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 bart@physics.rutgers.edu 732-445-5500 x4839

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

Laboratory for

RUTGERS
THE STATE UNIVERSITY OF NEW JERSEY

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(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

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. 215ML

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

Typical MQW Behavior: Cu/fccFe/Cu(100)

Photoemission (occupied states)
Binding Energy (eV)
0.0
0.2 0.4 0.6 0.8 1.0 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. Hochstrasser, D. Arena, J. Tobin (LBL)

Energy above E F (eV)

All spectra here obtained at k|| = 0 MQW states disperse up with increasing Cu overlayer thickness!

Since E = n2h2/8mL2 down when you increase the width of the well?
n+1 n+1 n d d+D

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

Bohr-Summerfeld Approx.
(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 - Dfc - Dfs

u=m-n

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, add a node (MQW states are characterized by the quantum number u = m - n)

k^

p/a

kp a

Sorting out n and n for MQW states of Ag/Fe(100)

T.C. Chiang

n+1

n+1 n

Do MQW state disperse discretely or continuously with film thickness?

Yes, they move discretely!

T.C. Chiang

Other System: Cu/fccNi/Cu(100)

Anomalous behavior above EF
Photoemission (occupied states)
0.0 0.0

12 ML Cu

Binding Energy (eV)

-0.2

-0.2 -0.4 -0.6 -0.8

0

Binding Energy (eV)

Inverse Photoemission (unoccupied states)

But

-0.4

-0.6

-0.8

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, APL 67, 1151 (1995)]

Ni

Behavior of electronic states depends on band alignment

Ni
Cu

Fe

EF

d bands

d bands d bands

Ni 4sp Cu 4sp

Cu 4sp Fe 3d

Dispersion with k||

Energy
Energy

T.C. 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

Energy (eV)

Quantum Size Effects and Materials Properties

Mediate oscillatory magnetic couplingGMR
Kawakami et al. PRL, 82, 4098 (1999)

MQW Intensity at EF (belly)

Low High

MQW Intensity at EF (neck) MXLD Calculation

MQW state-induced layer stability

Ag/Fe(100)
T.C. Chiang

Pb/Si(111)
Expt.
Weitering et al.

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

Chemisorption on MQWs
5 ML O O O O C C C C

Cu(100) f ccFe

Cu

215ML

Quantization of Cu sp band results in MQW states Cu sp electrons play a role in CO chemisorption (A. Nilsson et al.) 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

CO TPD from MQWs

CO/Cu/fccCo/Cu(100) CO/Cu/fccFe/Cu(100)
qCu(ML)
Cu(100)

Mass 28 Intensity (Arb. Units)

Mass 28 Intensity (Arb. Units)

13.75 10

q Cu

15 ML

10 ML

5 2.5 120 160 200 Temperature (K) 240

5 ML
2.5 ML 120 160 200 240

Temperature (K)

IPE Intensity and Desorption Temperature

185
180 175 170 Td
0 10

170
F

Cu(100)

168 166

Intensity at EF (Arb. Units)

Intensity at EF (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

10 20 Cu Film Thickness (ML)

Cu Film Thickness (ML)

Low Dimensionality and Hard Superconductivity

Weitering et al., Nature Physics (March 06)

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

Other routes to quantum wires (and dots)

Sprunger, Kurtz

Self-assembly Ag/Cu(110)

Atom-by-atom construction (Au/NiAl)

N. Nilius, T. M. Wallis, and W. Ho, Science 297 , 1853-1856 (2002).

Scanning tunneling spectroscopy of quantum wires (and dots)

dI/dV ~ N(E)
W. Ho

Y(x) = Scnsin(npx/L)

CDW within an atomic wire

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

 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, but band-like structure parallel to plane. Square well model NOT sufficient, must take into account 1-d structures can be fabricated and photoemission shows that
for 2-d and 1-d structures, respectively.

electronic structure of overlayer AND substrate to fully describe. metallic behavior is possible (undoubtedly owing to interaction with substrate).

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.

Can use STS to map electronic states of small (i.e. several atom long) 1-d structures to reveal dispersion with length.