverse For over 20 samples studied: Ionized donor density at 300K " d =2.2*10 10 to 6.1*10 11 cm -2 Barrier : & b = 0.5 to 0.7 ev

49 GO mobility di/dv=74 k!$ Burnt + - GO flake % d =1X101 1 /cm 2! = 850 cm 2 /Vs at breakdown breakdown

50 Tuning the gap 180! for 16 hours as deposited # b decreases from 0.7 to 0.55 ev " d increases from 3.8*10 11 to 9.1*10 10 cm -2

51 In situ patterned oxidation of graphene structure Optical image of a graphene cross after RIE etching. HSQ mask with window: in situ oxidation ) A ( µ I K V sd (V)

52 EG-GO-EG transistor (1) Pattern epitaxial graphene ribbon HSQ SiC Graphene ribbon (2) Chemical Oxidation Graphene oxide (3) Deposit dielectric and metal gate electrode Source Gate Drain insert afm image here

53

54

55

56

57 Examples of patterned Epitaxial Graphene structures! Hall bar (various ribbon widths) Side gated ribbon (FET) V source gate I I gate drain V Quantum Interference Device

58

59 The temperature dependence of the device parameters. a) The temperature dependence of the Schottky barrier height. b) The area density of ionized donors as a function of inverse temperature. Circle: experiment; Line: A fit to an exponential law (Nd=N0exp(-Ei/2kBT)) gives the ionization energy: Ei=62 mev.

60 Band structure of graphene: (used to explain graphite, Wallace 1947) DIRAC CONE Near E D, E=±v p = ± v hk v~ 10 8 cm/s

61 The epitaxial-graphene/graphite-oxide junction, an essential step towards epitaxial graphene electronics Xiaosong Wu, Mike Sprinkle, Xuebin Li, Fan Ming, Claire Berger, Walt A. de Heer Submitted to PRL, Dec (ConMat: v1)

62 For over 20 samples studied: Ionized donor density at 300K " d =2.2*10 10 to 6.1*10 11 cm -2 Barrier : & b = 0.5 to 0.7 ev 320K 300K 270K 240K 200K 150K 100K 77K EG-GO-EG, a 400nm gap V sd > 2 V

63 Optical absorbance of Graphene Oxide

64 GO MSM device a) A bilayer rectangular GO flake over a 400nm Au gap. b) A pentagon-shaped GO flake bridges two MEG electrodes. The bright spots on MEG are residue of e-beam resist: PMMA, while the bright lines are wrinkles that are often seen in C-face EG. c) I-V characteristics of an 800 nm device. d) An energy band diagram for a EG-GO-EG device. Two Schottky barriers form at the contact edges. i) zero bias. ii) finite bias.

65 Figure 2. I-V characteristics of a 400 nm device at various temperatures: 320, 300, 270, 240, 200, 150, 100, 77K. The sample was annealed at 180 C for 16 hours. a) Nonlinear I-V. The inset: I-V before (blue) and after (red) curing. b) I/T 3/2 as a function of V sd 1/4 /T.

66 Production of patterned structures

67 A Raman scattering study of epitaxially-grown graphite on silicon carbide; pyrolitic graphite and graphene: C. Faugeras, A. Nerriere,M. Potemski,A Mahmood,E. Dujardin,C. Berger,and W. A. de Heer cond-mat v3 19 Sep 2007 Graphite (HOPG) Epitaxial multilayer graphene q~k K K Graphene Monolayer on SiO layers q~k K K n layers (Graphitic residue) (SiC substrate) 60 #

68 Substrate-induced band gap opening in epitaxial graphene S.Y. Zhou, G.-H. Gweon, A.V. Fedorov, P.N. First, W.A. de Heer, D.-H. Lee,F. Guinea,A.H. Castro Neto, and A. Lanzara Nature Materials 6, (2007)

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