5.

16 Incident Ion Techniques for Surface Composition Analysis

5.16.1 Ion Scattering Spectroscopy (ISS)

At moderate kinetic energies (few hundred eV to few keV) ion scattered from
a surface in simple kinematic collision
- interaction distance short (<10 Å)
- scattered from corrugated surface potential
- interaction time short (<1ps)
- little electronic energy transfer
- ion scattered inelastically by simple momentum transfer

Equations based on simple momentum transfer for energy of incident ion (E0),
scattered ion (E1) and displaced surface atom (E2)

 2
E1 1  2  M2
= cosθ1 ±  A − sin θ1   A= > 1.0
E0 (1 + A)2    M1
E2 4A
= ⋅cos2 θ2
( )
E0 2
1+ A

CEM 924 12.1 Spring 2001

Since energy must be conserved
- E0 = E1 + E2
- unique relation between θ1 and θ2
Scattered particle emerges at particular angle with energy dependant only on
ratio of masses of incident and scattering particle
- technique called ion scattering spectroscopy (ISS) or low energy
ion scattering (LEIS)
If scattering angle (θ1) is 90°:

 2
E1 1  2 
= cosθ1 ±  A − sin θ1  
E0 (1+ A) 2   
θ1 = 90°, cosθ1 = 0, sin θ1 = 1
becomes
E1 A −1
=
E0 A +1

If we use ion such that A>1 (choices: H+, He+, Ne+, Ar+, Kr+)
If E0, M1, θ1 fixed, measurement of E1 allows unique determination of M2,
mass of scatterer

CEM 924 12.2 Spring 2001

Ion energy in ISS/LEIS 500 eV to 3 keV
Measure E1 with concentric hemispherical analyzer set to detect massive
positive particles - reverse potentials on hemispheres
Resolution R (ability to separate signals from scatterers of different masses)
depends on
- monoenergicity of incident ions (< few %)
- collimation of incident ion (< few °)
- angular acceptance of analyzer (< few °)
- large angular acceptance → more ions, better S/N but broad ion
peaks and poorer resolution
Resolving power:

1 M2
ρ= =
R ∆M 2

CEM 924 12.3 Spring 2001

where ∆M2 is range of masses indicated by width of scattered ion energy
distribution
Maximum resolving power if
- A is close to unity
- scattering angle is large (at least 90°)

Interaction between incident ion/surface atoms large - very surface sensitive

(usually considered top atomic layer only)

CEM 924 12.4 Spring 2001

CEM 924 12.5 Spring 2001
While energetics of collision depend only on mass, not atomic potentials,
cross-section (probability) of scattering at one particular angle depends on
atomic potentials of incident and scatterer particle
Scattering depends on incident angle - trajectory and "impact parameter"
which is sensitive to atomic potentials

- size of shadow cone greatest for low energy ions

- "head on" collisions give large momentum transfer - produce large
change in direction and energy
- "grazing" collisions (small θ1) give small momentum transfer -
produce smaller changes in direction and energy

CEM 924 12.6 Spring 2001

 - possibility of double collisions increases towards grazing incidence
- broader scattered ion energies

5.16.2 Sputtering

In ISS/LEIS surface atom (scatterer) recoils into surface - not accessible for
spectroscopy
But does produce collisional cascade in near-surface region
- may include incident ion
- can lead to multiple secondary collisions
- may lead to ejection of surface atoms or fragments by backscattered
particles in solid

CEM 924 12.7 Spring 2001

CEM 924 12.8 Spring 2001
Process of removal of material by ion bombardment called sputtering or ion
etching
At very high rates of removal called ion beam milling
- higher incident beam energies than ISS/LEIS
- more massive particles
- normal incidence
Useful technique for
(i) surface cleaning
(ii) depth profiling
(iii) spectroscopy through fragment analysis

CEM 924 12.9 Spring 2001

5.16.3 Surface Cleaning

Various ways to "clean" material and expose virgin surface

- cleaving
- electrochemical/chemical/mechanical polishing
- heating in vacuum/gas environment
- sputtering
Sputtering very popular but
- leaves embedded incident particle in solid
- substantial damage and interlayer mixing
- preferential sputtering of one component
# atoms sputtered
S= Sputtering Yield
# incident ions

Sputtering is quite efficient, S>1 for Ar+ of few keV

- energy of sputtered atoms is low (1 keV in, 10-20 eV out)

CEM 924 12.10 Spring 2001

 - energy dependence of S, S(E) peaks at 10-30 keV depending upon
material

- sputtering yields also vary with incident particle mass - incident ion
type

CEM 924 12.11 Spring 2001

 - sputtering yields vary considerably between elements (for fixed
incident particle and energy) - depends on cohesive energy U (≈
heat of sublimation)

- sputtering yield varies for element in different matrices - elements,

oxides

CEM 924 12.12 Spring 2001

 - sputtering yield varies as ~1/cosθ for moderate incidence angles
(more energy concentrated at surface) but falls off at very grazing
incidence (scattering dominates, no penetration)

- sputtering in elements best understood

- sputtering in single crystals, complex materials less well-
understood
- quantitation of sputtering or sputtering rate difficult because of
large number of variables

5.16.4 Depth Profiling

When used with other techniques (AES, XPS), sputtering can sequentially
remove layers of material and build-up depth distribution of elements

CEM 924 12.13 Spring 2001

 - straightforward to calibrate sputtering rate (Å·min-1) for
polycrystalline elements
- must use standards for complex materials

But differential sputtering in alloys, compounds leads to gradual modification

of elemental composition with prolonged sputtering
- XPS, AES will initially show true concentrations but change to new
equilibrium value

CEM 924 12.14 Spring 2001

 - Mixing, atom implantation and non-uniform ion beam limit depth
resolution (resolution decreases with sputtering time)

CEM 924 12.15 Spring 2001

5.17 Analysis of Sputtered Particles
Bombard surface with high energy ions and desorb ions (<1 %) and neutrals (>
99%). Measure with a mass spectrometer
Neutrals can be ionized postirradiation by electrons (EI) or photons (laser
ionization) in technique called secondary neutral mass spectrometry (SNMS)

For EI SNMS, ionization efficiency ~10-6 → ionize ~ 10-4 % of sample

For laser ionization SNMS efficiency up to 1 → ionize ~ 99 % of sample

Alternatively, use small fraction of ions produced during desorption (< 1%) -
technique called secondary ion mass spectrometry (SIMS)

CEM 924 12.16 Spring 2001

5.17.1 Secondary Ion Mass Spectrometry (SIMS)

Originally, a method developed to apply the high sensitivity/selectivity of mass

spectrometry to the analysis of solids
Later realized that SIMS ions originate from top one or two atomic layers -
surface sensitive
Primary information from ion signal can provide information on
(1) Quantitative chemical composition (mass spectrum of ions)
(2) Structural information (cracking pattern as conditions varied)

Positive SIMS (cation) spectrum dominated by electropositive atom ions

Negative SIMS (anion) spectrum dominated by electronegative atom ions
spectra contain complimentary information

CEM 924 12.17 Spring 2001

Characteristics of SIMS spectra
- small clusters abundant
- no large clusters
- no multiply-charged clusters
- few multiply-charged ions
- sensitive to isotopic abundance
- often observe (K+), Na+, Cl-, F-

But SIMS ions yield depends on surface concentration and sputtering yield -
what about differential sputtering in complex materials?
Example: Compound with bulk composition A0.5B0.5 but with sputtering yields
SA = 1, SB = 3
At time t = 0
AES or XPS analysis = A0.5B0.5 (correct bulk composition)
SIMS analysis = A0.75B0.25 (incorrect bulk composition)
CEM 924 12.18 Spring 2001
 At time t > 0
New equilibrium surface concentration established in ratio of sputtering
yields (cA·SA = cB·SB)
AES or XPS analysis = A0.75B0.25 (incorrect bulk composition)
SIMS analysis = A0.5B0.5 (correct bulk composition)

After short sputtering period, SIMS is unaffected by differential sputtering

yields!

5.17.2 Static versus Dynamic SIMS

Two extremes:

Static SIMS Dynamic SIMS

Low sputter rates
~1 nA·cm-2
<10 Å·hr-1
Essentially "non-destructive"
Surface analysis
High sputter rates
Up to 10 mA·cm-2
Up to 100 µ·hr-1
Destructive
Depth profiling

Static and dynamic SIMS are divided at the static SIMS limit of damage
• Incident ions can cause chemistry and interlayer mixing
• Generally limit incident ion to < 1% of surface species sputtered (< 1% ML)
If 1 ML = 1015 atoms·cm-2

CEM 924 12.19 Spring 2001

 Ion dose < 1013 ions·cm-2
−9 C
1x10
1 nA⋅ cm −2 =
s ⋅ cm2
1x10 −9 ions
=
1.6x10 −19 s ⋅ cm2
= 6.25x10 9 ions ⋅ s−1 ⋅ cm−2

or static SIMS limit reached in 1600 s or 25 mins

In fact, have good sensitivity in SSIMS at much less than 1 % ML

Static SIMS used to "fingerprint" polymers and biological adsorbates

CEM 924 12.20 Spring 2001

In case of polymers, mass spectrum is related to average MW and
polydispersity

CEM 924 12.21 Spring 2001

SSIMS ion yields dependent on "chemical environment" of surface atoms

Static SIMS can also be used to study adsorbed molecules:

CEM 924 12.22 Spring 2001

Change in ion yield at 250 K implies CO molecule dissociates to adsorbed O
and C at this temperature

Is there any structural information in SIMS?

CEM 924 12.23 Spring 2001

Azimuthal dependence of Cu+ and O- emission from Cu(100)-c(2x2)-O
suggests O lies in four-fold hollow
Evidence not tested - incident particles very damaging

5.17.3 Spatial Information from SIMS

Obtained in two ways:

(1) scan ion beam (raster) across surface - ion microprobe technique
(2) scan ion collection optics across surface uniformly irradiated - ion
microscopy technique
Can focus high energy ion beam to <10 Å diameter but SIMS emission occurs
from 50-200 Å outside impact area
- typical minimum resolution ~100 nm
CEM 924 12.24 Spring 2001
 ↑ Au ore contaminated with pyrite (FeS2)

↑ 5 mm Ti bars on Si wafer

↑ Positive TOF-SIMS of Al microcontacts deposited onto GaAs showing defect presence

CEM 924 12.25 Spring 2001

5.17.4 Quantitation of SSIMS

I +m = I p ⋅ Sm ⋅ α+ ⋅θ m ⋅ T

where
Im+ = secondary ion emission current
Ip = primary (incident) ion current
Sm = sputtering yield of element m (ions and neutrals)
α+ = proportion of positive ions
θm = fractional coverage of monolayer by element m
T = transmission function of mass analyzer

Absolute quantitation of SIMS very difficult, largely because of uncertainties

in sputtering yields, ionization probabilities and mass spectrometer sensitivity
to KE of sputtered particle
Is possible with sensitivity factors developed from standards
Generally not performed

5.17.4 Instrumentation for SIMS

CEM 924 12.26 Spring 2001

Energy filter necessary to "normalize" ion energy distributions - ions emerge
from surface with different KE's

Ion sources:
Use electronegative incident ion to increase emission of positive species (+ve
SIMS)
O2+ for metal analysis - but reacts with surface?
Use electropositive incident ion to increases emission of negative species (-ve
SIMS)
Cs+, Ga+, In+ for inorganics (F-, Cl-, O-) - liquid metal ion sources

(i) electron beam crossing noble gas or H beam - ions extracted and focussed
electrostatically
- not very bright or finely focussed but rugged
(ii) RF/microwave plasma operated in high pressure noble gas
- Bright, focussed but gradually decreases in brightness
- can use for O2+ beam

CEM 924 12.27 Spring 2001

(iii) surface ionization by spontaneous emission of ions from heated surface
(difference in work function important)
- bright, works for low IP metals - Cs+
- fragile and difficult to operate
(iv) field ionization liquid metal ion sources rely on ionization in high field
from liquid metal skin on fine needle
- brightest, most focusable beam
- difficult to operate

All sources can be pulsed (beam blanking) by sweeping deflection potential so

beam passes across small aperture

Mass analyzers:
(i) Magnetic sector relies on deflection of charged particle in fixed magnetic
field by varying accelerating potential V
0.5
1  2 ⋅ V ⋅ m
- ion radius is R =  
B  z 

CEM 924 12.28 Spring 2001

 - high transmission (up to 50 % of ions), can be used with position
sensitive detectors (ion microscope)
- bulky, poor maximum m/z, cannot be baked
(ii) Quadrupole analyzers apply fixed and RF-varying DC fields to drive ions
of one m/z into stable (helical) trajectories

- small, can incorporate EI source for RGA

- poor transmission (< 1% ions), poor maximum m/z, low resolution
(iii) Time-of-flight (TOF) analyzers measure "flight time" of ions with same
KE as they drift along tube: high m/z ions travel slower

 m  0.5
- t = L 
 2 ⋅ z⋅ V 
- needs short pulsed ion source

CEM 924 12.29 Spring 2001

 - "infinite" mass range, practically 10,000 Da
- high transmission (up to 50 %), high resolution, parallel detection
of all m/z's
- "Reflectron" design eliminates differences in TOF for ions of same
m/z but different initial KE

- need accurately pulsed, short ion pulse

Ion detectors:
(i) Microchannel plate (MCP) emits electrons when struck by ion. Multiple
collisions produce secondary electron cascade that is collected by positively-
charged anode

CEM 924 12.30 Spring 2001

5.18 Summary
Excellent SIMS sensitivity (<109 atoms·cm-2) <10-4 ML for some elements
Excellent SNMS sensitivity and chemical selectivity for laser ionization (not
EI)
Adaptable to imaging (microprobe or microscope modes) with good resolution
(<0.1 µm)
Used in both depth profiling (dynamic SIMS) and "non-destructive" (static
SIMS) modes
Isotope sensitivity - labeled surfaces?
ISS and SSIMS sensitive to top atomic layer only
Rich spectra for organics - biological samples, polymers - spectra are
fingerprints for adsorbed species
Semiquantitative if standardized
Some information about bonding geometry?
Works for insulators or conductors
BUT
Absolute quantification extremely difficult (matrix effects on sputtering yields
and ionization mechanisms poorly understood)
Difficult to model
Rich spectra difficult to rationalize
Interlayer mixing
TOF-SIMS expensive ($75,000+)

CEM 924 12.31 Spring 2001