Single-Spin Detection at Surfaces

M. Alexander Schneider
Max-Planck-Institut für Festkörperforschung, Stuttgart

... by STM based methods

 Magnetism of Nanostructures

Nanostructures
at surfaces !

„Single Spin Objects”

Atoms, Molecules
F9/2
4

S=3/2 L=3 J=9/2

Co2+ magnetic moment ?
<µZ>

Fe3+ anisotropy ?

B Cr3+ magnetic order ?

H/kT
 Why?

Data storage: High density recording

quantum computing: precise control over single spins:

q-bits

properties of nano- microscopic origin of anisotropy

structured magnets:

.....
or just because we want to know!
 Magnetic Moments As Function of
Shape

3.0 Ag(001)
Local Impurity Moment[ B]

2.5 4d
2.0 islands

1.5 chains

1.0

0.5

0.0
Y Zr Nb Mo Tc Ru Rh Pd
V. Stepanyuk et al., Surf. Sci. 377-379, 495 (1997)
 Magnetic Moment as Function of
Substrate

Ni/K

Ni

K Na
Cu

large (atomic-like) moment no magnetic moment

P. Gambardella, et al., Phys. Rev. Lett. 88, 047202 (2002)
 Magnetic (?) Supramolecular
Assemblies

Fe + TMLA
on Cu(100)

A. Dmitriev, et al., Angew. Chem. Int. Ed. 42, 2670 (2003)

 How ?

non-local probes (e.g. XMCD): ensemble average!

single atoms 

well defined (chemical, structural) state 

dimers, trimers: 
interaction between entities

Problem of monodispersity!
 Motivation: Why STM? – Local Probe!

Co atoms on Cu(111)

Co superlattice

single Co atom

Co dimer
Co atoms in a row

Long-range interactions N. Knorr et al.,

(image size 35nmx35nm) PRB 65, 115420 (2002)
Cu atoms on Cu(111) at 15 K, real duration of sequence: 20min
 B = 14T B = 14T

B = 5T
T = 5K

T ~ 0.5 K

T ~ 50 mK

increasing spectroscopic resolution (3.5 kBT)

Scanning tunneling spectroscopy

dI/dV

differential Conductance (dI/dV) ~ LDOS(r,E)

 Magnetic properties of atoms at
surfaces

Co on Au(111)
How to make the STM sensitive to these interactions ?

Kondo Effect
Spin-Flip Spectroscopy
Outline Superconducting tip STM
„ESR-STM”
+ Magnetic Resonance FM
 Single Magnetic Atom Spectra
Co adatoms on Au(111)

1.2 TK = 74 K

dI/dV (arb. units)

1.0

0.8
2kBTK

5 nm -60 -40 -20 0 20 40 60

Sample voltage (mV)

see also: V. Madhavan, et al., Science 280, 567 (1998)

V. Madhavan, et al., PRB 64, 165412 (2001)
J. Li et al., PRL 80, 2893 (1998) (Ce on Ag(111))
 Magnetic Impurities in Normal
Metals
unhybridized Hartree-Fock type hybridisation
<nd > = 1 <nd> = 0 <nd > 1 <nd>  0
d + U<nd >

d + U

EF EF

d
d + U<nd>

(non-)magnetic depending
magnetic
on d, , U
 E
d+U <nd>

F non-
EF   d magnetic
d+U<nd>
U

magnetic

F

non-magnetic
P.W. Anderson, Phys. Rev. 124, 41 (1961)
 Kondo Physics
magnetic impurities in metals in quantum dots

source drain

low-T resistance minimum

enhanced conductivity
anomalous , c, etc. at Vsd=0 for odd # electrons
-> spin flip scattering on dot

„New“: at surfaces with STM: direct access

 Kondo Spin-Screened State

|i>
 |f> 
 imp 2kBTk

EF E
Kondo - ground state T<<TK
• „Binding Energy“ TK ~ 0...500K
• Coherence length K ~ 1...1000 nm
• Spin flip scattering modifies the DOS at EF
 Magnetic Impurities : Kondo effect
with electron correlation: spin singlet has lower energy
singlet
E

S=1

kBTK
triplet S=0

T < TK:
singlet (spin-screened) state
see: G.Grosso G. Pastori Parravicini, Solid State Physics (AP, 2000)
A.C. Hewson, The Kondo Problem to Heavy Fermions (CUP,1993)
 „Transport” access to the Kondo resonance

resonant transport at EF

L.Kouwenhoven, L. Glazman, Physics Today, Jan. 2001

 Single Magnetic Atom Spectra
Co adatoms on Au(111)

1.2 TK = 74 K

dI/dV (arb. units)

1.0

0.8
2kBTK

5 nm -60 -40 -20 0 20 40 60

Sample voltage (mV)

see also: V. Madhavan, et al., Science 280, 567 (1998)

V. Madhavan, et al., PRB 64, 165412 (2001)
J. Li et al., PRL 80, 2893 (1998) (Ce on Ag(111))
 Kondo STS Spectra

Co/Ag(111) Co/Cu(111) Co/Cu(100)

Width
= 2kBTK

• TK : Ag(111) : 92K
Au(111) : 76K
Cu(100) : 88K
Cu(111) : 54K
• Line shape: Fano-type at EF
 Kondo Resonance Fano Line Shape

ta
ts

1 Tunneling process leads to 2 Resonance modifies the

possible interference of conduction band LDOS
channelsFano line Fano line shape
shape
t a (r )
q (r)  V. Madhavan,et al., Science 280, 567 (1998)
tS (r ) J. Li, et al, PRL 80, 2893 (1998)
O. Ujsaghy et al., PRL 85, 2557 (2000)
M. Plihal, J.W.Gadzuk, PRB 68, 085404 (2001)
 What determines TK at the surface?

Density of states at surfaces: - surface states

- bulk bands
- work function
Geometric effects: - bond length
- no. of nearest neighbours
Coupling matrix elements: - interaction strength with
s, p and d-bands

related to magnetic moments, diffusivity, reactivity, etc.

TK allows characterization of interaction with substrate

 TK in the Anderson Model

sp
d + U 
 U   d  d U
TK  e 2 U
2
EF
2
d   TK
d
d – E F   T K 

andd :inoverlap with (Kondo

certain limit host electron
model):density
TK ~ e-1/(J ) F
Overlayer Systems: Ag on Cu(111)
Surface State vs. Ag thickness
ML Ag
Cu(111)
0

dIdV (arb. u.)

1
2
50 nm
3
Ag(111) 
-0.5 0.0 0.5 1.0
Sample bias (V)

E0

Appl. Phys. A 78, 183 (2003)

 Tuning magnetic properties:
Co on Ag / Cu(111)
1.1 1.1

1.0
1.0

0.9

dI/dV

dI/dV
0.9
0.8

0.8 0.7
-40 -20 0 20 40 -40 -20 0 20 40
Bias (mV) Bias (mV)

Cu(111) Ag(111)
1ML Ag
TKCo-Cu(111) = 54 K TKCo-Ag/Cu(111) ~ 90 K TKCo-Ag(111) = 92 K
PRL 93, 176603 (2004)
 Tuning Hybridisation: Co on different
surfaces

on (111) :
n=3

on (100) :

?
Ag(111)
n=4

on (111)
@ step :
Ag(100)
n=5

N. Knorr et al., PRL 88, 096804 (03) increasing hybridisation

 Level Occupancy as Effective Parameter
fluctuation in the occupancy of adatom level
Co: 5 d-0rbitals
E
<nd>: effective ground state density
(unpaired spin only)

d+U nd=2 d = U(-<nd> + 1/2)


EF=0 nd=0   U  2 U  d  d U
TK  e
d 2
nd=1
U
 U    nd   12   nd   32
<nd> nd  e 2
2
O.Újsághy, et al., PRL 85, 2557(2000)
 Simple Model: Magnetic Adatoms
at surfaces: hybridisation ~ TB hopping term :

NN distance
a (from hard sphere model)

d
  nNN e extent of Co d-orbital (~ 1 Å)

a
coordination

Model assumptions:

• <nd> = <nd>0 +c b
• = 0.2 eV = const.
• U = 2.8 eV = const.

Estimates:  ~ 0.2 eV, U ~ 2.8 eV,

„true” nd ~ 8.8 for Co on Au(111)
O.Újsághy, et al., PRL 85, 2557(2000)
 Co on noble metals:
understanding the surface-adatom
interaction
d +U <nd >

EF
2

d >
d + <n d

increasing hybridisation
PRL 93, 176603 (2004)
 Other signs for hybridization

Reduction of magnetic moments:

„Hybridization reduces magnetic moments“

S. Frota-Pessôa, Phys. Rev. B 69, 104401 (2004)
 Kondo Physics – Single Particle
Calculations

Differences: Ag, Au, Cu

d-bands:

EF E

d : A. Ruban, J. Molec. Catal. A –Chem. 115, 421 (1997)

orb. µ: S. Frota-Pessôa, Phys. Rev. B 69, 104401 (2004)
 Tuning magnetism by ligands

Co

chemical reaction at
Cu(100) surface:
(110)

Coad +4 COg  Co(CO)4

(110) 2 nm
U=-0.2V,
other species by molecular manipulation I=2nA
 Cobalt- carbonyls

1 nm

Co Co(CO)3 Co(CO)4

dI/dV (a.u.)
dI/dV (a.u.)

dI/dV (a.u.)

-100 -50 0 50 100 -100 -50 0 50 100 -100 -50 0 50 100

Bias (mV) Bias (mV) Bias (mV)

TK=88±4K TK=166±16K TK=283±36K

P. Wahl, PhD Thesis, U Konstanz

 mapping of a spin
Co (CO)4 Co2 (CO)4



 


 

P. Wahl, PhD Thesis, U Konstanz

 Interaction of magnetic impurities
compact Co dimer on Au(111): No Kondo resonance (at 6K)

Cr:
dimer: AF – no Kondo

isotropic trimer:
no net moment- no Kondo

isocles trimer:
non-colinear moment: Kondo

T. Jamneala, et al., PRL 87, 256804 (2001)

Inelastic Tunneling Spectroscopy

Tip
dI/dV
Sample

EF
-ħ -ħ ħ ħ
eV eV
ħ

d2I / dV2

-ħ -ħ
adsorbed ħ ħ
molecule eV
 Molecule Characterization

C2HD
D

B. C. Stipe, M. A. Rezaei, and W. Ho, PRL 82, 1724 (1999)

 Mn atoms on NiAl

Mn

Al2O3
NiAl Bext

weak coupling to substrate: low TK

degree of alignment of spin: determined by B/kBT (Brillouin function)
 Spin flip tunneling

Zeeman

Spin-flip exited by inelastically tunneling electrons

 Spin-flip IETS spectra

at oxide edge

on oxide

g-factor depends on
adsorption size !

A. Heinrich et al., Science 306, 466 (2004)

Spin detection via Superconductors

Mn

Nb(110)
Spin detection via Superconductors

Sub-gap structure of
BCS tunneling spectrum
indicates magnetic moment

A. Yazdani et al., Science 275, 1767 (1997)

 Interaction SC - FM

Spin dependent scattering potential creates a bound

(spin-polarized) state
 ESR-STM
Idea: Detect the spin-precession of a localised spin!

Spectrum
analyser
100-1000MHz

„dc“ STM-
electronics

2d 2m
„Spin-noise” in current
   JS ( t )
T  T0e 

A. Balatsky, et al. PRB 66, 195416 (2002)

 Landé g-Factor of a single molecule

BPDA Molecules on HOPG

C. Durkan, M.E. Welland, Appl. Phys. Lett. 80, 458 (2002)

Magnetic Resonance Force Microscopy

D. Rugar et al., Nature 430 329 (2004), IBM Almaden

 summary / take home messages

atomic magnetic moments can be detected & studied by STM

(Kondo effect, inelastic spin-flip tunneling, ESR-STM ...)

magnetic properties of atomic scale objects depend on local environment

(binding sites, material, ligands, ....)

Kondo-effect specific:
TK determined on atomic not on spin-coherence length scale

Co2 (CO)4 