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Surface analysis with ion beams

Two parts:
Surface structure determinations
Thin film analysis
L. C. Feldman, J. W. Mayer and S. T. Picraux, Materials Analysis by Ion Channeling,
Academic Press (1982)
L. C. Feldman and J. W. Mayer, Fundamentals of Surface and Thin Film Analysis,
North-Holland (1986)
I. Stensgaard, Surface studies with high-energy ion beams. Reports on Progress in
Physics 55 989-1033 (1992).
H. Niehus, W. Heiland and E. TagIauer, Low-energy ion scattering at surfaces.
Surface Science Reports 17 (1993) 213-303.
J.F. van der Veen, Ion beam crystallography of surfaces and interfaces. Surface
Science Reports 5 199-288 (1985).
R. Hellborg, H. J. Whitlow and Y. Zhang, Ion Beams in Nanoscience and
Technology, Springer (2009)

Ion backscattering for materials


analysis: 3 energy regimes
Low energy ion scattering (~10 keV or less):
LEIS
Hard to quantify, very surface specific

Medium energy (~ 50 200 keV)


Quantitative, somewhat elaborate equipment,
surface specific

High energy (1 2 MeV)


Quantitative, simpler equipment

Advantages of ion beams*

Penetrating (can access buried interfaces!)


Mass specific
Known interaction law (cross sections are known)
Excellent depth resolution
*High

and medium energy beams

Elementary considerations in ion


backscattering (1)
Relation between incoming and
backscattered ion energies

k = the kinematic factor

Cross section for backscattering

Elementary considerations in ion


backscattering (2)
Depth profiling

Now on to more detailed structural


work using Medium Energy Ion
Scattering (MEIS)!!

MEIS lab at Rutgers


XPS

ALD

IR
MEIS

NRP

XPS
7

Electrostatic ion detector

Energy

Al

18O

16O

~20
Angle

Depth resolution of ~3 near surface


Angular resolution 0.2
Mass-sensitive: E = E(M, )
Quantitative (cross sections are known)
8

From the Ion beam analysis laboratory at Kyoto university; note the magnetic
spectrometer.

The Kyoto Kobelco very compact MEIS facility

Footprint:
~ 2.1 x 1.5 m

New development: 3D-MEIS


TOF

S. Shimoda and T. Kobayashi


3D-MEIS

2D blocking pattern
Pulsed ion beam
Scattered (and/or recoiled) particles are flight times of scattered
(and/or recoiled) particles
detected

x
3D detector
position-sensitive and time-resolving MCP
detector
wide solid angle
incident beam
Ion : He+
Energy : 100 keV
Repetition : 500 kHz

sample
periodic atomic structure

Structural analysis of an Er-silicide


on Si(111) substrate using 3D-MEIS
S. Shimoda and T. Kobayashi
f-2

1 = 62.2

f-4

1 = 52.2
70

Er

Si

60

4
2

b-1

b-2

b-3

[011
2]
22.3

-2

[022
3]
28.8

[011
1]
39.3

50

Er

40
30
20

20

22

24

26

(a)
f-1

28
30
32
34
Scattered angle 2()

f-2

1 = 67.2
6

10

-4
18

Angle from the Si(11


0) plane ()

f-3

1 = 57.2

Intensity (counts)

Angle from the Si(11


0) plane ()

f-1

1 = 67.2

1 = 62.2

36

f-3

38

40

42

280

300

320
TOF (ns)

340

1 = 52.2

Si

b-1

b-2

b-3

[331]
22.0

-2

Er
a1

18

20

22

b-1 : [0112]
_
b-2 : [0223]
_
b-3 : [0111]

[110]
35.3

-4

(b)

360

Fig. 2 TOF spectra obtained from the data detected in


regions indicated by A and B in Fig.1.

f-4

1 = 57.2

260

24

26

28
30
32
34
Scattered angle 2()

36

38

Fig.1 3D-MEIS images of the intensities of He particles


scattered (a) from Er atoms in the Er-silicide film
and (b) from Si atoms in the Si substrate.

40

42

__
(2110)

Si

c=0.403nm
a2

3a=0.665nm

Cross section
__ cut
by the ErSi2(2110) plane

Fig. 3 Structural model of the ErSi2

Surface structure and dynamics

blocking cone

d12

Monte Carlo simulation in the


binary-encounter approximation
Input:
individual atomic positions
anisotropic rms vibration amplitude
Yi calc Yi exp
1


Output: R 100
exp
N i 1
Yi

d23

shadow cone
10
[011]

Yield (ML)

[211]

II

[011]

[110]

[011]

III

2
50 60 70 80 90 100 110 120 130

Scattering angle (deg)

d 12 (%)

[101]

-5
-10
-15

(a)

-5

10

d23 (%)

15

0.6000
0.8200
1.040
1.260
1.480
1.700
1.920
2.140
2.360
2.580
2.800
3.020
3.240
3.400

An (oversimplified) picture of the origin of the oscillatory


relaxation

Reconstruction of
the (110) surface of
Au:

Possible structural
models consistent
with a (1x2)
symmetry

Conclusions:

Missing row structure


Large first layer inwards
contraction

Buckling in the lower layers,


results in charge density
smoothing

Another research example: Surface structure of TiC(001)

Y. Kido et al, PRB 61 1748 (2000)

Surface relaxation and rumpling!

The angular shifts from the first and second layers


are displaced in opposite directions!

Melting of Pb(110) Frenken et al PRB 74, 7506 (1986)

Melting starts at the surface


Partial disorder already at ~ Tmbulk
At Tm 20 the top layer is disordered
The thickness of the disordered layer diverges logarithmically

Motivation for a lot of work in this field today


The SiO2/Si system: interface
of choice in microelectronics for
40+ years

Gate
Gate oxide

Source

Barrier?

>10nm

Silicon

Drain

CMOS Gate Structure

SiO2 needs to be replaced by a


higher dielectric constant
material (high-k)

Moores law says that the


gateoxide thickness will soon be
too small (~ 1 nm) due to large
leakage currents from quantum
mechanical tunneling

II. Nuclear Resonance Profiling


- a light projectile (proton)
penetrates the nucleus and induces a
nuclear reaction; the reaction
product ( or ) is detected.

Resonant nuclear reactions


Seo de choque diferencial (b/sr)

106
5

10

O(p,)15N

18

629

846

730

151

10

334

10

10

216

10

10

95

-2

10

15N

18O

-1

10

-3

10

-4

10

-5

10

100

200

300

400

500

600

700

Energia
Reaction cross section (b/sr)
vs. (keV)
proton energy (keV)

800

900

Resonant nuclear reactions


Seo de choque diferencial (b/sr)

106
5

10

O(p,)15N

18

629

846

730

151

10

334

10

10

216

10

raios

amost ra

(b)

10

-1

10

E Er

95

-2

10

detector (BGO)

p,
mylar (13 m)

-3

10

-4

10

-5

det ect or (a)


semicondut or

10

100

200

300

400

500

Energia (keV)

600

700

800

Reaction cross section (b/sr) vs. proton energy (keV)

900

Seo de choque diferencial (b/sr)

106
5

10

Resonant nuclear reactions


O(p,)15N

18

629

846

730

151

10

334

10

10

216

10

ER

10

-1

10

E1

95

-2

10

ER

-3

10

-4

10

E2 (> E1)

ER

-5

10

Amostra

100

200

300

400

500

600

700

800

Energia (keV)
Reaction cross section (b/sr) vs. proton energy (keV)

900

Some low energy nuclear resonances

Examples
15N

profile

As prepared

0
0

15

2 4 6 8 10 12
Profundidade
Depth (nm)(nm)

-3

Rendimento (u.a.)

Depth (nm)

15

433

Energia dos Prtons (keV)

12

N(p,) C

12

431

0
0 2 4 6 8 10 12
Profundidade (nm)

N(p,) C

429

15N

19
15

-3
19

15N

N (10 .cm )

N (10 .cm )

15

Rendimento (u.a.)

Vacuum annealed

429

431

433

Proton Energy (keV)

Nuclear resonance depth


profiling of Al2O3 on Si(100)
(Baumvol et al., Porto Alegre)

Overlapping peaks in MEIS


spectrum (M. Copel et al., IBM)

Some advantages of NRP:


Detects only one specie at a time
Very well suited for analysis of light elements

Some disadvantages of NRP:


Detects only one specie at a time
If no suitable resonance exists

III. Medium Energy Ion Scattering (MEIS)


- a low-energy, high resolution
version of conventional Rutherford
Backscattering (RBS)

A comparison between RBS and MEIS


RBS
Ion energy
~ 2 MeV
Detector resolution ~ 15 keV

MEIS
~ 100 keV
~0.15 keV

Depth resolution

~3

~ 100

2 basic advantages vs. RBS: Often better dE/dx, superior


detection equipment

Energy Dependence of dE/dx for Protons in Silicon

Energy (MeV)

Maximum of ~ 14 eV/ at ~ 100 keV!


This helps, but the greater advantage is the use
of better ion detection equipment!

Early High Resolution Work


K. Kimura et al. (Kyoto)
NIM B99, 472 (1995)

Sb on Si(100) with caps of


varying thickness; some
Sb segregates to the
surface

Determining interface strain


using monolayer resolution
ion scattering and blocking
(Moon et al.)

Ozone oxide, no strain

Thermally grown oxide,


significant strain

Spectra and information content


Backscattered proton
energy spectrum

100 keV p+
ZrO
?

(ZrO2)x(SiO2)y
Si(100)

depth
profile

Sensitivity:
10+12 atoms/cm2
10+14 atoms/cm2

(Hf, Zr)
(C, N)

Accuracy for determining total amounts:


5% absolute (Hf, Zr, O), 2% relative
10% absolute (C, N)

Depth resolution: (need density)


3 near surface
8 at depth of 40

Depth resolution and concentration profiling


Depth resolution for 100 keV protons (resolution of the spectrometer 150 eV)
Stopping power SiO2 12 eV/; Si3N4 20 eV/; Ta2O5 18 eV/
"Near surface" depth resolution 3-5 ; worse for deeper layers due to energy straggling

Layer model:
H+

raw spectrum

layer numbers

Layer 1

Layer 2

Layer 3

SUBSTRATE

Layer n

Energy, keV

Areas under each peak


corresponds to the concentration
of the element in a 3 slab
Peak shapes and positions come
from energy loss, energy
straggling and instrumental
resolution.
The sum of the contributions of
the different layers describes the
depth profile.

Oxygen Isotope Experiments: SiO2 growth mode

1. O18 uptake at the surface!


2. Growth at the interface
3. O16 loss at the surface

4. O16 movement at the


interface!

Gusev, Lu, Gustafsson, Garfunkel, PRB 52, 1759 (1995)

Schematic model
Surface
exchange
SiO2
Transition zone,
Growth

SiOx
Si (crystalline)

Deal and Grove

Work on high-k films: MEIS spectra of La2SiO5


before and after vacuum anneal
high-K La-Si-O film
20

(1)
(2)
(3)

(1) as deposited film


o

(2) vacuum anneal at 600 C


o

(3) vacuum anneal at 800 C

yield (a.u.)

15

minor rearrangement
of La upon annealing

10

no change in
O or Si profiles

0
75

80

85

90

95

proton energy (keV)

Annealing up to 800 C in vacuum shows no significant change in


MEIS spectra.
Surface remains flat by AFM.

La2SiO5 before and after in-air anneal


high-K La-Si-O film

25

La

(1) as deposited film


20

surf

int

(2) anneal in air at 400 C


o

(3) anneal in air at 800 C

yield (a.u.)

stoichiometry and thickness


consistent with other analyses
400C anneal leads to minor
broadening of the La, O and Si
distributions
800C anneal shows significant
SiO2 growth at interface
La diffusion towards the Si
substrate

15

Si

O
10

int

surf

surf

int

(1)
(2)
(3)

(1)
(2)
(3)

MOx
Si

+ O2

MOx
SiO2+MOx

Si

75

80
o

SiO2 growth at 800 C

85

90

proton energy (keV)

95

La diffusion

Higher temperature annealing


high-K La-Si-O film
20

(1)

(1) as deposited film


o

(2) vacuum anneal at 845 C


o

(3) vacuum anneal at 860 C

(2)

yield (a.u.)

15

surface Si
10

La diffusion

(3)

loss of O at 860 C
5

0
75

80

85

90

95

proton energy (keV)

The film disintegrates!

18

3 Torr O2 at 400, 500, 600, 700 C for 5 min

500

as-deposited film
18
o
O2 reox. (1 Torr, 500 C, 5 min)

ZrO2 film re-oxidized in 18O2

Zr

300

Si

16

200

18

30 Al2O3 annealed in
3 Torr 18O2

yield (a.u.)

Yield (a.u.)

400

x5

400 C
o
500 C
o
600 C
o
700 C

oxygen exchange
16

Al

Si interface

18

100

1
0
76

78

80

82

84

86

88

90

92

94

96

0
76

Proton Energy (keV)

78

No change in Zr profile
Surface flat by AFM

84

86

88

30 ZrO2
30 Al2O3

20

SiO2 Growth ()

Significant interfacial SiO2 growth for


ZrO2, less for Al2O3
Dramatic oxygen exchange:
18O incorporation and 16O removal
SiO2 growth rate faster than for O2 on Si
Growth faster under ZrO2 than Al2O3

82

proton energy (keV)

25

Deeper O and Si

80

15
10
5
0

200

400

600

800
o

O2 Anneal Temp ( C)

1000

Epitaxial Oxides
Very versatile materials:
Small changes in composition big changes in
properties (high-Tc!)
Combining two different oxides may give
multifunctionality and/or entirely new
phenomena.

49

Metallic LaAlO3/SrTiO3 (LAO/STO) interface


2D Electron Gas
LaAlO3 (Eg = 5.8 eV)
by PLD or MBE
band insulator

Metallic conductivity
Ohtomo & Hwang, Nature (2004)

Superconductivity
SrTiO3 (Eg = 3.2 eV)
band insulator

Reyren et al, Science (2007)

Magnetic order
Brinkman et al, Nat. Mat. (2007)

T(K)
Ohtomo & Hwang, Nature (2004)

Reyren et al., Science (2007)

Brinkman et al., Nat. Mat. (2007)


50

Origin of metallic state at the interface


Polar catastrophe: polar-nonpolar discontinuity

Ohtomo &Hwang, Nature 427 (2004)

This model assumes an abrupt interface


51

Important points
Oxygen vacancies have been shown by many to influence carrier concentrations
Conductivity only observed on TiO2 terminated substrates

Cationic interdiffusion Nakagawa et al, Nature 5 (2006), Kalabukhov et al, PRL 103
(2009); Willmott et al, PRL 99 (2007).

52

Samples
We have investigated samples from three
different labs.
None of the samples were made at Rutgers.
All made by PLD on TiO2 terminated
substrates.
Post-annealed in oxygen.
Most data presented today from samples by
Prof. H. Hwang, Tokyo (now Stanford).
53

He+ channeling spectrum of 4-unit-cell LAO/STO(001)


198.6 KeV He+
[001]
[111]

Tokyo-LO4

Counts

150

La

Experiment
Simulation-no outdiffusion
of Sr and Ti

4 u.c. LAO
STO (001)

x4

100

rastering beam

Sr
50

Ti

0
140

150

160

170

He+ Energy [keV]

180

The measured Sr and Ti peaks fall


at significantly higher ion energies
than those calculated for a sharp
interface:
The energies for the Sr and Ti
peaks are those of both species
present within the outermost u.c.
of LAO outdiffusion of Sr and Ti
to the LAO film
54

H+ channeling spectrum of a 4-unit-cell LAO/STO film


600

Tokyo-MID4
500

La

Experiment
Simulation-no outdiffusion of Sr and Ti

Yield

400

300

200

Al

100

Ti

Sr

85

90

95

H Energy [keV]
55

H+ channeling spectrum of a 4-unit-cell LAO/STO film


Augsburg

500

La

Experiment
Simulation-no outdiffusion of Sr and Ti

400

Yield

300

200

Al

100

Ti

Sr

85

90

95

H Energy [keV]
56

Angle dependent XPS shows poor agreement


with sharp interface model (Chambers et al)

57

Conclusions
The LaAlO3/SrTiO3 interface shows evidence for
substantial interdiffusion, a useful result for
understanding the origin of the many interesting effects
shown by this system.
More details: Surf. Sci. Rep. 65, 317 (2010)

58

A novel instrument for surface


structure studies using energetic ion
beams: the Helium Ion Microscope HIM

Ion source

Diffraction in He microscope and in SEEM

Advantages

Very high source brightness


Large depth of view
Very small beam spot
High secondary electron yield allowing currents as low as 1 fA
(typically 0.2 pA).
Topographic, material, crystallographic, and electrical
properties sampled.
Great for insulators
Does not rely on sample periodicity
Little sample damage due to relatively light mass of the
helium ion (but ).

Overview of the Helium Ion Microscope


Imaging mechanism (so
far): Secondary electrons

FOV: 200 nm
Sample: Asbestos fiber (crocidolite)
FOV:and
300carbon
nm
membrane
Single Walled Carbon Nanotube

Why is Helium So Different?

Case Study: Imaging Structures in the Inner Ear

Three areas were studied, with the goal


of obtaining direct observation and/or
measurement of nano-scale structures
that are related to the functioning of the
ear.
Tectorial Membrane: structure and layout
of collagen fibers.
Stereocilia, (sound transducers) including
The nature of their membranes
The tip links, which connect the tips
of stereocilia in adjacent rows in
their bundles
Otoconia: nanostructure of the calcitecontaining minerals employed in the ear
for balance.
Observe these in HIM without usual
staining (OTOTO method) and conductive
coating.

Helium Ion Microscope: What is there beyond imaging?


Lithography with a helium beam
Beam chemistry with a helium beam
Implantation of helium atoms
Milling, drilling with a helium beam
Analysis with a helium beam

Ion beam milling of graphene

SECONDARY ION MASS SPECTROSCOPY


SIMS

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)

Fundamentals of Surface and Thin Film Analysis, L.C. Feldman and J.W. Mayer, North Holland-Elsevier, N.Y. (1986)