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Quantum Confinement of Electrons at Surfaces

Robert A. Bartynski
Department of Physics and Astronomy Laboratory for Surface Modification and NanoPhysics Lab Rutgers University Piscataway, NJ 08854
NPL 203 732-445-5500 x4839

Surface/Interface Science Course (Phys 627/Chem 542) 25 March2013
Laboratory for


NanoPhysics Laboratory

Quantum Confinement  Interference of Electron Waves

M.F. Crommie, C.P. Lutz, D.M. Eigler. Science 262, 218-220 (1993)

Confinement of electrons to quantum corrals on a metal surface.
M.F. Crommie, C.P. Lutz, D.M. Eigler, E.J. Heller.

Waves on a metal surface and quantum corrals.

Surface Review and Letters 2 (1), 127-137 (1995) Physics Today 46 (11), 17-19 (1993).

STM rounds up electron waves at the QM corral.

Electronic Quantum Size Effects: Dimensionality


y(z) y(z) y( x ) y( x )

(thin film, quantum well)

2-d structure

confinement in 1-d

(atomic chain, quantum wire)

1-d structure

confinement in 2-d

confinement in 3-d

(cluster, quantum dot)

0-d structure

• Electron density acquires nodal structure along confinement direction. • Energy spectrum acquires discrete character.

Scanning Tunneling Microscopy/Spectroscopy .

Photoelectron Spectroscopy KE KE Valence Band Photoemission Core level Photoemission hu2 hu1 > hu1 EV VB EF Intensity Intensity Auger Electron Emission CLB CLS .

Complementary Spectroscopic Techniques Photoemission (Occupied States) e- Inverse Photoemission (Unoccupied States) e- eeEV EF EF Einitial Electron Counts EV EF Photon Counts EF  k X  k X Vertical transitions in the reduced Brillioun Zone Efinal ee- .

Angle Resolved Photoelectron Spectroscopy • Direct transition in solid  kin = ko • Periodicity in plane of surface  k||-in = k||-out + G|| •  k||-out = k||-o k|| = (2mE/h2)1/2sinq kout k||-in q k||-out Map E(k||) For 2d system obtain all information about energy bands kin Surface ko Crystal Vacuum .

1-d confinement: Quantum Wells .

Metallic Quantum Well (MQW) States 5 ML Cu(100) f ccFe Fe Cu Cu Surf. 215ML 200 x 200 nm 200 x 200 nm 300 x 300 nm Cu(100) Fe/Cu(100) Cu/Fe/Cu(100) .

Effect of Confinement on Electronic States 1) Free electron bands E  k2 2) Continuous paraboloid shown as grid [Dkx = 2p/Na] 3) Confinement allows only fixed values of k^ 4) Projected on E axis: sub-bands Energy E(k||)= En + h2k||2/2m For square well: En = n2h2/8mL2 k_parallel k_perpendicular k_perpendicular .

2 0. J.0 0 10 20 30 qCu 19 ML Inverse Photoemission (unoccupied states) 10 ML Thickness (ML) Cu Fe 0 1 2 3 3 ML 4 Cu Fe @ALS w/ M. Tobin (LBL) Energy above E F (eV) All spectra here obtained at k|| = 0 MQW states disperse up with increasing Cu overlayer thickness! .4 0.Typical MQW Behavior: Cu/fccFe/Cu(100) Photoemission (occupied states) Binding Energy (eV) 0. Arena.0 0.8 1. D.6 0. Hochstrasser.

Since E = n2h2/8mL2 down when you increase the width of the well? n+1 n+1 n d d+D n … they do. but by how much? u -1 u = (m – n) n+2 n+1 n+1 n n u -1 u u +1 ma (m + 1)a .

•But the Electrons are NOT in a Square Well e- Vin Fe Vin Cu Fe Cu We must include the effect of the atomic potential .

Quantum Well States in a Band 0 5 Bohr-Summerfeld Approx.Dfs u=m-n .Dfc . (Phase Accumulation Model) Phase/2p 10 15 20 2k^ma + Dfc +Dfs = n 2p Phase shift on Existence from condition vacuum Phase shiftaccumulated onreflection reflection from crystal Phase in well 2k^ma = n 2p .

add a node… (MQW states are characterized by the quantum number u = m .n) 0 k^ p/a kp a  2 a .MQW states disperse up with increasing Cu overlayer thickness 10 n nodes 4 3 2 1 0 m+1 ML m ML Electron Energy (eV) 8 6 4 2 0 -2 -4 States near BZB (n+1) nodes Add a layer.

Chiang n+1 n+1 n n .C.Sorting out n and n for MQW states of Ag/Fe(100) T.

C. Chiang .Do MQW state disperse discretely or continuously with film thickness? Yes. they move discretely! T.

APL 67.4 -0.8 0 Binding Energy (eV) Inverse Photoemission (unoccupied states) But… -0.0 12 ML Cu Binding Energy (eV) -0.2 -0.2 -0.4 -0.0 0.6 -0.6 -0.Other System: Cu/fccNi/Cu(100) Anomalous behavior above EF Photoemission (occupied states) 0.8 0 Cu Thickness (ML) 10 20 30 Cu Thickness (ML) 10 20 30 40 40 Cu Ni 2 ML Cu Cu 0 2 4 6 Energy Above EF (eV) Similar to Cu/Ni(100) [Himpsel and Rader. 1151 (1995)] Ni .

Behavior of electronic states depends on band alignment Ni Cu Fe EF d bands d bands d bands  C  C  C Ni 4sp  Cu 4sp Cu 4sp  Fe 3d .

C.Dispersion with k|| Energy Energy T. Chiang k|| = (2mEh 2)1/2sinq k_parallel k|| k_perpendicular Free electron-like dispersion of sub-bands .

Dispersion with k|| Flat dispersion !! Downward dispersion !! Nearly parabolic Upward dispersion Projected bands of Cu and Co 0 2 4 6 Energy (eV) .

PRL.Quantum Size Effects and Materials Properties • Mediate oscillatory magnetic couplingGMR Kawakami et al. 82. 4098 (1999) MQW Intensity at EF (belly) Low High MQW Intensity at EF (neck) MXLD Calculation .

Chiang Pb/Si(111) Expt. Theory Theory Quantum size effects stabilize island height Low T = 6 ML Low T = 3 ML High T = 5 & 7 ML High T = 2 & 4 ML .MQW state-induced layer stability Ag/Fe(100) T.C. Weitering et al.

Nilsson et al.Chemisorption on MQW’s 5 ML O O O O C C C C Cu(100) f ccFe Cu 215ML Quantization of Cu sp band results in MQW states Cu sp electrons play a role in CO chemisorption (A.) Changing Cu thickness modifies electronic levels without changing geometric structure Corresponding modification in CO chemisorption? .

Measuring Bonding Strength Temperature Programmed Desorption (Bond Strength) Mass 28 signal (Arb. Units) Mass Spec TP(th) TPD of CO/Cu(100) -C-O -C-O -C-O 150 200 250 Temperature (K) 300 .

5 120 160 200 Temperature (K) 240 5 ML 2.5 ML 120 160 200 240 Temperature (K) . Units) 13. Units) Mass 28 Intensity (Arb.75 10 q Cu 15 ML 10 ML 5 2.CO TPD from MQWs CO/Cu/fccCo/Cu(100) CO/Cu/fccFe/Cu(100) qCu(ML) Cu(100) Mass 28 Intensity (Arb.

Units) CO/Cu/fccCo 172 CO/Cu/fccFe Cu(100) Td (K) Td (K) Td IPE Intensity at E F 164 162 165 160 IPE Intensity at EF 20 30 0 10 20 Cu Film Thickness (ML) Cu Film Thickness (ML) . Units) Intensity at EF (Arb.IPE Intensity and Desorption Temperature 185 180 175 170 Td 0 10 170 F Cu(100) 168 166 Intensity at EF (Arb.

. Nature Physics (March 06) .Low Dimensionality and “Hard” Superconductivity Weitering et al.

2-d confinement: Quantum Wires .

How to make quantum wires (and dots) CaF/Si as mask Highly regular steps on Si(111) (Himpsel et al.) .

Electronic structure of quantum wires Si Au Si Metallic Au wires Semiconducting Au film Si(557) .Au (Himpsel et al.) .

Fermi “surface” of quantum wires (and dots) 2D Energy EF E_F Energy kx 1D k_y k_x ky .

M. T. Nilius. 1853-1856 (2002).Other routes to quantum wires (and dots) Sprunger. Ho. Kurtz Self-assembly Ag/Cu(110) Atom-by-atom construction (Au/NiAl) N. Wallis. Science 297 . . and W.

Scanning tunneling spectroscopy of quantum wires (and dots) dI/dV ~ N(E) W. Ho Y(x) = Scnsin(npx/L) .

Rogge. S.C.H. Snijders.CDW within an atomic wire Competing periodicities in fractionally filled one-dimensional bands. 2006) . H. Weitering Physical Review Letters (February 24. P.

electronic structure of overlayer AND substrate to fully describe. • Square well model NOT sufficient. • Can use STS to map electronic states of small (i. . metallic behavior is possible (undoubtedly owing to interaction with substrate).e.• Direct and Inverse Photoemission spectroscopies are powerful techniques for exploring the electronic structure of nanometer scale structures. Summary • 2-d structures show discrete electronic structure ^ to plane of the film. respectively. must take into account • 1-d structures can be fabricated and photoemission shows that for 2-d and 1-d structures. several atom long) 1-d structures to reveal dispersion with length. but band-like structure parallel to plane. • Fermi surface mapping shows closed or open curves as expected • Scanning tunneling spectroscopy (STS) is powerful tool for fabricating and characterizing 1-d and 0-d structures.