Istituto per la Microelettronica e Microsistemi IMM The network on graphene at IMM OUTLINE • The IMM graphene research network • The agreement with Industry • Competences and acquired know how at IMM Agrate (MDM) • Competences and acquired know how at IMM CT Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 1/15 The graphene research network at IMM IMM Graphene like materials (silicene, germanene, …) Memories and logics Milano Advanced characterisation & sensors See V. Morandi, R. Rizzoli Bologna Roma Lecce Napoli Catania materials fundamentals & devices (Rf, power, …) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 2/15 The graphene research network at IMM IMM Graphene like materials (silicene, germanene, …) Memories and logics Milano Advanced characterisation & sensors See V. Morandi, R. Rizzoli Bologna Roma Lecce Napoli Catania materials fundamentals & devices (Rf, power, …) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 3/15 The graphene research network at IMM IMM Graphene like materials (silicene, germanene, …) Memories and logics Milano Advanced characterisation & sensors See V. Morandi, R. Rizzoli Bologna Roma Lecce Napoli Catania materials fundamentals & devices (Rf, power, …) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 2/15 The graphene research network at IMM IMM Graphene like materials (silicene, germanene, …) Memories and logics Milano Bologna Roma Lecce Advanced characterisation & sensors See V. Morandi, R. Rizzoli The industrial cluster Napoli Catania 3Sun materials fundamentals & devices (Rf, power, …) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 2/15 The graphene research network at IMM IMM Graphene like materials (silicene, germanene, …) Memories and logics Milano Bologna Roma Lecce Advanced characterisation & sensors See V. Morandi, R. Rizzoli The industrial cluster Napoli Catania 3SunJ.D.A. materials fundamentals & devices (Rf, power, …) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy J.D.A. J.D.P. Slide 2/15 IMM-Agrate expertise on ReRAM memory devices Challenge: Resistive Random Access Memory (ReRAM) in graphene. IMM CNR- IMM- Agrate EMMA Project-FP6 (1/9/2006-30/11/2009): Emerging Materials for Mass-storage Architectures (contact: Marco Fanciulli and Sabina Spiga) MORE Project 2010-2012 (CARIPLO): Advanced MetalOxide heterostructure for nanoscle ReRAM (contact: Sabina Spiga) single layer graphene as electrode on Nb-doped STO substrate for Pt/NiO/graphene nano-ReRAM graphene Top electrode A resistive material Bottom electrode ReRAM: a large class of emerging non-volatile memory concepts is based on a 2-terminal resistor as a memory element that can be programmed in a high and low conductive state Memristor concept introduced by HP J. Y. Son et al., ACS Nano 4, 2010, 2655-2658 Graphene Oxide Thin Films (as switching element) for Flexible Nonvolatile Memory applications H.Y. Jeong at al., Nanoletters 2010, 10, 4381–4386 Large interest from worldwide industries on ReRAM for post high-density FLASH and for Flexible Nonvolatile Memory Applications IMM-Agrate expertise up to now: NiO, Nb2O5, TiO2 based metal/oxide/metal thin film- and nanowireheterostructures Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 3/15 Challenge: Graphene-like materials IMM CNR- IMM- Agrate Graphene like semiconductors (silicene, germanene) valuable option for active material in Post-CMOS ditital logic devices and circuits Option 1: silicene on metals, (in analogy with graphene) Option 2: encapsulation silicene with 2D hexagonal dielectric lattices MBE of Si on Ag(110), Ag(111) substrates Ref. Aufray et al, Appl. Phys. Lett. 97, 223109 (2010); Aufray et al, ibidem 96, 183102 (2010) graphite-like AlN 2D top lattice functionalized silicene graphite-like AlN 2D bottom lattice • Molecular beam epitaxy apparatus for growth, functionalization amd in situ characterization of graphene like materials • in situ SPM and spectroscopic diagnostic tools @ CNR-IMM (Lab. MDM) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy • dielectric capping for prototypical MOS-like devices Slide 4/15 GRAPHENE at IMM-CT: highlights IMM More than 30 papers since 2005 by two groups (theory & Exp.) growth methods Synthesis methods Mechanical exfoliation of highly oriented pyrolityc graphite (HOPG) Chemical exfoliation of highly oriented pyrolityc graphite (HOPG) Epitaxial graphene on SiC by controlled graphitisation of the surface at high temperatures (1500 –2000 °C) in inert gas ambient High material quality: Low defects density, High mobility Can be placed on different substrates: SiO2 , SiC, high-k dielectrics High production yield Can be placed on different substrates: SiO2 , SiC, high-k dielectrics Large area (wafer scale) sheets on semiconductor substrate Small sheets; Low production yield Small sheets; Defects Substrate cost S. Sonde, F. Giannazzo, V. Raineri, and E. Rimini, J. Vac. Sci. Technol. B 27, 868 (2009). S. Sonde, F. Giannazzo, V. Raineri, and E. Rimini, Phys. Status Solidi B, 1–4 (2010) S. Sonde, F. Giannazzo, V. Raineri, R. Yakimova, J.-R. Huntzinger, A. Tiberj, and J. Camassel, Phys. Rev. B 80, 241406(R) (2009). Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 5/15 GRAPHENE at IMM-CT: highlights IMM More than 30 papers since 2005 by two groups (theory & Exp.) growth methods Synthesis methods Mechanical exfoliation of highly oriented pyrolityc graphite (HOPG) Chemical exfoliation of highly oriented pyrolityc graphite (HOPG) Epitaxial graphene on SiC by controlled graphitisation of the surface at high temperatures (1500 –2000 °C) in inert gas ambient High material quality: Low defects density, High mobility Can be placed on different substrates: SiO2 , SiC, high-k dielectrics High production yield Can be placed on different substrates: SiO2 , SiC, high-k dielectrics Small sheets; Low production yield Small sheets; Defects BEYOND STATE OF THE ART Large area (wafer scale) sheets on semiconductor substrate Substrate cost First EG on 4H-SiC off axis Patended substrates S. Sonde, F. Giannazzo, V. Raineri, and E. Rimini, J. Vac. Sci. Technol. B 27, 868 (2009). S. Sonde, F. Giannazzo, V. Raineri, and E. Rimini, Phys. Status Solidi B, 1–4 (2010) S. Sonde, F. Giannazzo, V. Raineri, R. Yakimova, J.-R. Huntzinger, A. Tiberj, and J. Camassel, Phys. Rev. B 80, 241406(R) (2009). High mobility Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 5/15 GRAPHENE at IMM-CT: Highlights IMM Transfer to substrates: methods and functionalization Silanization of SiO2 Phosphonization of SiO2 Few-layers graphene on metal Transfer by nanoimprinting Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 6/15 GRAPHENE at IMM-CT: Highlights IMM Transfer to substrates: methods and functionalization Silanization of SiO2 Phosphonization of SiO2 Few-layers graphene on metal Transfer by nanoimprinting CHALLENGES • From nanoscale properties to large area EG on 4H-SiC (150 mm) • Functionalisation (to control the G carrier concentration, to control the G layer transfer to other substrates) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 6/15 GRAPHENE at IMM-CT: Highlights Quantum capacitance and local transport 10 IMM 0 Graphene -1 10 Graphene n-SiC n+ C (a.u.) SCM Electronic Module Qscr Aeff Qdepl -2 -3 10 -4 10 Qdepl SiC SiO 2 10 0.0 0.5 1.0 1.5 2.0 V g (V) 25 2 A eff (×10 nm ) 20 5 0.5 1.0 11 Aeff ΔVdepl SiO leff 1.5 -2 n (×10 cm ) 300 200 SiC + Vg F. Giannazzo, S. Sonde, V. Raineri, E. Rimini, Nano Lett. 9, 23 (2009). F. Giannazzo, S. Sonde, V. Raineri, and E. Rimini, Appl. Phys. Lett. 95, 263109 (2009). Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy l eff (nm) C’depl 10 0 0.0 ΔVgr C’q 15 4 Under the influence of electric field, 2DEG+ Vg manifests itself as a Gnd capacitor, Quantum capacitor. 100 0 0 10 20 30 n (× 10 m ) Slide 6 -1 40 7/15 IMM GRAPHENE at IMM-CT: Highlights The role of interfaces on mobility DG-SiC 10 6 10 5 10 4 2 23000 cm2V-1s-1 cm /Vs EG-SiC Epitaxial graphene 10 6 10 5 4 10 Nci_EG=2.5x1011cm-2 10 10 Giannazzo F, Roccaforte F, Raineri V, Liotta SF, Europhys. Lett., 74, 686 (2006) 10 S. Sonde, F. Giannazzo, C. Vecchio, V. Raineri, E. Rimini, App. Phys. Lett., 97, 132101 (2010) Also selected for publication on Virtual Journal of Nanoscale Science & Technology. Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy 6 SPP ci equi exp DG-SiO 2 5 4 0.5 1.0 11 1.5 2 nVg-n0 (×10 cm /VS) Slide 8/15 GRAPHENE at IMM-CT: Highlights IMM From thin to fat FET Atomic force microscopy Optical microscopy 1 m 60 nm nm m Gate HSQ Source Pt Pt Drain Pt EG Lg=10m 4H-SiC (0001) n- 4H-SiC (0001) n+ F. Giannazzo, C. Vecchio, V. Raineri, E. Rimini, submitted Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 9/15 GRAPHENE at IMM-CT: Highlights IMM fat FET characteristics Output characteristics -6 6.0x10 VD = 0.8 V VD = 0.6 V VD = 0.4 V VD = 0.2 V VD = 0 V -6 4.0x10 -6 6.0x10 -4 3.0x10 -4 VG = 14 V VG = 12 V VG = 10 V VG = 8 V VG = 6 V VG = 4 V VG = 2 V VG = 0 V STEP = 1V 0.0 0 5 VD(V) 10 Transfer characteristics Hole conduction ID(A) 8.0x10 -5 0.0 6.0x10 -5 -6 4.0x10 -5 -6 2.0x10 0.0 2.0x10 gm(S) -4 ID(A) Ambipolar transport Transconductance 9.0x10 0V < VD< 10V 0V < VG< 14V -2.0x10 Electron conduction Dirac point VD = 0 V VD = 0.2 V VD = 0.4 V VD = 0.6 V VD = 0.8 V -5 -4.0x10 -2 0 2 4 6 VG(V) 8 10 12 14 -5 Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy 0 5 VG(V) 10 Slide 10/15 GRAPHENE at IMM-CT: challenges 100 3000 first processing end of processing 80 2000 60 1000 0 0 10 20 Vgs (V) 30 Mapping distribution Frequency (%) 2 -1 -1 eff (cm V s ) IMM 40 20 0 0 20 40 60 l (nm) 80 100 6000 8000 100 80 60 40 20 0 0 2000 4000 (cm2V-1s-1) Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 11/15 GRAPHENE at IMM-CT: challenges 100 3000 first processing end of processing 80 2000 60 1000 0 0 10 20 Vgs (V) 30 Mapping distribution Frequency (%) 2 -1 -1 eff (cm V s ) IMM 40 20 0 0 20 40 60 l (nm) 80 100 6000 8000 100 80 60 40 20 0 New devices architectures (a) Source Gate Insulator Vg 2000 4000 (cm2V-1s-1) Vg>Vth (b) Vg 0 FLG Insulator MIS inversion layer n+-type p-type SiC Buried gate Id FLG Vg n-type CMIS n+-type Drain Vd CHALLENGES • Physical model nano- macro properties • New devices architectures Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy CMIS Rsource CFLG Rch,MIS (c) Rc,FLG-SiC RFLG Rdrift Vd Slide 11/15 GRAPHENE at IMM-CT: ELECTRON STRUCTURE AND COHERENT TRANSPORT IN CONFINED GRAPHENE IMM Methodology Electronic Structure Quantum transport Ab initio Semiempirical Transport Density functional theory, LDA and GGA exchangecorrelation functionals, GAUSSIAN and SIESTA codes Tight-Binding (TB): single π-orbital Hamiltonian, further parameterizations based on DFT Non-equilibrium Green’s functions methods coupled to Landauer-Büttiker approach Extended Hückel Theory (EHT): real-orbital basis, parameters from DFT calculations or experimental data Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Electrostatics 3D Poisson solver, computational box with Neumann/Dirichlet boundary conditions Slide 12/15 GRAPHENE at IMM: Highlights IMM the simulation approach to transport properties Previous activity overview Computation apparatus: self-consistent transport calculations Atomistic modeling of disorder in graphene based systems: from the single defect/impurity to a finite density of scattering centers GNR-metal junction At CNR-IMM Catania Epitaxial GNR on SiC(0001): role of interface states • In house programming codes for Focus on defective and functionalized epitaxial GNR electronic structure and quantum Complete device simulation A. La Magna et al, PRB 80, 195413 (2009) I. Deretzis and A. La Magna, Appl. Phys. Lett. 95, 063211 (2009) I. Deretzis et al., J. Phys. Cond. Mat. 22, 095504 (2010) I. Dertzis et al., Phys. Rev. B 81, 085427 (2010) I. Deretzis et al., Phys. Rev. B 82, 161413(R) (2010) I. D. and A. La Magna, accepted Appl. Phys. Lett. Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy transport based on atomistic semiempirical Hamiltonians (Extended Hückel and Tight-Binding), NEGFPoisson scheme • Full-device simulation for 103 – 107 atoms (in the case of GNRs) • Atomistic treatment of local alterations in the atomic structure, disorder, etc. • Multiscale approach (electronic Hamiltonians calibrated or evaluated by first-principles calculations) Slide 13/15 Challenges IMM IMM - Agrate • Memories and logics in graphene • Graphene-like materials IMM - CT • From nanoscale properties to large area (150 mm wafers) • Physical model considering nano-properties for macro-effects • New devices architectures • Functionalisation (to control the G carrier concentration, to control the G layer transfer to other substrates) • Computational transport properties: multi scale approach IMM - Bo • see coming presentations for details Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy Slide 14/15 IMM Catania: Bologna: Antonino La Magna* Vittorio Morandi* Giuseppe Angilella** Luca Ortolani*** Ioannis Deretzis*** Rita Rizzoli* Giulio Paolo Veronese* Raffaella Lo Nigro* Alberto Roncaglia* Filippo Giannazzo* Vito Raineri* Emanuele Rimini** Thank you for your attention Sushant Sonde*** Carmelo Vecchio **** Agrate: Marco Fanciulli** Alessandro Molle* Sabina Spiga* Atom_based Nanotechnology workshop, 19th January 2011, Arcetri (FI), Italy * Ricercatori CNR di ruolo ** Associati *** Post-doc **** Dottorandi Slide 15/15