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Chun Ning Lau (Jeanie) Quantum Transport! in! 2D Atomic Membranes! Because most of the ‘low-hanging graphene fruits’ have already been harvested, researchers have now started paying more attention to other two-dimensional (2D) atomic crystals6 such as isolated monolayers and few-layer crystals of hexagonal boron nitride (hBN), molybdenum disulphide (MoS2), other dichalcogenides and layered oxides. During the first five years of the graphene boom, there appeared only a few stack represents an artificial material assembled in a chosen sequence—as in building with Lego—with blocks defined with one-atomic-plane precision (Fig. 1). Strong covalent bonds provide in-plane stability of 2D crystals, whereas relatively weak, van-der-Waals-like forces are sufficient to keep the stack together. The possibility of making multilayer van der Waals heterostructures has been demonstrated experimentally only 2D Materials and Heterostructures! Figure 1 | Building van der Waals heterostructures. If one considers 2D crystals to be analogous to Lego blocks (right panel), the construction of a huge variety of layered structures becomes possible. Conceptually, this atomic-scale Lego resembles molecular beam epitaxy but employs different ‘construction’ rules and a distinct set of materials. Graphene hBN MoS2 WSe2 Fluorographene Geim, Nature 2013. 1 School of Physics and Astronomy, University of Manchester, Manchester M13 9PL, UK. 2Centre for Mesoscience and Nanotechnology, University of Manchester, Manchester M13 9PL, UK. • Conductors, e.g. graphene, few-layer graphene 2 5 J U LY 2 0 1 3 | V O L 4 9 9 | N AT U R E | 4 1 9 ©2013 Macmillan Publishers Limited. All rights reserved • Semiconductors, e.g MoS2, WS2, • Superconductors, Nb2Se3 • Insulators, e.g. hBN • Charge density waves, e.g. NbSe • Ferromagnets, e.g. VSe2 April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Outline! • There is still life in graphene…. • Beyond graphene • Few Layer MoS2 • Few-layer Phosphorene April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Dual-Gated Suspended ABC Trilayer Graphene 4 2 100 G (µS) G (µS) 400 200 4 2 10 4 0 0 mobility 20,000 – 90,000 cm2/ Vs 40 2 80 0.00 T (K) 0.05 1/T (1/K) 42 mV 4 • Metal – insulator transition, Tc ~ 35K • Thermal activation measurement yields Δ ~ 41 meV • G(Vbias) curves at E⊥=n=0 yield Δ ∼ 42 meV April 2015 dI/dV (µS) 2x10 0 -40 VV (mV) bias bias (V) NSF US EU Workshop on 2D Layered Materials & Devices 40 Effect of electric and magnetic fields Differential conductance G vs source drain bias V at n=0" V (mV) 40 G(µS) 3 10x10 5 0 0 -40 0 B|| (T) 30 • gap educed symmetrically by |E⊥|! à not layer polarized; arises from electronic interactions" • gap reduced by parallel magnetic field at 30T" Y. Lee, D. Tran, K. Myhro, J. V. Jr., N. Gillgren, C. N. Lau, Y. Barlas, J. M. Poumirol, D. Smirnov, and F. Guinea, Nature Communications, 5, 5656 (2014) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Proposed Phase Diagram! U⊥ Quantum Valley Hall Layer Anti- Canted AntiFerromagnet Ferromagnet Ferromagnet B|| Current EU collaboration: Paco Guinea (CSIC, Spain; Machester) Frank Koppens (ICFO; Spain) April 2015 Y. Lee, D. Tran, K. Myhro, J. V. Jr., N. Gillgren, C. N. Lau, Y. Barlas, J. M. Poumirol, D. Smirnov, and F. Guinea, Nature Communications, 5, 5656 (2014) NSF US EU Workshop on 2D Layered Materials & Devices MoS2 • gapped, On/Off ratio >106 • direct-to-indirect band gap transition as function of thickness • valley physics But Mobility <~ 200 – 500 cm2/Vs Radisavljevic et al, Nat. Nanoetchnol. 2011. What is the mobility bottlenck? Wu et al, Nat. Phys. 2013. and many others April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Suspending MoS2 • the mobility is even lower, 0.1 -50 cm2/Vs • gas annealing à 200 cm2/Vs • Removing substrates does not significantly improve mobility • Other mobility bottlenecks: • Schottky barriers at contact F. Wang, M. Gray, P. Stepanov and C.N. Lau, Nanotechnology, in press (2015) April 2015 • impurity scattering • defects NSF US EU Workshop on 2D Layered Materials & Devices Ionic liquid gating of MoS2 In collaboration with Robert Haddon at UCR • Ionic liquids are molten salts with low melting point • can induce high carrier density (up to 1014 cm-2) • To date all IL gating are performed on substrate-supported devices • Suspended devices – enable gating from both surfaces IL" S" SiO2" D" IL"gate" Si" VILg" F. Wang, M. Gray, P. Stepanov and C.N. Lau, in preparation (2015) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Comparing Suspended and non-suspended devices Performed IL gating of 9 suspended and 9 substrate-supported samples • use DEME-TFSI • all suspended devices are more conductive by at least 1-2 orders of magnitude à IL gating is more effective in freestanding devices Mechanism: 1. Higher charge density 2. Better screening F. Wang, M. Gray, P. Stepanov and C.N. Lau, in preparation (2015) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Transport Mechanism VIlg=0 Schottky emission at MoS2-electrode interfaces (a) I (µΑ) 8 (e) $a V −Φ ' B I ∝ exp & ) % k BT ( -16 -1 Vds (V) 1 a=e 5 e 4πε 0εr d I (µΑ) slope yields εr ~ 11 à dielectric constant of DEME-TFSI ~ 14.5 à agrees with literature values -5 -1 Vds (V) 1 Fujimoto, T.; Awaga, K. Phys Chem Chem Phys 15, 8983 (2013). April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Charge Density Induced in Suspended MoS2 Compare ΔVbg and ΔVIL needed to induce the same change in conductance ratio of ionic liquid gate to back gate: up to 450 à α up to 4.6x1013 cm-2 V-1 > 2-4x previous values F. Wang, M. Gray, P. Stepanov and C.N. Lau, in preparation (2015) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices IL-tuned Metal Insulator Transition VILg =3V 2V 100 VILg =3V 2V 1.5V σs (µS) 1.5V 10 1V 1V 0V 1 0V -0.5V -0.5V 0.1 120 200 T (K) 0.004 1/T (1/K) 0.008 • metal insulator transition observed as VILg is tuned • At small VILg, transport via thermal activation $a V −Φ ' B I ∝ exp & ) k T % ( B April 2015 a=e e 4πε 0εr d obtained from I-V curves NSF US EU Workshop on 2D Layered Materials & Devices Conclusion • Mobility not limited by substrate in current generation of devices • Bottleneck: Schottky barrier at MoS2-electrode interface see Cui et al, arXiv 1412.5977 (2014) à critical: contact engineering • Ionic liquid gating of suspended devices à ion accumulation on both surfaces à higher charge density, enhanced screening • Further optimization à Ultra-high density regime for new phases • p-doping à spin/valley transport F. Wang, M. Gray, P. Stepanov and C.N. Lau, in preparation (2015) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Outline! • Few Layer Graphene • Few Layer MoS2 • Fabrication and annealing of suspended MoS2 • Ionic liquid gating • Few-layer Phosphorene • Fabrication of air-stable, high mobility devices • Observation of quantum oscillation April 2015 NSF US EU Workshop on 2D Layered Materials & Devices “Curse of 2D Materials” • Mobility ~ 105 – 106 cm2/Vs MoS2,WS2, MoSe2, WSe2, etc • Gapless • Mobility ~ 100 cm2/Vs Graphene • Gapped Black Phosphorus • • • most stable form of phosphorus layered structure bulk mobility up to 60,000 cm2/Vs peroidictable.com April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Black Phosphorus • only other layered element • Puckered atoms within layers • Anisotropic • Thickness dependent band gap, 0.3 - 2 eV Tran et al, PRB 2014 April 2015 Asahina & Morita, J. Phys. C, 1986 • Direct band gap for all thickness NSF US EU Workshop on 2D Layered Materials & Devices Few-Layer Black Phosphorus Transistors • ambipolar transport • gapped, on/off ration ~105 • Anisotropic Transport • Mobility ~100-1000 cm2/Vs for thickness ~2 – 20 nm Li et al, Nature Nanotechnol 2014 Liu et al, ACS Nano 2014 April 2015 • Best of both worlds! Xia et al, Nature Comm. 2014 NSF US EU Workshop on 2D Layered Materials & Devices Challenges Kroenig et al, APL 2014 Island et al, 2D Materials 2014 Instability in air • react with water and O2 to form phosphoric acid • reaction accelerated by light April 2015 Favor et al, arxiv 2014 NSF US EU Workshop on 2D Layered Materials & Devices Encapsulation for stable, high mobility Devices hexagonal boron nitride (hBN) from wikipedia • atomically flat • no dangling bonds à little trapped charges • high mobility graphene/hBN devices demonstrated Columbia group, Nature Nanotechnol. 2012 Encapsulate few-layer phosphorene with hBN? April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Device Fabrication phosphorene hBN top gate PDMS hBN electrode SiO2 Si/SiO2 • Dry transfer to form hBN/few-layer phosphorene/hBN heterostructure sandwiches • etch to expose edges of phosphorene • 1D metallic contact to 2D layers Wang et al, Science 2013 April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Device Stability Encapsulated in hBN (our data) Wood et al, Nano Letters 2014 • Device left in air for 2 weeks • Slight shift in charge neutrality point • Only slight decrease in conductance & mobility N. Gillgren, D. Wickramaratne, Y. Shi, T. Espiritu, J.Yang, J. Hu, J. Wei, X. Liu, Z. Mao, K. Watanabe, T. Taniguchi, Marc Bockrath, Yafis Barlas, R. K. Lake, C.N. Lau, 2D Materials, 2, 011001 (2014) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Rxx (Ω) Rxx (Ω) Device mobility • Ambipolar transport • On/off ratio ~ 105 • linear I-V à ohmic contact April 2015 • Metal-insulator transition • highly hole-doped: metallic, µ up to 4000 • towards band edge: insulating, µ ê with T NSF US EU Workshop on 2D Layered Materials & Devices Quantum Oscillations ΔRxx (Ω) Rxx with smooth background subtracted • oscillations periodic in 1/B • oscillations periodic in Vg ~n • doubling frequency in for B>8T à Zeeman splitting a c d N. Gillgren, D. Wickramaratne, Y. Shi, T. Espiritu, J.Yang, J. Hu, J. Wei, X. Liu, Z. Mao, K. Watanabe, T. Taniguchi, Marc Bockrath, Yafis Barlas, R. K. Lake, C.N. Lau, 2D Materials, 011001 (2015) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Temperature Dependence Quantum Oscillations Oscillations’ amplitude dependence on T b • effective mass of charge carriers ~0.25 to 0.31 me as Fermi energy increases towards band edge • agree with DFT calculations within 50% N. Gillgren, D. Wickramaratne, Y. Shi, T. Espiritu, J.Yang, J. Hu, J. Wei, X. Liu, Z. Mao, K. Watanabe, T. Taniguchi, Marc Bockrath, Yafis Barlas, R. K. Lake, C.N. Lau, 2D Materials, 011001 (2014) April 2015 NSF US EU Workshop on 2D Layered Materials & Devices Conclusion • Few layer phosphorene has both high mobility and band gap • Stable via hBN encapsulation Outlook • Physics b • strain-dependent band gap • large anisotropy (up to factor of 60, electrical and thermal transport, thermopower) • electric field effect • quantum Hall effect • Electronics and optoelectronics • hBN encapsulation of reactive 2D materials Number 20 see Cao et al, arXiv: 1502.03755 0 April 2015 NSF US EU Workshop on 2D Layered Materials & Devices 1 2014 month 12 Acknowledgments! Graduate Students Undergraduate Students Tim Espiritu Kevin Thilahar Mason Gray Ziqi Pi Yongjin Lee" Jhao-wun Huang " Fenglin Wang" Kevin Myhro " Yanmeng Shi" Nathaniel Gillgren" UCOP Petr Stepanov" April 2015 Son Tran " NSF US EU Workshop on 2D Layered Materials & Devices Collaborators! UCR Physics UCR Chem. & CEE Marc Bockrath Robert Haddon Florida Mag Lab Dmitry Smirnov Tulane Zhiqiang Mao UCR Physics Yafis Barlas Tulane Jiang Wei Jean-Marie Poumirol April 2015 NSF US EU Workshop on 2D Layered Materials & Devices UCR EE Roger Lake CSIC Paco Guinea