Ultralow Energy SIMS

A STUDY OF THE EFFECTS OF ULTRALOW-ENERGY
SECONDARY ION MASS SPECTROMETRY (SIMS) ON

SURFACE TRANSIENT AND DEPTH RESOLUTION

AB RAZAK CHANBASHA
(M.Sc. University of Strathclyde, UK)

A THESIS SUBMITTED
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY

DEPARTMENT OF PHYSICS
NATIONAL UNIVERSITY OF SINGAPORE
(2007)
Acknowledgements
i
Acknowledgements
This has been one of the most arduous projects that I have undertaken. This
would not have been possible without the opportunity and the trust that has been
given to me by my mentor and supervisor, Professor Andrew Wee Thye Shen. Prof.
Wee has been most encouraging and had never failed to keep up with my progress
throughout the course of this research. To him, I am indebted.
I would also like to thank Mr. Ridzuan Wu Chia Chung, Managing Director at
Omega Scientific Pte Ltd for the use of the ATOMIKA SIMS without which this
research would not have taken place. I am also grateful to my colleague Mr. Amir
Jantan for maintaining the SIMS instrument in excellent condition.
I am also fortunate to have research colleagues Dr. Liu Rong and Dr. Md.
Abdul Kader Zilani, formerly of Surface Science Laboratory (NUS), both of whom I
have had regular discussions with throughout the course of my study. Thank you, Liu
Rong and Zilani.
Finally, my utmost gratitude goes to my family. To my wife, Aishah for her
untiring support, constant encouragement and having to tolerate my spending family-
time away from home. To my children, Irshaad, Muneerah, Shafeeq and Nazheef, I
hope to have inspired them to continuously quest for knowledge. I am also grateful to
my parents for instilling in me the value of education.

Table of contents
ii
Table of contents

Acknowledgments i
Table of contents ii
Summary vi
Abbreviations and symbols viii
Figure captions x
List of Tables xii
Publications xiii

Chapter 1: Introduction 1

1.1 The need for SIMS in the semiconductor industry. 1
1.2 Challenges of ultralow-energy SIMS 3
1.2.1 Surface transient effects 3
1.2.1.1 Surface transient effects with ultralow-energy
O
2
+
sputtering 4
1.2.1.2 Surface transient effects with ultralow-energy
Cs
+
sputtering 6
1.2.2 Sputter rate 9
1.2.3 Depth resolution 10
1.2.3.1 Factors affecting depth resolution 10
1.2.3.2 Methods used to improve depth resolution: O
2
+

bombardment 13
(a) Lower primary ion energy 13
(b) Varying the incident angle 13
(c) Oxygen flooding and sample rotation 15
1.2.3.3 Methods used to improve depth resolution: Cs
+

bombardment 15
1.3 Outline of research project 17
References 19

Chapter 2: SIMS Principles 25

2.1 Introduction 25
2.2 Fundamentals of SIMS 26
2.2.1 Sputtering & collision theory 26
2.2.2 Sputtering yield 30
2.2.3 Sputter rate 31
2.2.4 Secondary ion emission 32
2.2.4.1 Secondary ion yield and ionisation probability 35
2.2.4.2 Ionisation mechanism with O
2
+
ion beam 35
2.2.4.3 Ionisation mechanism with Cs
+
ion beam 36
2.2.4.4 Secondary ion species 38
2.3 Factors affecting depth profiling 38
Table of contents
iii
2.3.1 Primary ion species 39
2.3.2 Primary ion energy 39
2.3.3 Primary ion angle of incidence 40
2.3.4 Crater edge effect 41
2.3.5 Sample charging effect 42
2.4 Quantification of depth profiles 43
2.4.1 Relative sensitivity factors and absolute standards 43
2.4.2 Depth calibration 45
References 47

Chapter 3: Experimental and instrumentation 51

3.1 SIMS instrumentation 51
3.1.1 Introduction 51
3.1.2 Vacuum system and sample handling 52
3.1.2.1 Vacuum system and monitors 52
3.1.2.2 Sample introduction 54
3.1.2.3 Sample manipulator 55
3.1.3 Primary ion gun 56
3.1.3.1 O
2
+
source 56
3.1.3.2 Cs
+
source 57
3.1.3.3 FLIG 58
3.1.4 Secondary Ion Optics 60
3.1.5 Quadrupole mass spectrometry 60
3.1.6 Secondary ion detection 63
3.1.7 Data acquisition and electronics 63
3.2 Atomic force microscopy 64
3.2.1 Principles 64
3.2.2 Contact mode 66
3.2.3 Non-contact mode 66
3.2.4 Tapping mode 67
3.3 Experimental 68
3.3.1 Sample 68
3.3.2 Analysis parameters with O
2
+
SIMS 69
3.3.3 Analysis parameters with Cs
+
SIMS 70
3.3.4 Sputter rate determination 71
References 71

Chapter 4: Effect of ultralow-energy O
2
+
SIMS on Si surface transient 73

4.1 Introduction 73
4.2 Results & discussion 74
4.2.1 Surface transients 74
4.2.1.1 Surface spikes and incomplete oxidation 75
4.2.1.2 Transient width 79
Table of contents
iv
4.2.2 Sputter rates 82
4.3 Summary 88
References 89

Chapter 5: Effect of ultralow-energy O
2
+
SIMS on depth resolution 91

5.1 Introduction 91
5.2.1.1 Depth resolution in terms of FWHM 93
5.2.1.2 Depth resolution in terms of exponential decay 100
5.2.1.3 MRI model and evaluation 103
5.2.2 Dynamic range 107
5.3 Summary 108
References 110

Chapter 6: Effect of ultralow-energy Cs
+
SIMS on Si surface transient 111

6.1 Introduction 111
6.2.1 Surface transients 112
6.2.1.1
30
Si
-
profiles 113
6.2.1.2 Transient width 117
6.2.1.3 Steady state intensity of
30
Si
-
profiles 119
6.2.2 Sputter rates 120
6.3 Summary 125
References 126

Chapter 7: Effect of ultralow-energy Cs
+
SIMS on depth resolution 128

7.1 Introduction 128
7.2.1.1 Depth resolution in terms of FWHM 131
7.2.1.2 Depth resolution in terms of exponential decay 137
7.2.1.3 Depth resolution evaluated with MRI model 141
7.2.2 Dynamic range 146
7.3 Summary 148
References 151

Table of contents
v
Chapter 8: Conclusion 152

8.1 Surface transient 152
8.2 Sputter rate 154
8.3 Depth resolution 155
8.4 Dynamic range 156
8.5 Optimum conditions for analysis 157
8.6 Proposed future work 158

Appendix A 159
Depth profiles with O
2
+
primary ion beam

Appendix B 171
Depth profiles with Cs
+
primary ion beam

Summary
vi
Summary
Ultralow-energy secondary ion mass spectrometry (SIMS) has been
introduced to meet the increasing demand for depth profiling of ultrashallow junctions
(< 20 nm) and ultrathin films following the developments in device miniaturisation in
the semiconductor industry. This challenge for accurate profiling at the near surface
(SIMS transient region) and for achieving high depth resolution is directly influenced
by the probe energy and the incident angle of the primary ion used. However, issues
such as surface roughening, atomic mixing, secondary ion yield, sputter rates and for
ultralow-energy Cs
+
, a poorly focused beam are important considerations.
The objective of this research is to understand the trends, characteristic
behaviour and processes involved with the use of ultralow-energy SIMS. Obtaining
such information will aid method development and the optimization of parameters for
accurate depth profiling. In this research, an ATOMIKA 4500 SIMS depth profiler
with O
2
+
and Cs
+
primary ion beams at an ultralow-energy (< 1 keV) and incidence
angles between 0 - 70
o
without oxygen flooding was used.
The dependence of sputter rate and transient width as a function of primary
ion energy (E
p
) and incident angle (u) is studied. Sputter rate variations with depth are
also evaluated to determine the accuracy of using average sputter rates for depth
calibrations.
The minimum transient width (z
tr
) is achievable at normal and near normal
incidence with an O
2
+
primary ion beam. When E
p
is reduced to less than 500 eV,
there is no significant reduction in z
tr
but the range of u in which this can be achieved
is greater. This corresponds to achieving steady state sputtering earlier because of
complete oxidation of silicon. The critical angle at which incomplete oxidation begins
is also ascertained.
The narrowest transient widths achieved with Cs
+
were at u ~ 30-50
o
and were
achieved when the Cs concentration stabilizes in the vicinity of the Cs
+
penetration
depth. An extended transient effect was observed when profiled at u > 50
o
suggesting
that u ~ 60
o
, which is widely used for depth profiling with Cs
+
, is not suitable for
ultrashallow junction depth profiling. The best achieved detection sensitivity is at u ~
30
o
for all energies investigated.
Summary
vii
Depth resolution is improved by lowering E
p
and good depth resolution can be
achieved not only at normal incidence but over a wider range of incident angles with
O
2
+
. The best depth resolution observed is with E
p
~ 250eV and u ~ 40
o
throughout
the depth profiled (120nm).
High depth resolution with Cs
+
is achieved at u ~ 50
o
. It is also established that
the relationship between improvements in depth resolution is linear and gradual with
increasing u. Increasing u is noted to be more sensitive in improving depth resolution
than reducing E
p
at ultralow-energy.
Based on the mixing-roughness-information model (MRI), it is possible to
differentiate the effects of atomic mixing and surface roughness on the depth
resolution of o-layers. MRI is also found to be a more sensitive indicator of surface
roughness compared to another method where an increase in the Si
+
matrix signal
were used. The dynamic range is also evaluated.

Abbreviations and symbols
viii
Abbreviations & Symbols
AES Auger Electron Spectroscopy
AFM Atomic Force Microscopy
APCVD Atmospheric Pressure Chemical Vapour Deposition
ASF Absolute Sensitivity Factor
ASTM American Society for Testing and Materials
Standards
CMOS Complementary Metal-Oxide-Semiconductor
DC Direct Current
E
p
Primary Ion Energy (probe energy)
FLIG
tm
Floating Low Energy Ion Gun
FWHM Full Width at Half Maximum
LDD Lightly Doped Drain
m/e Mass-to-charge Ratio
MQW Multi-Quantum Well
MRI Mixing-Roughness-Information
M-SIMS Double Focussing Magnetic Sector SIMS
PLC Programmable Logic Controller
PVR Peak-to-Valley Ratio
QMS Quadrupole Mass Spectrometer
Q-SIMS Quadrupole SIMS
RF Radio Frequency
R
norm
Penetration Depth
RSF Relative Sensitivity Factor
SIMS Secondary Ion Mass Spectroscopy
SIO Secondary Ion Optics
SOI Silicon-on-Insulator
S/D Source and Drain
SDE Shallow Drain Extension
STM Scanning Tunnelling Microscopy
STS Sample Transfer System
TOF-SIMS Time-of-Flight SIMS
TRIM Transport of Ions in Matter
UHV Ultra High Vacuum
XPS X-ray Photoelectron Spectroscopy

A
Screening radius
ao
Bohr radius
E Electron charge
I Material of interest
i
M
Secondary ion yield of species M
M Species
M
n
Mass of atom
N Number of atoms in primary ion
T Time
t
ox
Gate oxide thickness
Abbreviations and symbols
ix
X Penetration depth of primary ion
x
j
Junction depth
Z Depth
Erosion rate (sputter rate)
z
tr
Transient width

A Area of crater
A
n
Electron affinity
C
M
Fractional concentration of species M
E Initial energy
E
b
Lattice binding energy
E
F
Fermi level
E
v
Vacuum level
F
D
Density of energy deposited
I Secondary ion intensity
I
n
Ionisation potential
I
p
Primary ion current
L Transistor gate length
M Matrix
N Atomic density of target atoms
P
Sputtered ion emission yield

R Reference material
R
c
Resolution contrast
S
e
(E) Electronic stopping cross-section
S
n
(E) Nuclear stopping cross-section
T Transferred energy (recoil energy)
U DC voltage
U
o
Surface binding energy
V Peak amplitude of the RF voltage
W
s
Source depletion depth
W
d
Drain depletion depth
V
t
Threshold voltage
Y Sputtering yield
Z Atomic number

Ionisation probability
d
Decay length
Density of material
o(t) Applied potential
Angular frequency
u
Angle of incidence
Elastic collision cross-section
o
Dose
Workfunction
Transmission probability

Figure captions
x
Figure captions
Fig. 2.1 Ion-solid interaction processes resulting in the emission of ions.
Fig. 2.2
Relative positive ion yields for 13.5 keV O
-
, u ~ 0
o
. represents that a
compound sample was used and B.D. means barely detectable.
Fig. 2.3
Relative negative ion yields for 16.5 keV Cs
+
, u ~ 0
o
. represents that a
compound sample was used and N.D. means not detectable.
Fig. 3.1 Front view of the ATOMIKA 4500.
Fig. 3.2 The ATOMIKA 4500 SIMS Depth Profiler.
Fig. 3.3 Schematic of the vacuum system for SIMS 4500.
Fig. 3.4 Schematic of duoplasmatron ion source.
Fig. 3.5 Schematic of cesium surface ionisation source.
Fig. 3.6 Schematics of the FLIG.
Fig. 3.7 Schematic of the quadrupole mass spectrometer connections.
Fig. 3.8 Interatomic force vs. distance curve.
Fig. 3.9 Schematic of an atomic force microscope in tapping mode.
Fig. 4.1
Depth profile obtained with E
p
~ 250eV at u ~ 20
o
. The dips in the matrix
profiles and the peaks correspond to the positions of the Ge delta-layers.
Fig. 4.2
30
Si
+
profiles for (a) E
p
~250 eV (b) E
p
~500eV and (c) E
p
~1keV.
Fig. 4.3 The XPS Si 2p spectra of the surface at steady state for 4 keV O
2
+

bombardment: (a) virgin Si(100) sample; (b) sputtering at 0; (c)
sputtering at 15; (d) sputtering at 30; (e) sputtering at 45; (f) sputtering
at 55; (g) sputtering at 70.
Fig. 4.4 Measured transient width based on both
44
SiO
+
and
30
Si
+
.
Fig. 4.5 Sputter rates vs. angle of incidence. d1 shows the average sputter rate from
the surface to the first Ge delta-layer and the other is the average sputter
rate observed from the surface to the tenth Ge delta-layer.
Fig. 4.6 Normalized sputter rates throughout the depth.
Fig. 5.1 Profiles of
70
Ge
+
obtained with different E
p
(normalized to the first peak of
E
p
~ 250 eV) at a) u ~ 0
o
and b) u ~ 40
o
.
Fig. 5.2 Depth resolution of Ge delta-layer as a function of profile depth, measured
by FWHM for a) E
p
~ 250 eV b) E
p
~ 500 eV c) E
p
~ 1 keV at various
incident angles.
Fig. 5.3 Ion image of
70
Ge
+
taken at the depth where the cursor position is. a) E
p
~
250 eV, u ~ 70
o
at the 2nd delta-layer b) E
p
~ 250 eV, u ~ 70
o
at the 4
th

delta-layer c) E
p
~ 1 keV, u ~ 40
o
at the 4
th
delta-layer.
Fig. 5.4
Depth resolution of Ge o-layer at various primary ion incident angles.
Fig. 5.5
Comparison of the normalized
70
Ge
+
profiles of the first o-layer at various
E
p
.
Fig. 5.6
Plot of decay length (
d
) versus incident angle (u).
Figure captions
xi
Fig. 5.7 The projected ion range of O
2
+
primary ion beam at various incident
angles calculated from TRIM.
Fig. 5.8 Depth resolution parameters (FWHM and
d
) dependence on energy for
the first delta-layer profile at u ~ 0
o
.
Fig. 5.9 Dynamic range averaged over the first nine Ge peaks vs incident angle.
Fig. 6.1
Depth profile obtained using E
p
~320eV at u ~50
o
.
Fig. 6.2
30
Si
-
profiles for (a) E
p
~320 eV (b) E
p
~500 eV and (c) E
p
~1 keV.
Fig. 6.3
AFM images of crater bottoms resulting from E
p
~ 320 eV a) u ~ 0
o
, b) u
~ 10
o
, c) u ~ 20
o
and d) u ~ 60
o
taken at 2-3 nm depth. The rms roughness
values for craters from u ~ 0
o
, 10
o
and 20
o
are ~ 0.18 nm and for u ~ 60
o
is
~ 0.27 nm, where the onset of roughening is noted.
Fig. 6.4 Measured transient width based on
30
Si
-
profiles for E
p
~320 eV, 500 eV
and 1 keV. The plot of R
norm
of Cs
+
primary ion at various E
p
is also
shown. For conditions where extended transient effects is not observed,
the z
tr
< 2R
norm
.
Fig. 6.5
30
Si
-
intensity at steady state for various E
p
and u. Si
-
intensity from high
energy of E
p
~ 8 keV is also shown.
Fig. 6.6 Sputter rates vs angle of incidence. For each E
p
, d1 represents the average
sputter rate from the surface to the first delta-layer and the other is the
average sputter rate from the surface to the tenth delta-layer.
Fig. 6.7 Normalized sputter rates to the last delta-layer throughout the depth.
Fig. 7.1 Typical depth profiles (a)
98
SiGe
-
profiles with
30
Si
-
and
59
Si
2-
(b)
98
SiGe
-

profiles with various E
p
at u ~ 60
o
(c)
98
SiGe
-
profiles with E
p
~ 320 eV at
various u.
Fig. 7.2 Depth resolution of Ge delta-layers as a function of profile depth,
measured by FWHM for (a) E
p
~ 320 eV, (b) E
p
~ 500 eV and (c) E
p
~ 1
keV at various incident angles.
Fig. 7.3 Depth resolution of Ge delta-layers at various primary ion incident angles.
Fig. 7.4 (a) Depth resolution of the first Ge delta-layer peak at various E
p
. (b)
Linear relationship between depth resolution in terms of FWHM with u
when no surface roughening is present.
Fig. 7.5 (a) (c) Plot of decay length against incident angle for various E
p
at
selected depth. (d) Comparison of
d
at the first o-layer for various E
p
.
Fig. 7.6 Comparison of the normalized
98
SiGe
-
profiles of the first delta-layer at
various E
p
.
Fig. 7.7 Penetration depth of Cs
+
primary ions at various incident angles calculated
from TRIM.
Fig. 7.8
Depth resolution parameters (FWHM and
d
o
.
Fig. 7.9 Dynamic range averaged over the first nine
98
SiGe
-
peaks vs incident
angle.

List of tables
xii
List of tables
Table 1.1 Summary of published work on surface transients with ultralow-
energy O
2
+
sputtering
Table 1.2 Summary of published work on surface transients using ultralow-
energy Cs
+
sputtering.
Table 1.3 Summary of ripple formation observed in previous work published
using ultralow-energy Cs
+
sputtering.
Table 4.1 Summary of surface transient width, sputter rate and the onset of
roughening observed for O
2
+
sputtering on silicon wafer.
Table 5.1 Summary of depth resolution and dynamic range observed with O
2
+

sputtering.
Table 6.1 Summary of results from this work using ultralow-energy Cs
+

sputtering.
Table 7.1 Primary ion penetration depth and FWHM at u with best depth
resolution.
Table 7.2 Summary of results observed with ultralow-energy Cs
+
sputtering.
Publications
xiii
PUBLICATIONS
1. A. R. Chanbasha and A. T. S. Wee, Surface transient effects in ultralow-
energy O
2
+
sputtering of Si, Surface and Interface Analysis, 37, 628 (2005).
2. A. R. Chanbasha and A. T. S. Wee, Depth resolution studies in SiGe delta-
doped multilayers using ultralow-energy O
2
+
secondary ion mass
spectrometry, Journal of Vacuum Science and Technology B, 24, 547 (2006).
3. A. R. Chanbasha and A. T. S. Wee, Narrow surface transient and high depth
resolution SIMS using 250 eV O
2
+
, Applied Surface Science, 252, 7243
(2006).
4. A. R. Chanbasha and A. T. S. Wee, Surface transient effects in ultralow-
energy Cs
+
sputtering of Si, Surface and Interface Analysis, 39, 397 (2007).
5. A. R. Chanbasha and A. T. S. Wee, Depth resolution studies in SiGe delta-
doped multilayers using ultralow-energy Cs
+
secondary ion mass
spectrometry, Journal of Vacuum Science and Technology B, 25, 277 (2007).

Chapter 1: Introduction
1
Chapter One
Introduction

1.1 The need for SIMS in the semiconductor industry
Secondary Ion Mass Spectrometry (SIMS) is widely used as a surface analysis
tool in the semiconductor industry for dopant depth profiling, contamination
monitoring
1,2
and determination of dopant concentrations because of its ability to
detect all elements, high sensitivity, large dynamic range, unrivalled depth resolution
and minimal sample preparation. Other techniques such as Auger Electron
Spectroscopy (AES) are commonly used due to its excellent spatial resolution (< 100
nm), and X-ray Photoelectron Spectroscopy (XPS) for its ability to provide surface
chemical information and thin film thickness.
Rapid progress in complementary metal-oxide-semiconductor (CMOS)
integrated circuit technology has been associated with successful device
miniaturization with the objective of increasing packing density and switching speed.
This is best done by reducing the transistor gate length (L). Inevitably, the vertical and
lateral dimensions of doped regions in the silicon substrate must be shortened as well.
However, when L is reduced, short-channel effects arise, such as threshold voltage
(V
t
) reduction and high sub-threshold leakage current, hot-electron effects, and
source-to-drain punchthrough breakdown.
3
These effects are directly related to
channel length and drain voltage, and all are affected, directly or indirectly, by the
dimensions of the source and drain junction (x
j
).
2
To reduce the channel length while maintaining acceptable long channel
behaviour, an empirical relationship was developed
4

L
min
= A [x
j
t
ox
(W
s
+ W
d
)
2
]
1/3
(1.1)
where L
min
is the minimum transistor gate length, A is a constant, x
j
is the junction
depth where the doping concentration in the diffused profile falls to the concentration
of the background doping, and t
ox
is the gate oxide thickness. W
s
and W
d
are the
source and drain (S/D) depletion depths, which are functions of the channel doping
and supply voltage.
To reduce the peak electric fields in drain regions, a very shallow, lightly-
doped drain region (LDD)
5
may be placed between the drain and channel (also called
drain extension) so that the drain voltage drop is shared between the LDD and the
channel. These shallow drain extensions (SDE) are often called ultrashallow
junctions. The 65 nm technology node, will require drain extensions of 13-30 nm
depth depending on the type of devices.
6

Besides the channel length, the gate dielectric thickness has also been scaled
down (1 ~ 3 nm for SiO
2
/SiON)
7,8
to improve performance. There are, however,
concerns that ultrathin SiO
2
introduces other problems such as boron penetration and
high leakage currents. Such reliability issues have led to research into alternative
high-k dielectric materials.
9
In the meantime, oxynitrides and oxide/nitride stacks are
being used. The addition of N reduces boron penetration through the dielectric. Small
amounts of N (~ 0.1 atomic %) at or near the Si channel interface have been shown to
improve device performance
10
but larger amounts are undesirable.
9

Devices such as semiconductor lasers, photonic and electronic integrated
devices based on multi-quantum well (MQW) structures are gaining much attention.
3
Such periodic structures with well widths of less than 10 nm demand a high depth
resolution to resolve the individual quantum wells.
11-13

With the miniaturization of devices, current depth scales required in the
profiling of ultrashallow junctions and ultrathin oxynitride gate dielectrics coincide
with the surface transient depth region, i.e. the depth after which sputtering yield is
constant, of SIMS. This has created a challenge for accurate SIMS profiling at
ultrashallow depths of < 10 nm. This challenge for accurate profiling at the near
surface (SIMS transient region) is directly influenced by the probe energy (E
p
), the
angle of incidence (u), and the primary ion used.
14
These parameters determine the
penetration depth of the primary ion beam and the development of surface roughening
which also has implications on depth resolution.

1.2 Challenges of ultralow-energy SIMS
1.2.1 Surface transient effects
Upon bombardment of the surface by primary ions, the altered surface is
accompanied by a combination of secondary ion yield variations,
15
sputter rate
variations,
16,17
and under some conditions, surface roughening.
18-20
These variable
conditions are experienced mainly at the initial stages of profiling, and are referred to
as the surface transient. The depth up to which the surface transient effect prevails is
referred to as the transient width (z
tr
). Wittmaack
21
and Dowsett et al.
22
reported that
in this pre-equilibrium region, the ion yield and sputter rate vary by more than a factor
of 10. After this transient region, the profiling sputter rate and the secondary ion yield
stabilize and only then can a quantitative depth scale and concentration scale be
4
derived. It is therefore imperative that the width of the transient region be known so
that the first reliable data point can be ascertained.
Most work on the surface transient has been done using O
2
+
beams. However,
owing to instrument geometry and a lack of ultralow-energy ion sources, isolated data
have been published covering limited incident angles from normal to grazing angles
using ultralow-energy (E
p
< 1 keV) primary ion beams.

1.2.1.1 Surface transient effects with ultralow-energy O
2
+
sputtering
The surface transient has been shown to shorten with the use of ultralow-
energy SIMS. To reduce the transient width for O
2
+
beams, many have attempted
reducing the impact energy and/or increasing the incident angle
23,24
with respect to the
surface normal, while others have found normal incidence to be advantageous.
21,25
Clegg et al.,
26
Wittmaack
21
and Dowsett
27
pioneered studies on surface transients in Si
and GaAs for normal-incident O
2
+
beams at energies down to 230 eV. Chu et al.
28

reported a transient width of 0.5 nm using 230 eV O
2
+
at normal incidence, and
Dowsett et al.
27
reported z
tr
to be < 1 nm at E
p
~ 500 eV, and 0.4 nm at E
p
~ 300 eV at
normal incidence. Jiang and Alkemade
19
obtained z
tr
in the range 3-3.5 nm at E
p
~
600-700 eV and 70
o
< u < 80
o
. z
tr
has been observed to increase with impact energy
27

for E
p
> 1 keV and incident angle up to 45
o
,
21
followed by a decrease with increasing
incident angle beyond 45
o
.
19
No equivalent comprehensive data are available for
ultralow-energy SIMS using E
p
< 1 keV. A summary of published work is given in
Table 1.1.

5
Table 1.1 Summary of published work on surface transients with ultralow-energy O
2
+

sputtering

Transient width E
p
of O
2
+
u References
z
tr
~ 3-3.5 nm 600700eV 70
o
< u < 80
o

19

z
tr
increased with E
p
z
tr
decreased with E
p
> 1 keV
u < 45
o
u > 45
o

21

19

z
tr
~ 0.5nm 230 eV u ~ 0
o

28

z
tr
~ 0.4 nm
z
tr
< 1 nm
300 eV
500 eV
u ~ 0
o

27

z
tr
~1.5-2 nm 600 eV u ~ 73
o

24

Oxygen flooding has also been used to overcome the surface transient effect.
29

The presence of oxygen effectively promotes complete oxidation thus stabilizing the
ion yield and suppressing the onset of roughening. However, the presence of oxygen
alters the erosion rate initially resulting in shallower profiles.
30,31
Other techniques
such as silicon capping
32
and backside depth profiling
33,34
have been successful in
circumventing the surface transient effect.
Ng et al. demonstrated that with an appropriate silicon capping layer
thickness, the sputtering equilibrium is reached before the impurity depth profile
begins.
32
This approach ensures transient-free SIMS depth profiling of the
ultrashallow implant. Yeo et al. developed a backside profiling technique using
silicon-on-insulator (SOI) substrates.
33,34
The backside of the wafer was carefully
thinned down by a combination of mechanical grinding and chemical etching prior to
SIMS depth profiling. Besides reaching sputtering equilibrium well in advance of the
implant profile, the technique also demonstrated a significant improvement in depth
6
resolution compared to conventional front-side depth profiling. This technique was
successfully used to demonstrate accurate measurement of ultrashallow implants
33

and B penetration through de-coupled plasma nitrided thin gate oxides.
35

Nevertheless, the sample preparation prior to SIMS depth profiling in both techniques
can be very tedious.

1.2.1.2 Surface transient effects with ultralow-energy Cs
+
sputtering
When using a Cs
+
primary ion beam, the transient width can be reduced by
decreasing E
p
, since E
p
is related to the primary ion range in the material being
analysed.
36-38
Alternatively, increasing the incident angle has also helped.
39
The
transient width has also been observed to increase at u ~ 70
o
even though E
p
is
reduced.
40
Beyond a certain energy and incident angle as defined by the following
relationship, the increase in the transient width has been observed up to 30 nm:
40

u
(min)
= 14 log (E
p
) + 65 (1.2)
where u is degrees and E
p
is in keV.
For instance with E
p
~ 250 eV, the enhanced transient effect was observed at u
> 57
o
, for E
p
~ 500 eV when u > 60
o
, and for E
p
~ 1 keV when u > 65
o
. This
phenomenon has been associated with a decrease in the sputter rate (by almost half),
the formation of ripples at the crater bottom
15,17,41
and an increasing Cs concentration
on the surface.
16
The amount of Cs retained increases while the sputter rate decreases
with depth in the transient region. The ripple formation slows down the sputter rate
which in turn allows for a greater Cs build-up in the near surface region.
16,17
The Cs
concentration continues to increase until a steady state sputtering is achieved.
15,42,43

7
As the Cs concentration increases, so does the sputtering yield, which is much higher
than at steady state.
44

The variations in the concentration of primary ions in the substrate causes
variations in the secondary ion yield
15
of up to an order of magnitude higher as
compared to O
2
+
. The presence of Cs is known to induce a significant reduction in the
substrate work function,
15,45,46
thus enhancing negative secondary ion yield.
The transient width has been reported to be less than 5 nm with E
p
< 1 keV and u
~ 60
o
.
44,47
These and other work on the transient width using Cs
+
primary ions are
summarized in Table 1.2.

Table 1.2 Summary of published work on surface transients using ultralow-energy
Cs
+
sputtering.

Transient width E
p
of Cs
+
u References
z
tr
decreased with E
p

500 eV - 1 keV
9.5 keV
u ~ 60
o

u ~ 25
o

37

38

z
tr
decreased as u increased. 250 eV 5 keV u > 80
o

39

z
tr
increased when E
p
is
decreased
250 eV 2.5
keV
u ~ 70
o

40

Enhanced z
tr
( ~ 30 nm)
observed
250 eV
500 eV
1 keV
u > 57
o
u > 60
o

u > 65
o

40

z
tr
< 5 nm 250 eV 1 keV u ~ 60
o

44

47

8
Surface transient effects using Cs
+
primary ions have also been associated with
crater bottom roughening. No ripple formation was reported at u < 50-60
o
during Si
sputtering with E
p
< 1 keV.
44,48
Rapid formation of ripples was noted at incident
angles between 50-80
o
resulting in poorer depth resolution.
48,49
The critical angles
above which ripples form are: E
p
~ 250 eV/ u ~ 50
o
, E
p
~ 500 eV/ u ~ 55
o
and E
p
~ 1
keV/ u ~ 60
o
.
48,50
Ripple formation or its absence in the transient region is
summarized in Table 1.3.

Table 1.3 Summary of ripple formation observed in previous work published using
ultralow-energy Cs
+
sputtering.

Ripple formation E
p
of Cs
+
u References
No ripple formation < 1 keV u < 50 - 60
o

44

48
No ripple growth as observed
by AFM
250 eV u ~ 45, 55, 65
o

45

Rapid ripple formation < 1 keV u ~ 50 - 80
o

48

49

Critical angles for ripple
formation
250 eV
500 eV
1 keV
u ~ 50
o
u ~ 55
o
u ~ 60
o

48

50

Ripple growth increases with u 500 eV u ~ 50/ 60 - 75
o

48

Ripples growth from 2nm deep 500 eV u ~ 65
o

48

Ripple topography begins after
5 nm
250 eV,
1 keV
u ~ 75
o

16

17

9
Kataoka et al. recommended operating at u ~ 45-50
o
with E
p
~ 250 eV, u ~ 50-55
o

with E
p
~ 500 eV and u ~ 55-60
o
with 1 keV, these being conditions where there is no
ripple formation and minimal profile shift.
50
Other suggestions to reduce the transient
width include coating a thin layer of Cs on the surface prior to analysis and
introducing an O
2
leak during analysis, which almost completely removes the
transient, but the disadvantage is a loss in sensitivity and depth resolution due to
roughening.
51

There is still insufficient consistent experimental data on the transient width for
ultralow-energy Cs
+
depth profiling. Cs
+
, being of higher mass, has a shallower
penetration depth and reduced ion beam broadening effects. Thus, it is expected to
have a narrower transient width extending to ~ 2-2.5 times the Cs
+
penetration depth
(R
norm
), provided there is no roughening.
17,51,52

1.2.2 Sputter Rate
The rate of recession of the sample is known as the sputter rate. It is dependent on
the primary ion parameters (E
p
, u, mass, current density) and the nature of the target
(mass, crystallinity, topography, surface binding energy).
53,54
In depth profiling, the
sputter rate is not only important for analysis speed, but more importantly for depth
conversion, where a constant erosion rate is usually assumed. However the erosion
rate at the near surface is not constant due to transient effects
21
or the onset of
roughening,
18,55
thus producing distorted profiles i.e. a depth scale offset of about 1nm
per keV O
2
+
beam energy increment, resulting in the profile appearing nearer the
surface. Wittmaack
21
however, observed that the effect is negligible at E
p
< 500 eV
when using O
2
+
at normal incidence. Napolitani et al.
55
also confirmed that there is
10
negligible variation (+/-2%) in sputtering yield during the surface transient or from
the eventual onset of roughening working at grazing angles with 1.5 keV O
2
+
.
Alkemade et al.
24
observed that the sputter rate decreases as the incident angle is
increased from 60
o
to 80
o
for E
p
~ 600 eV O
2
+
. They attributed this to an increase in
the fraction of backscattered ions.

1.2.3 Depth resolution
Depth resolution, as defined by the ASTM E-42 committee, is the distance
over which a 16-84% (or 84-16%) change in signal over an interface is measured.
56

More recently, depth resolution is also taken to be a measure of the ability to
discriminate between features in adjacent thin layers.
57
It is often annotated by the full
width at half maximum (FWHM) of signals from atomic layer delta-doped samples as
well as decay length (
d
) which is the distance over which the intensity drops by a
factor of e as in:
I
2
z
= I
d
z z
z
e
/ ) (
1 2
1

, (1.3)
where I is the secondary-ion intensity, z
2
and z
1
are the depths between which the
decay length is determined.

1.2.3.1 Factors affecting depth resolution
In SIMS, the attainable depth resolution is affected mainly by three factors;
instrument related factors, sample characteristics and ion-solid interactions.
18,58
Non-
uniform irradiation from a poorly focused beam and poor rastering quality cause
erosion inhomogeneity (crater edge effects),
59
resulting in a deterioration of depth
resolution with depth. Re-deposition from crater walls (crater sidewall effects)
29
has
11
been known to affect the quality of the depth profiles. Intrinsic surface roughness on
the sample will affect topography development as depth profiling progresses.
Instrumental factors can be minimized with good ion source design and electronic or
optical gating. Near-atomically flat surfaces are now possible to achieve, thus
minimizing sample roughness.
Amongst the three factors, ion-solid interactions cannot be completely
eliminated as they are part of the sputtering process. Upon surface bombardment, ion-
solid interactions cause atomic mixing, recoil implantation, radiation-enhanced
diffusion and chemically driven segregation.
59
Atomic mixing or bombardment-
induced atom relocation is a dominant factor affecting depth resolution; ion
bombardment induced roughness and segregation are other ionsolid interactions that
affect depth resolution. By minimizing the effect of atomic mixing and thereby
maintaining the structure in the altered layer, nanometer scale depth resolution can be
achieved.
14
This ability to obtain high depth resolution in the order of nanometers is
directly influenced by the probe energy of the SIMS tool.
14,60,61
Besides using a lower
E
p
, an improved depth resolution has also been achieved by primary ion bombardment
at oblique incidence.
23,60,62
The shorter penetration depth at oblique incidence results
in a shallower altered layer and consequently, a better depth resolution.
Ion bombardment induced roughness has been attributed to a heterogeneous
oxide layer in the case of O
2
+
bombardment.
63
It has been observed that at lower
energy, the onset of surface roughening begins earlier for oblique angles.
31,55
At
normal incidence, the onset of roughening has not been observed, at least for Si and
GaAs for E
p
< 2 keV.
64
When roughening occurs, the magnitude of the roughness
depends on the incident angle.
65

12
During Cs
+
primary ion sputtering of Si, the root cause of surface roughening
and ripple formation remains unclear. It has been suggested that ripple formation
appears to occur via competing roughening and smoothing effect on/in amorphous
substrate.
17
Though the root cause is unclear, it was thought to be initiated by sputter
induced surface stress which results in microscopic surface curvature. This effect,
together with the agglomeration of Cs on the surface causes a variation in the primary
ion incident angle which effectively alters the sputtering yield. As a result, hillocks
and valleys are propagated over time in the direction of the incident beam.
Conversely, smoothing is also induced via atomic diffusion either thermally or
ballistically by the sputtering process. Another possible mechanism proposed is that
microetch pits grows into ripples due to fluctuations in beam density in a microarea.
66

Depth resolution is element dependent; B in silicon differs from Ge in
silicon.
23,60,67
Jiang et al.
68
for instance, observed 50% better depth resolution
parameters for Ge delta-layers compared to B delta-layers analysed at grazing angle
with O
2
+
primary ions. However, at normal incidence, B delta-layers gave better depth
resolution. At normal incidence, where the oxygen concentration is greater, SiGe is
oxidized and Ge segregates near the oxidebulk interface, thus degrading the depth
resolution. At grazing incidence, the oxygen incorporation is low and hence Ge
segregation is minimal. The depth resolution is then determined by atomic mixing
only, which appears to be less for Ge than B in silicon.

13
1.2.3.2 Methods used to improve depth resolution with O
2
+
bombardment
(a) Lower primary ion energy
In an early work done in the sub-keV range, Ormsby et al.
64
observed that the
depth resolution deteriorates as the impact energy is increased. Besides atomic
mixing, they also attributed the deterioration in the depth resolution to the onset of
roughening. At normal incidence, Ormsby et al.
64
obtained

high depth resolution
across the whole energy range of 230 eV < E
p
< 1 keV with FWHM < 3 nm. At
oblique angles, although a higher depth resolution was observed as the energy was
lowered, the onset of roughening occurred earlier.
31,65,68,69
Several other works
63,68,70

cited that the advantages of lowering the impact energy were compromised by
significant surface roughening, particularly at oblique angles. Another setback is the
decrease in sputtering yield.
At E
p
~ 300 eV, Clegg et al.
26
performed SIMS measurements on Ge delta-
layers in Si at normal incidence and reported a FWHM = 1.7 nm and
d
= 1.0 nm.
Similar results were achieved by Jiang et al.
23
using E
p
~ 700 eV and u ~ 71
o
. At
about the same time, Smith et al.
71
reported FWHM of better than 1 nm at normal
incidence using a 16-period Ge/Si superlattice sample. More recently, Jiang et al.
68

achieved a FWHM of 1.1 nm using E
p
~ 158 eV and u ~ 45
o
, better than their results
at normal incidence.

(b) Varying the incident angle
Besides lowering the impact energy, oblique incidence angles have been used
when normal incidence is not possible due to instrument geometry. High depth
resolution at sub-keV has been achieved at normal incidence,
26,64,68,71,72
and the depth
14
resolution was observed to be constant with depth at E
p
~ 230 eV, E
p
~ 250 eV and E
p

~ 158 eV.
68
Besides normal incidence, profiling at u ~ 20
o
and u ~ 40
o
with E
p
~ 500
eV showed a constant depth resolution throughout the depth range of 190 nm
studied.
64
In another work, the optimum depth resolution showed no difference
whether profiling was done at u ~ 0
o
or 34
o
. Wittmaack
72
concluded that below some
critical angle (u
c
) for oxidation, with measurements done at E
p
~ 1 keV, the depth
resolution should not differ much.
At oblique angles, a severe drop in depth resolution was observed above a
critical incidence u ~ 50-60
o
with E
p
~ 500 eV.
64
This phenomenon was attributed to
micro-roughening of the crater bottom. Even at very low energy of E
p
~ 158 eV, Jiang
et al.
68
noticed the onset of roughening and consequently poor depth resolution for Ge
delta-layers at u ~ 60
o
, but at u ~ 45
o
and 50
o
, good depth resolution was observed.
Wittmaack
72
also noted ripple growth at u ~ 38

- 62
o
, E
p
~ 1 keV and extrapolated that
at E
p
~ 500 eV, the ripples may grow as early as at a depth of a few nanometers.
Liu et al.
69
working at E
p
~ 500 eV and u ~ 46
o
, 56
o
and 69
o
, observed that the
onset of roughening occurs earlier at ultralow-energy and concluded that u ~ 69
o
gives
the best depth resolution, with the onset of roughness observed only at 110 nm.
The depth resolution improved with an increasing incident angle for u > 60
o
to
u ~ 80
o
using E
p
~ 600 eV.
24
However, there is a limit to the improvement in depth
resolution as the incident angle is further increased. Eventually, at very grazing
incident angle, the lateral straggling will limit the improvement in depth resolution.
73

15
(c) Oxygen flooding and sample rotation
There have also been attempts to reduce roughening by rotation and oxygen
flooding, mainly at grazing incidence, with the objective of removing or reducing
roughening. Oxygen flooding, however, has no particular advantage over normal
incidence without oxygen flooding,
14,30,31,64,74
at ultralow energies. Nevertheless, for
instruments that cannot operate at normal incidence, oxygen flooding and sample
rotation
75
have been demonstrated to be effective in reducing surface roughening
70
at
E
p
~ 500 eV and u ~ 56
o
.

1.2.3.3 Methods used to improve depth resolution with Cs
+
bombardment
There are a few reported studies on the influence of Cs
+
primary ion energy
and incident angle on depth resolution. Generally, beam induced broadening effects
have been observed to decrease with the use of heavy primary ions
59
, lower E
p
,
76,77

and increasing u
78
from 0
o
to 60
o
as it minimizes the width of the atomic mixing zone
in the sample. However, these observations were made at higher beam energies of
greater than 1 keV. At ultralow-energy (E
p
< 1 keV), depth resolution improves by
increasing u only to a certain critical u
c
before the onset of surface roughening.
17,79

Another consideration is that by lowering E
p
, the beam current density is lower and so
is the sputtering yield. The consequence is a trade-off between depth resolution and
detection limits.
78

At ultralow Cs
+
primary energy (u ~ 0-75
o
), Kataoka et al.
79
observed an
improvement in depth resolution (defined as resolution contrast R
c
= (I
max
-I
min
)/(I
max
+
I
min
) of Sb delta-layers up to a critical angle of u ~ 50
o
with E
p
~ 250 eV, u ~ 55
o

with E
p
~ 500 eV and u ~ 60
o
with E
p
~ 1 keV. van der Heide et al.
17
made similar
16
conclusions based on observations of surface roughness while working on B delta-
layers. The deterioration in depth resolution was attributed to rapid ripple formation at
oblique incidence.
17,79
Kelly et al.
80
observed the best depth resolution on B delta-
layers at u ~ 50
o
(E
p
~ 1 keV). Similar resolution can only be achieved at u ~ 60
o

when a trapezoidal scan correction is used. This technique corrects for the inclined
crater bottom caused by projection of the beam raster and spot shape onto the sample
at glancing angles, by creating a rectangular projection on the sample.
Li et al.
81
used ultralow-energy Cs
+
on B delta-layers in Si at u ~ 45-80
o
, and
observed that the depth resolution (estimated from I
max
/I
min
) degrades as u is increased
up to u ~ 70
o
. This observation, however, contradicts those made by Kataoka et al.
79

and van der Heide et al.
17
cited earlier, where depth resolution improves up to only u ~
50-60
o
. A similar conclusion could have been reached if profiles were done at u ~ 50
o
.
Li et al. observed the worst resolutions at 70
o
(E
p
~ 250-500 eV) and u ~ 75
o
(E
p
~ 1
keV), before improving to the best depth resolution at u ~ 80
o
. Others have also
observed good depth resolution at glancing angle, u ~ 85
o
using E
p
~ 1 keV.
82
To
obtain the best depth resolution whilst avoiding surface roughening, Kataoka et al.
50

recommended the use of u ~ 45-50
o
(E
p
~ 250 eV), u ~ 50-55
o
(E
p
~ 500 eV) and u ~
55-60
o
(E
p
~ 1 keV).
Techniques such as oxygen flooding used with O
2
+
sputtering, have the
opposite effect when used with Cs
+
sputtering. Ripple topography was observed at the
crater bottom when sputtered at E
p
~ 750 eV / u ~ 60
o
in the presence of oxygen.
83

17
1.3 Outline of Research Project
Given the trends in the industry, there is a need to better understand the
capability and limitation of SIMS as an analytical tool to meet the more stringent
demands. The push from the industry has led to the development of ultralow-energy
SIMS by Dowsett et al.
84
Though the use of ultralow-energy SIMS was initially
limited only to quadrupole SIMS, the capability is now possible also with magnetic
sector instruments.
85
However, due to the design of the sector instrument, the incident
angle for the primary ion beam is limited to oblique angles. With the benefit of
ultralow-energy ion sources and a quadrupole analyzer, the ATOMIKA 4500 SIMS
Depth Profiler can cover a wide range of incident angles by simply tilting the
eucentric sample stage accordingly.
The objective of this work is to comprehensively study the effect of ultralow-
energy O
2
+
and Cs
+
primary ion beams on the Si transient width and depth resolution
over a wide range of incident angles and to a depth of about 120nm. The depth
resolution was systematically evaluated with established indicators: FWHM and
d
of
delta layers. Sputter rate variations, sensitivity and the dynamic range achievable were
also investigated. From the observations of this study, we will be able to draw
conclusions on the optimum conditions necessary to minimise the transient width and
to obtain high depth resolution.
The sample used was a Ge delta-doped Si sample with ten delta-layers at
regular intervals. The delta-layers are suitable for depth resolution studies as the effect
on band broadening can be observed. The sample was first subjected to O
2
+

bombardment at normal incidence and sputtered to beyond the last delta-layer before
the profile was terminated. Subsequently, the sample was tilted at 10
o
interval to
18
cover a wide range of angles from normal incidence to 70
o
. The scan sizes chosen
were sufficiently large to avoid crater wall effects. The sample current was also
monitored throughout the profile to observe for beam stability. A similar procedure
was done with the Cs
+
primary ion beam.
The depth profiles obtained were analyzed for sputter rates, transient width,
depth resolution and dynamic range. Observations made with O
2
+
SIMS suggest that a
narrow transient width is possible not only at normal incidence but also at near-
normal incidence. There is no significant improvement in transient width going down
in energy from E
p
~ 500 eV to E
p
~ 250 eV. We also observed that although the
sputter rate during the transient is normally different from that at steady state, only at
E
p
~ 250 eV will the sputter rate remain fairly independent of depth. We confirmed
that depth resolution can be improved by lowering E
p
to ultralow-energy. By varying
u from 0
o
to 70
o
, we noted that a better depth resolution is achievable not only at
normal incidence but over a wider range of incident angles as the probe energy is
reduced. Contributions from roughening and atomic mixing to the depth resolution of
o-layers were discussed using the mixing-roughness-information depth (MRI) model.
Observations made with Cs
+
SIMS suggested that the narrowest transient
width can be achieved at 30
o
< u < 50
o
. At ultralow energies, reducing E
p
does not
have a significant effect in reducing the transient width. An extended transient effect
was observed when profiled at u > 50
o
. We demonstrated that high depth resolution is
achievable with E
p
~ 320 eV and E
p
~ 500 eV at u ~ 50
o
, and with E
p
~ 1 keV at u ~
60
o
, over a significant depth (120 nm). We established that the relationship between
improvements in depth resolution (FWHM) is linear and gradual with increasing u.
We also demonstrated that good depth resolution is achievable across a broader range
19
of u. By using the MRI model, we were able to differentiate the effect of atomic
mixing and surface roughness on the depth resolution of o-layers. The impact of
atomic mixing, surface roughness and instrument conditions (poor focus) on depth
resolution are discussed.
Finally, optimum conditions for depth profiling of ultrashallow junctions and
MQW are suggested.

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Chapter 2:SIMS Principles
25
Chapter Two
SIMS principles

2.1 Introduction
In the SIMS process, a beam of high energy ions bombards a solid surface
resulting in a range of particles being sputtered from a finite volume at the surface.
1

The energy of the primary ions is usually in the range of 1-20 keV, though more
recent instruments are capable of generating 100 eV beams. If the primary ion dose is
limited to less than 10
13
cm
-2
, then the analysis is restricted to the first few monolayers
of the surface causing minimal damage. This technique is referred to as static SIMS.
2

When the primary ion dose exceeds 10
17
cm
-2
, the surface is continuously being
eroded thus generating a depth profile. This process is often referred to as dynamic
SIMS.
3
Only dynamic SIMS will be discussed here, as it is the technique used in this
thesis. The secondary ions emitted are monitored with a mass analyzer as a function
of sputtering time, which corresponds to the depth at which the ions are located. The
depth scale or sputter rate can be calculated by measuring the physical depth of the
sputtered crater, assuming that the sputter rate is constant for a given bombardment
condition in the same matrix. The interaction of the secondary ions with the substrate
may result in neutralization or further ionization. The fraction or yield of secondary
ions produced from this interaction is dependent on the composition of the substrate
and the properties of the secondary ions.
4,5
This is referred to as the matrix effect.
6

The presence of chemically active species on the surface will also affect the
ionization yield. The implantation of chemically actives species such as O
2
+
enhances
26
the positive secondary ion yield from electropositive elements, while Cs
+
ions
enhance negative secondary ion yields from electronegative elements.
4,7
This matrix
effect has been favourably employed for signal enhancement, and O
2
+
and Cs
+
ion
sources are now commonly installed as primary ion sources in SIMS.
When a highly focused primary ion beam such as Ga
+
is used, it is possible to
achieve microanalysis and imaging. Lateral imaging of pre-selected elements can be
performed by raster scanning the Ga
+
beam.
8
Three dimensional concentration
distributions are also possible if the image is continuously developed as the depth
profile progresses.
9

2.2 Fundamentals of SIMS
2.2.1 Sputtering and collision theory
When a solid surface is irradiated with energetic ions, the ions that penetrate
the surface will lose energy by two main energy transfer process: nuclear stopping
when dominated by elastic atomic collisions with target atoms, and electronic
stopping when dominated by a non-collisional inelastic process of energy loss to
electrons in the target.
10
Sigmund described the elastic collision process as knock-on
sputtering and the latter as sputtering by electronic excitation.
11

Knock-on sputtering occurs mainly in metals and is distinguished by:
i) Single knock-on, where the impact is a direct energy transfer from the
primary ion to a surface atom in a single collision or a small number of
further collisions which results in the emission of a surface particle.
ii) Linear cascade, where the primary ion energy is dissipated via a series of
collisions among the lattice atoms. The recoil atoms involved in the
27
primary collision will in turn collide with other atoms resulting in a
collision cascade. Some target atoms and molecules near the surface may
acquire enough energy to overcome the surface binding energy and leave
the surface. The spatial density of moving atoms in this regime is small.
The linear cascade is the main process which is of interest in SIMS.
iii) Spike regime, where the process is similar to the linear cascade except that
the spatial density for moving atoms is large i.e. a majority of atoms within
a certain volume are in motion. Figure 2.1 illustrates some ion-solid
interactions.

Figure 2.1 Ion-solid interaction processes resulting in the emission of ions.

Emission
zone
(~1 nm)
Implantation
zone
(~10 nm)

Secondary ion
Single knock-on Linear cascade
Primary
ion
28
Sputtering by electronic excitation occurs mainly in insulators as the excited
electronic states have longer lifetimes, sufficient to allow energy to be transferred into
atomic motion.
The elastic binary collision theory as propounded by Sigmund is summarised
here.
12
When a primary ion penetrates the surface of the target, it is slowed down by
the nuclear stopping cross-section, S
n
(E) described as:
= T T E d E S
n
) , ( ) ( o , (2.1)
where o is the elastic collision cross-section, E is the initial energy and T is the
transferred energy (recoil energy) in a single collision. It is assumed that the energy
transferred in an elastic collision between two atoms obeys the conservation laws of
energy and momentum. An atom with mass M
1
can transfer at most T
m
energy to an
atom with mass M
2
in a head-on collision.

E
M M
M M
E T
m
2
2 1
2 1
) (
4
+
=
=
(2.2)
The nuclear stopping cross-section can be summarized in another form:
) ( 4 ) (
2 1
1 2
2 1
c t
n n
s
M M
M
e Z aZ E S
+
= , (2.3)
where s
n
(c) is a universal function based on the Thomas-Fermi model of atomic
interaction,
11
Z is the atomic number, e is the electron charge, a is the screening
radius, a
o
is the Bohr radius and
2
1
3
2
3
2
) ( 885 . 0
2 1
+ ~ Z Z a a
o
(2.4)
529 . 0 =
o
a (2.5)
29
If the recoil energy exceeds the lattice binding energy of an atom E
b
, then the
impacted atom is set in motion and will in turn collide with other atoms in the
material. The resulting collision cascade will cease when T E
b
i.e. the energetic
condition when atomic displacement can no longer occur. During the collision
cascade, each atom is displaced from its original lattice position thus giving rise to
atomic mixing, which is an isotropic process. A small fraction of the these back-
scattered target atoms with momentum towards the surface will remove the outermost
target atoms, if the energy transferred is sufficient to overcome the surface binding
energy of the surface atoms. This whole process is known as sputtering.
We have so far only considered elastic collisions. The non-collisional inelastic
electronic stopping process occurs mainly with higher projectile energies not used in
SIMS. In most sputtering situations in SIMS, the primary ion energies involved are
lower. At such lower velocities, a correction due to Lindhard and Scharf is normally
added to the nuclear stopping cross-section.
13
The electronic stopping cross section is:
2
1
1
2
3
3
2
2
3
2
1
2
6
7
1
83 . 3 ) (
|
|
.
|
\
|
|
.
|
\
|
+
=
M
E
Z Z
Z Z
E S
e
(2.6)
Sputtering from the surfaces produces mainly neutrals. Secondary ion yields
are 1% or less for most materials. In addition to the emission processes, ion
bombardment also results in changes to the surface zone of the solid. These regions in
the vicinity of the point of impact of the primary ion remain in a deformed or altered
state.

30
2.2.2 Sputtering yield
The erosion in the sputtering process is measured by the sputtering yield, Y
which is defined as the average number of atoms released at the solid surface per
incident ion. The sputtering yield is proportional to the number of displaced or recoil
atoms. In the linear cascade regime, the number of recoil atoms is proportional to the
energy deposited per unit depth in nuclear energy loss. The sputtering yield for
primary ions at normal incidence can be expressed as:
14

) , , ( ) , , ( x E F x E Y
D
u u A = (2.7)
where x is the penetration depth of the primary ion, u is the angle of incidence, F
D
is
the density of energy deposited at the surface and A represents the target properties.
F
D
is dependent on the mass, energy and direction of the incident ions as well as the
composition of the target:
) (E S N F
n D
=o , (2.8)
where o is a correction factor which takes into account the incident angle and
contributions due to large angle scattering events, and N is the atomic density of the
target atoms. The value of o varies between 0.2 and 0.4 and increases with the
incident angle due to an increase in the amount of energy deposited at the surface.
The derivation of A involves a description of the number of recoil atoms that
can overcome the surface energy and leave the solid. For the linear cascade regime,
Sigmund derived that

o
NU
042 . 0
~ A (2.9)
where U
o
is the surface binding energy. Thus,
31
) (
168 . 0
) (
042 . 0
2 1
1 2
2 1
c ot
o
n
o
n
o
s
M M
M
e Z aZ
U
E NS
NU
Y
+
=
=
(2.10)
Hence, from equation 2.10 we can see that sputtering yield is dependent on both the
primary ion and the target parameters. The impact energy, atomic number, mass, and
incident angle of the primary ions are critical parameters. For the target, the surface
binding energy, atomic number, mass and screening radius of the target atoms directly
influence the sputtering yield. Other factors include the crystallinity and crystal
orientation of the solid, topography, and preferential sputtering.
15

Sigmunds theory relates to normally incident ions. However, as the angle of
incidence is varied from the surface normal to some incident angle u, the penetration
of the ion into the surface will decrease by cos u ( for a constant range), and the whole
scattering cascade will therefore become more concentrated nearer the surface region.
The sputtering yield is then expected to increase
11
by a factor 1/cos u. The minimum
sputtering yield occurs at normal incidence, increasing gradually to a maximum at 60-
70
o
before decreasing at grazing angles.
16
The maximum is achieved due to a larger
cascade surface interaction. At grazing angles, less collision cascades occur due to a
significant scattering of primary ions from the surface.

2.2.3 Sputter rate
The sputter or erosion rate () of a sample due to ion bombardment is
eA
n YI
p
p
= z , (2.11)
32
where n is the number of atoms in the primary ion (n=2 for O
2
+
), p is density of the
material (atoms cm
-3
), e is electron charge, Y is sputtering yield, A is the area of the
crater and I
p
is the primary ion current.
15
Thus, the sputter rate is directly proportional
to sputtering yield and primary ion current density.

2.2.4 Secondary ion emission
In SIMS, only the charged atomic and molecular species are mass analysed.
The process involved in the production of secondary ions is strongly dependent on the
electronic state of the target material (matrix), ionization potential of the atoms for
positive secondary ions or the electron affinity for negative secondary ions and the
primary ion reactivity. Particles sputtered from the target surface are in the excited
metastable state, which may de-excite through photon or electron emission. Positive
ions are formed by electron emission. Alkali and alkaline earth metals have low
ionization potentials, thus these atoms have a high probability to form positive ions
compared to elements with higher ionization potentials. Conversely, negative ions are
formed by electron capture as the sputtering process also emits electrons. Halogens
and group IVA elements forms negative ions preferentially because of their high
electron affinity. These periodic trends for the elements are shown in figures 2.2 and
2.3.
17

Besides the dependence on secondary ion generation, the intensity is also
dependent on the survivability of the generated secondary ions as they leave the
surface. In the case of positive ions, the survivability decreases with increasing
availability of electrons. Thus, targets with low workfunction such as gold have low
33

Figure 2.2 Relative positive ion yields for 13.5 keV O
-
, u ~ 0
o
. represents that a
compound sample was used and B.D. means barely detectable.
17

positive secondary ion yields. However, the electronic state of the target materials
such as metals can be modified by the presence of oxygen or the absorption of other
electronegative species on the surface.
18
The absorption of such species increases the
work function of the surface and therefore increases the probability of positive metal
ions escaping the surface.
Conversely, the emission of negative secondary ions is enhanced when more
free electrons are made available by using electropositive ions such as Cs
+
. Thus, to
attain high sensitivity, the choice of primary ion species and the polarity of the
34
secondary ion are paramount. The ionisation probability also increases with mass of
the primary ion, but mainly because of an increase in sputtering yield.

Figure 2.3 Relative negative ion yields for 16.5 keV Cs
+
, u ~ 0
o
. represents that a
compound sample was used and N.D. means not detectable.
17

35
2.2.4.1 Secondary ion yield and ionisation probability
Secondary ion yield is defined as the average number of detected ions of a
selected species and polarity, per primary ion. The secondary ion yield, i
M
(counts s
-1
)
of species M is given by the following equation, also known as the basic SIMS
equation:
n o
M p M
C Y I i

= , (2.12)
where I
p
is the primary ion beam current, Y is the sputtering yield, o
is the ionization
probability of M, C
M
is the fractional concentration of M in the surface layer and n is
the transmission probability of the analytical system. Thus, sensitivity is very much a
function of ionization probability and the instrument transmission probability. Even
though n can be optimised, it is limited by the geometry and the type of mass analyzer
used; for instance, magnetic sector SIMS has better transmission probability than
quadrupole SIMS. As mentioned in the previous section, the ionization probability
can be enhanced by modifying the surface electronic state to achieve greater
sensitivity.

2.2.4.2 Ionisation mechanism with O
2
+
ion beam
The presence of electronegative species such as oxygen due to oxygen
flooding or ion bombardment can enhance the positive secondary ion yield.
19
The
enhancement has been observed to be as much as three orders of magnitude.
20
The
most likely explanation for this enhancement effect is the bond-breaking
mechanism.
21-23

36
The ionisation of the sputtered atom results from the breaking of chemical
bond with oxygen.
24
The electron transfer is localised between the atomic state of the
sputtered atom and a particular localised substrate electronic state.
The local bond-breaking mechanism is based on the assumption that
secondary ion yield from ionic surfaces can be described using the Landau-Zener-
Stueckelberg theory
25
of curve crossing for the ionic dissociation of diatomic
molecules. It also assumes that the ionisation/neutralisation takes place via resonance
charge transfer as the bond between the departing ion/atom and the substrate surface
breaks. The anion leaving a surface site can trap an electron from the outgoing atom
when the covalent and ionic curves for the original molecule cross at a certain
distance from the equilibrium position. Hence, the ion yield is related to the local
breaking of bonds.

2.2.4.3 Ionisation mechanism with Cs
+
ion beam
When Cs
+
or other electropositive elements such as alkaline and alkaline earth
metals were deposited or implanted onto/into solid surfaces, a strong correlation
between the secondary ion yield and work function of the sample surface was
observed.
26,27
Negative ion yields were enhanced while positive ion yields were
suppressed.
26-28

The work function , which is the difference between the Fermi level (E
F
) and
the vacuum level (E
V
) is the minimum energy that is required to remove an electron
from the solid surface. The ionisation process involves interaction with electrons
coming from atoms beyond the immediate neighbours suggesting a non-local
interaction. The electron tunnelling model describes this phenomenon best.
26,26

37
The presence of Cs
+
causes a reduction in the surface work function,
effectively enabling electrons to tunnel from the surface into the unoccupied valence
states of sputtered atoms, resulting in ionisation or neutralisation of the departing
atoms. This model assumes the dominance of the resonance charge transfer process
taking place between electronic states within the substrate close to the Fermi edge
(valence electrons) and unoccupied valence states of the departing ion/atom. Only
valence electrons are considered since their wavefunctions extend furthest from the
nucleus.
26
Hence, the efficiency of the electron transfer process depends on the
overlap of the wavefunctions of substrate and departing ion/atom.
The model predicts that the sputtered ion emission yield relates to exponential
scaling as:
] / ) ( exp[
o n
I P c u
+
(2.13)
] / ) ( exp[
o n
A P c u
(2.14)
where I
n
and A
n
are the ionisation potential and the electron affinity respectively of
the departing ion/atom.
29-31

o
is a specific parameter describing the electronic
interaction and its relation with the normal component of the ion emission velocity.
Lang found
o
to be 0.5 -1 eV but experimental evidence shows that
o
is independent
of emission velocity with values between 0.2-0.4 eV.
32
The relationship has been
verified by Yu
26,33
for static conditions and Gnaser
27
for dynamic conditions. Villegas
et al. recorded a greater work function change, the greater the Cs concentration on the
Si surface.
34

38
2.2.4.4 Secondary ion species
The most predominant species observed in SIMS are the singly charged atomic
ions M
; cluster ions M
n
, and molecular ions M

x
A
y
. Doubly charged ions are

normally less abundant, though group II elements may be an exception.
35
Higher
order molecular ions diminish in abundance as the order increases.
36
Molecular ions
are formed by a combination of matrix atoms or by molecular species present on the
surface. Molecular ions have narrower energy distributions than monoatomic ions,
thus the use of energy bandpass can discriminate them. For example,
31
P
-
in Si can be
profiled without interference from cluster ion
30
SiH
-
in quadrupole SIMS by use of
energy bandpass or more simply by appropriate sample biasing.
37
The cluster ion
MCs
+
has been noted to reduce matrix effects during Cs
+
SIMS profiling, and the so-
called MCs
+
method is now commonly used in semi-quantitative SIMS.
38,39

2.3 Factors affecting depth profiling
There are numerous factors that need to be considered in SIMS depth
profiling. The most critical factors that influence sensitivity and depth resolution are
the primary ion species, primary ion energy and primary ion angle of incidence. In
addition, crater edge effects must also be taken into consideration and avoided. When
insulators are analysed, sample charging needs to be minimized. An understanding of
the effects, influences and techniques developed to overcome such issues is important
for obtaining accurate depth profiles.

39
2.3.1 Primary ion species
The choice of primary ion beam species depends on several factors such as
sputtering yield, secondary ion yield, detection limits, depth resolution, lateral
resolution, crater topography and the most important consideration, availability. Many
primary ion species have been used in SIMS; for instance, O
2
+
, Cs
+
, O
-
, Ar
+
, Xe
+
, Ga
+
,
SF
5
+
and more recently C
60
+
. Ga
+
is widely used for SIMS imaging because of its
small beam diameter giving good lateral resolution (200-20 nm).
40
The heavier the
primary ion mass
41
such as Xe
+
, the better the depth resolution since it has a shallower
penetration depth. Moreover, molecular ion species such as C
60
+
disintegrate upon
reaching the surface thus dissipating their energy in the top few layers.
42
Atomic ions
such as Ar
+
and Xe
+
and molecular ions such as SF
5
+
, are used in the analysis of
polymers as they give high secondary ion yields of molecular fragments.
43
However,
the most widely used primary ion species are O
2
+
and Cs
+
. These two species provide
a good combination for general dynamic SIMS applications. The use of O
2
+
and Cs
+

result in respectable positive and negative secondary ion yield enhancement
respectively.

2.3.2 Primary ion energy
The choice of primary ion energy has a significant impact on ion yield and
sputtering yield
44-46
as well as depth resolution.
47,48
Generally, the lower the primary
ion energy, the narrower the ion-beam mixing depth and therefore the better the depth
resolution. However, lower primary ion energies will also lower the sputtering yield
resulting in longer analysis time. Similarly, the ion yield is also affected. The
secondary ion yield has been reported to increase with increasing primary ion energy
40
with Ar
+
and Xe
+
(for Si
+
and Si
-
), decrease with Cs
+
(for Si
-
) and to remain constant
with O
2
+
(for Si
+
) bombardment of silicon at normal incidence.
46,49,50
However, it has
been observed that at ultralow-energy (< 1 keV), the onset of roughening occurs
earlier i.e. at a shallower depth under conditions when surface roughening prevails.
51-
53
This effect often negates any improvement in depth resolution in ultralow-energy
SIMS.

2.3.3 Primary ion angle of incidence
Changing the angle of incidence has an impact on the secondary ion yield,
sputtering yield and depth resolution since increasing the angle of incidence results in
a shallower penetration depth. The sputtering yield has been observed to increase with
increasing angle of incidence to a certain angle, about 60-70
o
for Si, before
decreasing.
49,54

The secondary ion yield decreases as the angle of incidence is increased when
profiled with O
2
+
and Ar
+
. The dependence is greater with O
2
+
as the silicon surface is
completely oxidised at normal incidence. Less oxidation occurs with increasing angle
of incidence due to a drop in the primary beam incorporation into the silicon surface
and therefore less oxidation.
16
Hence, the decrease in the ion yield since ion yield
increases with oxidation.
Generally, the depth resolution improves with increasing angle of incidence.
The improvement in depth resolution is a result of a narrower atomic mixing length
since the collision cascade occurs nearer the surface with increasing angle of
incidence. However, the onset of surface roughening at certain angle of incidence has
a negative impact on depth resolution as has been described in 1.2.3.1 earlier. Hence
41
the depth resolution improves with increasing angle of incidence as long as there is no
onset of roughening.

2.3.4 Crater edge effect
In a depth profile, the total rastered area cannot be used for detection of
secondary ions. This is because of contributions from the crater edges and side walls.
Re-deposition of ions sputtered from crater walls (crater-sidewall effects) has been
known to affect the depth profiles.
41,55
Such sidewall contributions when detected are
seen as an increase in the ion concentration but are not representative of the depth
profile. During raster scanning of the primary ion beam, secondary ions are emitted
from all over the crater. The greatest contribution is at the crater edge when the
primary beam is near the end of the scan in the x or y direction.
15
This is made worse
by non-uniform irradiation from a poorly focused beam and poor rastering quality
causing erosion inhomogeneity.
1

To eliminate such crater edge effects, electronic and/or optical gating has been
implemented in SIMS instruments. In electronic gating, there will be no detection
during the raster scan except when the beam is scanning over the specified area near
the centre of the crater. Therefore, only secondary ions emitted from the flat centre of
the crater are collected for analysis. Similarly, in optical gating, the ion optics in the
secondary ion optics column determines the field of view of the crater base for
analysis. The overall effect of gating results in an improvement of the dynamic range
over which the secondary ions of interest are monitored.
15

42
2.3.5 Sample charging effect
Positive primary ion bombardment emits secondary ions, neutrals and
secondary electrons, giving a net electric charge at the sample surface. Thus, for
insulating surfaces, a positive charge will build up at the surface since there is no
conduction path to ground. The effect of this charging is that the energy distribution
and paths of positive secondary ions are altered, accelerating them beyond the
acceptance energy of the mass analyzer. This is particularly a problem with a
quadrupole analyzer which has a narrow energy acceptance window (typically 5 eV).
In the case of negative secondary ions, their emission will be inhibited by the
presence of a positive surface potential.
To neutralize the charging effect on the surface, low energy electron flooding
(0.1 5 keV) has been used effectively.
56,57
This has been found to be successful for
almost all matrices attempted.
58
However, this electron beam neutralization procedure
is difficult with magnetic sector SIMS and TOF-SIMS instruments because of the
high secondary ion extraction fields used and the restricted geometry of the sample
stage.
In magnetic sector instruments, a normal incidence electron beam
neutralisation technique is used.
59
High energy electrons are directed along the surface
normal in the opposite direction to the secondary ion extraction also optimised at
normal to the surface. The high ion extraction field at the sample repels the incoming
electrons such that they arrive at the sample surface with virtually zero energy as
required to neutralise the charge build-up. Recently, a combined electron and
focussed ion-beam system has also been demonstrated to be effective in eliminating
sample charging in sector instruments.
60
In TOF-SIMS, charge compensation is done
43
by exposing low-energy electron beam to the sample in between the primary ion beam
pulses.
61

Another common method to overcome the surface charging is to coat the
sample with conductive materials like gold or carbon.
62,63

2.4 Quantification of depth profiles
The raw data obtained in SIMS is the intensity (counts s
-1
) of the profiled
element against the sputtered time (s). To quantify, we will need to convert the
secondary ion counts to atomic concentrations and the sputtering time to a depth
scale. Quantitative analysis in SIMS is complicated because of the varying elemental
ion yields and the various factors that affect secondary ion yields as discussed earlier.
As such, quantification based on fundamental theories has not been very forthcoming.
The use of absolute standards and relative sensitivity factors (RSF) has been more
acceptable and practised.

2.4.1 Relative sensitivity factors and absolute standards
The relative sensitivity factor (RSF) is a factor converting the secondary ion
intensity to atom density. The RSF of an element of a particular isotope is determined
by measuring the isotopes ion intensity from a known matrix and recording it as a
ratio to a reference element.
41
The matrix element is usually chosen as the reference
as it is the most abundant. Normalising to the reference element effectively removes
possible variations in primary ion current, sputtering yield and instrument
transmission factors. The RSF of the element of interest i in matrix m can thus be
expressed as follows:
44
RSF
I
I
m
i
i
= p , (2.15)
where I is the secondary ion intensity and
i
is the concentration or atom density of
the element of interest (atoms cm
-3
). Rearranging equation 2.15 gives:
i
m
i
I
I
RSF p = , (2.16)
For accurate quantification, the instrument and analysis conditions must be
identical for the standards and samples. The conditions include the primary ion energy
and incident angle, primary ion current density, energy bandpass and detection
efficiency of the mass spectrometer.
However, elemental standards with fixed concentration level for various
impurity/matrix combinations are not always possible. This is a major setback of the
RSF method.
5
Ion implanted standards in the matrix of interest are an ideal
alternative.
64
Such standards are available commercially or can be made by
implanting a specified dose (expressed in atoms cm
-2
) of a specific isotope of the
element of interest into an undoped matrix. The unknown element of interest and the
implanted standard in similar matrices must be profiled under identical conditions.
Thus, the absolute sensitivity factor (ASF) is:
=
stop
start
x
R
x
R
I
ASF
o
(2.17)
where o
R
x
is the dose (atoms cm
-2
) of the reference material for species x and I
R
x
is the
yield or secondary ion intensity (counts s
-1
) of the implant profile for species x of the
45
reference material, summed up from the beginning (start) of the profile to the end
(stop) of the profile.
A conversion of intensity (counts s
-1
) to concentration (atoms cm
-3
) for the
element of interest involves the erosion rate as:
total
x
i
i
z
ASF I
=
.
p , (2.18)
or
z
ASF I
x
i
i
A
=
.
p , (2.19)
where z
total
is the total depth of the implant and z is the depth increment. The
equation involving ASF can also be normalized to a matrix ion signal similar to the
RSF concept.

2.4.2 Depth calibration
To convert the time scale to a depth scale, the resulting crater after sputtering
must be physically measured. The measurement can be done with a stylus
profilometer. The physical depth measured is then converted to a depth scale with the
assumption that the erosion rate is constant throughout the sputtered time. This
assumption is valid provided that the matrix composition and the beam current
remains constant throughout the depth profiled.
The assumption of a constant erosion rate can be erroneous in a number of
circumstances. Firstly, a sample with particles and/or roughness will give a distorted
depth information, characteristic of the surface topography prior to sputtering.
Secondly, at the initial stage of primary ion bombardment, the presence of surface
46
impurities such as native oxide will result in a higher ion yield when bombarded with
O
2
+
. Subsequently, as the concentration of the probe ions build up in the near surface
region, the sample forms an altered layer. As discussed earlier, in the surface transient
region the erosion rate varies until a steady state is achieved at equilibrium. Thirdly,
the incorporation of the probe ions will also cause swelling of the crater base. The
swelling will result in the final crater depth to be slightly underestimated.
65

The error in the depth profile is also known as differential shift.
66
The size of
the displacement is energy dependent and may amount to 2 nm keV
-1
of primary ion
energy. The differential shift in the profile can be calculated and corrected for, by
profiling a referenced delta-layer. By plotting the position of the delta-layer centroid
versus energy, it is possible to extrapolate the position of the feature at 0 keV.
67

However, at ultralow-energy it is difficult to ascertain the differential shift effect as
the accuracy of the profilometer does not exceed 3-4%.
68

For multilayer samples, the erosion rates will differ from layer to layer. The
erosion rate of each layer will have to be determined separately and computed into the
depth scale calibration.
47
References

1. A. Benninghoven, F. G. Rudenauer, and H. W. Werner, Secondary Ion Mass
Spectrometry: Basic Concepts, Instrumental Aspects, Applications and Trends
(John Wiley & Sons, New York, 1987).
2. M. G. Dowsett and E. A. Clark, Dynamics SIMS and its Application in
Microelectronics, in Practical Surface Analysis Vol II, edited by D. Briggs and
M. Seah (Wiley, Chichester, 1992), p. 229
3. M. G. Dowsett, C. Jeynes, E. A. Clark, R. Webb, and S. M. Newstead,
Secondary Ion Mass Spectrometry SIMS VII, edited by A. Benninghoven, C. A.
Evans, K. D. McKeegan, H. A. Storms and H. W. Werner (Wiley, Chichester,
1990), p. 615.
4. M. L. Yu, in: Sputtering by Particle Bombardment III, edited by R. Behrisch
and K. Wittmaack (Springer-Verlag, Berlin, 1991), p. 92
7. V. R. Deline, C. A. Evans, P. Williams, Applied Physics Letters 33, 578 (1978).
8. S. Seki, H. Tamura, S. Horita, N. Ito, Surface and Interface Analysis 36, 896
(2004).
9. P. A. W. van der Heide, Secondary Ion Mass Spectrometry SIMS XI, edited by
G. Gillen, R. Lareau, J. Bennett, and F. Stevie (Wiley, Chichester, 1998), p.
821.
10. M. Nastasi, J. W. Mayer, and J. K. Hirvonen, Ion-Solids Interactions:
Fundamentals and Applications (Cambridge University Press, Cambridge,
1996), p. 99.
11. P. Sigmund, Sputtering by Ion Bombardment: Theoretical Concepts in
Sputtering by Particle Bombardment I ( Springer - Verlag, Berlin, 1981), p. 9.
12. P. Sigmund, Physical Review 184, 383 (1969).
1996), p. 110.
14. H. H. Andersen and H. L. Bay, in Sputtering by Particle Bombardment I
(Springer-Verlag, Berlin, 1981), Chap. 4.
48
Spectrometry: Principles and Applications (Oxford University Press, New York,
1989).
16. K. Wittmaack, Nuclear Instruments and Methods in Physics Research B 218,
307 (1983).
17. H. A. Storms, K. F. Brown, J. D. Stein, Analytical Chemistry 49, 2023 (1977).
18. J. L. Maul and K. Wittmaack, Surface Science 47, 358 (1975).
19. A. Benninghoven, Surface Science 53, 596 (1975).
20. M. L. Yu and N. D. Lang, Nuclear Instruments & Methods in Physics Research
B 14, 403 (1986).
21. P. Williams, Surface Science 90, 588 (1979).
22. G. Slodzian, Surface Science 48, 161 (1975).
23. M. L. Yu, Nuclear Instruments & Methods in Physics Research B 15, 151
(1986).
24. M. L. Yu and K. Mann, Physical Review Letters 57, 1476 (1986).
25. C. Coudray, and G. Slodzian, Physical Review B 49, 9344 (1994).
26. M. L. Yu, Physical Review Letters 40, 574 (1978).
27. H. Gnaser, Physical Review B 54, 16456 (1996).
28. M. L. Yu, Physical Review B 24, 1147 (1981).
29. N. D.Lang, Physical Review B 27, 2019 (1983).
30. J. K. Norskov and B. I. Lundqvist, Physical Review B 19, 5661 (1979).
31. M. L. Yu, in Sputtering by Particle Bombardment III, edited by R. Behrisch and
K. Wittmaack (Springer-Verlag, Berlin, 1991), p. 98.
32. M. Bernheim and F. Le Bourse, Nuclear Instruments and Methods in Physics
Research B 27, 94 (1987).
34. A. Villegas, Y. Kudriavtsev, A. Godines, R. Asomoza, Applied Surface Science
203-204, 94 (2003).
35. R. Holland and G. W.Blackmore, International Journal of Mass Spectrometry
and Ion Physics 46, 527 (1983).
49
36. R. J. Colton, M. M. Ross, D. A. Kidwell, Nuclear Instruments and Methods in
Physics Research B 13, 259 (1986).
37. K. Wittmaack, Surface Science 53, 626 (1975).
38. Y. Gao, Journal of Applied Physics 64, 3760 (1988).
39. T. Wirtz, H. N. Migeon, H. Scherrer, Applied Surface Science 203-204, 189
(2003).
40. P. Williams and C. A. Evans, Applied Physics Letters 30, 559 (1977).
41. R. G. Wilson, F. A. Stevie, and C. W. Magee, Secondary ion Mass
Spectrometry: A Practical Handbook for Depth Profiling and Bulk Impurity
Analysis (John Wiley and Sons, New York, 1989).
42. R. Hill, R. Blenkinsopp, A. Barber, C. Everest, Applied Surface Science 252,
7304 (2006).
43. F. Kotter and A. Benninghoven, Applied Surface Science 133, 47 (1998).
46. P. C. Zalm, Journal of Applied Physics 54, 2660 (1983).
47. P. Williams and J. E. Baker, Nuclear Instruments & Methods 182, 15 (1981).
48. K. Wittmaack, Vacuum 34, 119 (1984).
49. A. E. Morgan, H. A. M. de Grefte, N. Warmolts, H. W. Werner, H. J. Tolle,
Applied Surface Science 7, 372 (1981).
50. K. Wittmaack, Applied Surface Science 9, 315 (1981).
51. Z. X. Jiang and P. F. A. Alkemade, Applied Physics Letters 73, 315 (1998).
55. C. W. Magee and R. E. Honig, Surface and Interface Analysis 4, 35 (1982).
56. B. Guzman de la Mata, M. G. Dowsett, R. J. H. Morris, Journal of Vacuum
Science & Technology A 24, 953 (2006).
57. I. S. Gilmore, and M. P. Seah, Surface and Interface Analysis 23, 191 (1995).
50
58. K. Wittmaack, Applied Physics 12, 149 (1977).
59. G. Slodzian, M. Chaintreau, R. Dennebouy, Secondary ion Mass Spectrometry
SIMS V, edited by A. Benninghoven, R. J. Colton, D. S. Simmons and H. W.
Werner (Springer, Berlin,1986), p. 158.
60. L. Ji, Q. Ji, K. N. Leung, and R. A. Gough, Applied Physics Letters 89, 164103
(2006).
61. B. Hagenhoff, D. van Leyen, E. Niehuis, and A. Benninghoven, Journal of
Vacuum Science & Technology B 7, 3056 (1989).
62. H. W. Werner and A. E. Morgan, Journal of Applied Physics 47, 1232 (1976).
63. D. S. McPhail, M. G. Dowsett and E. H. C. Parker, Journal of Applied Physics
60, 2573 (1986).
64. D. P. Leta, and G. H. Morrison, Analytical Chemistry 52, 277 (1980).

65. R. D. Barlow, M. G. Dowsett, H. S. Fox, R. A. A. Kubiak, S. M. Newstead,
Nuclear Instruments and Methods in Physics Research B 72, 42 (1992).


67. M. G. Dowsett, R. D. Barlow, P. N. Allen, Journal of Vacuum Science &
Technology B 12, 186 (1994).

Chapter 3: Experimental and instrumentation
51
Chapter 3
Experimental and instrumentation

3.1 SIMS instrumentation
3.1.1 Introduction
There are three main types of SIMS instrumentation that are commercially
available namely; time-of-flight SIMS (TOF-SIMS),
1,2
double focusing magnetic
sector SIMS (M-SIMS)
3
and quadrupole SIMS (Q-SIMS).
4
Each of these instruments
has their strengths and has been known to excel in certain applications. TOF-SIMS is
best suited for static SIMS and organics analysis, M-SIMS is best known for its high
mass resolution and Q-SIMS for its ultralow-energy capability and charge
compensation with insulators.
The SIMS instrument used for this work is the ATOMIKA SIMS 4500
instrument with a quadrupole mass analyzer.
5
The system is equipped with two
Floating Low energy Ion Guns (FLIG
tm
) which are mounted perpendicular to each
other on the main analysis chamber.
6
Each FLIG can produce a mono-energetic ion
beam in the range of 150 eV to 5 keV. The ion beams are mass filtered by a Wien
filter to ensure ion beam purity.
7
The ions produced at source are extracted and
directed to the sample via the ion optics in the ion gun column. The sample
manipulator allows for flexibility in positioning the sample. A fine focus electron
beam gun is also positioned at the analysis chamber for the purpose of sample charge
equilibration that is normally required for non-conducting samples. The secondary
ions produced are extracted with a low field via an acceleration - deceleration type
52

Figure 3.1 Front view of the ATOMIKA 4500

secondary ion optics, designed to maximize the secondary ion collection efficiency.
Finally, the secondary ions are mass analysed with the quadrupole mass analyzer and
detected by a channeltron. A schematic of the SIMS apparatus is shown in figure 3.1
and a photo of the system is shown in figure 3.2.

3.1.2 Vacuum system and sample handling
3.1.2.1 Vacuum system and monitors
An ultra high vacuum (UHV) environment is necessary to maintain
reproducibility and good detection limits especially for species present in the residual
gas. UHV conditions are necessary to minimise collisions in the path of the primary
and secondary particles with other particles in the vacuum and to prevent gas
adsorption onto the clean sputtered surface. Typically, at a vacuum pressure of 10
-6

Sample holder
Ion Sources
FLIG Ion Optics
Main Chamber
Quadrupole Mass
Spectrometer and
Secondary Ion
Detector

Sample
Transfer
System
Cesium Ion Gun Oxygen Ion Gun
Secondary Ion
Optics
53

Figure 3.2 The ATOMIKA 4500 SIMS Depth Profiler

mbar, a surface will absorb one monolayer of air molecules in about 2.5 s.
8
Thus, to
ensure that a surface can remain clean beyond 250 s, a vacuum pressure of less than
10
-8
mbar must prevail. To maintain a good vacuum, the chambers are constructed of
stainless steel and divided into three isolated volumes; the sample transfer system
(STS), the analysis chamber and the differential stage at the primary ion guns.
Stainless steel is used because of its strength, low vapour pressure and resistance to
corrosion. The STS and the differential stage are pumped by individual 70 l s
-1

turbomolecular pumps with a diaphragm pump each for roughing and backing. The
analysis chamber is equipped with a 220 l s
-1
ion pump and also a titanium
sublimation pump. The base pressure in the main chamber is 3 x 10
-10
mbar under

54
Figure 3.3 Schematic of the vacuum system for SIMS 4500
9

optimal conditions. The working pressure is monitored by ion gauge controllers at
several locations. Figure 3.3 shows a schematic of the vacuum system.

3.1.2.2 Sample introduction
Samples for analysis are mounted onto a sample holder and held down by a
spring. Several samples of between 5-10 mm
2
can be accommodated. Only the surface
to be analyzed is exposed through the sample holder window. This ensures that all
samples are at the same height and also acts to shape the local extraction field above
them. This type of holder is preferred to the top-loading design which consists of a
metal plate onto which samples are glued with colloidal silver or carbon tape. The
loaded sample holder is then transferred into the sample transfer system which is
vented with nitrogen prior to opening to the atmosphere. The STS allows fast sample
Forepump
Cs+ source
Forepump
STS
Titanium
sublimation
pump
Ion pump
Forepump
O2
+
source
Bottle valve
Reducing
valve
Bypass
valve
Leak valve
Bypass
valve
Gate
valve
Gate
valve
Gate valve Ventilation
valve
Ventilation
valve
Ventilation
valve
Analysis
Chamber
TMP
IG-Ion gauge
IGC-Ion gauge controller
TMP-Turbo molecular pump
IG
IG
IG
IGC
IG
IGC
IGC
IGC
TMP
TMP

Cs
+

Source
O2
+

Source
55
loading/exchange via the load lock without affecting the analysis chamber vacuum. It
is separated from the main chamber by a gate valve. An interlock is maintained to
prevent the gate valve from opening before the STS reaches a vacuum of 6 x 10
-6

mbar to prevent the main analysis chamber from being exposed to poor vacuum. In
the STS chamber, there are two stubs for mounting two sample holders. When the
necessary sample holder has been loaded, the chamber is evacuated again to the
acceptable vacuum pressure before the gate valve to the main analysis chamber can be
opened. The sample holder can now be transferred to the analysis chamber onto the
sample stage.

3.1.2.3 Sample manipulator
The sample manipulator provides three degrees of sample motion. The
primary ion impact angle can be varied in a eucentric manner from 0
o
to 85
o
with
respect to the ion beam by tilting the sample holder.
5
Hence, 0
o
incident angle is when
the ion beam is normal to the sample surface. The eucentric sample manipulator
ensures that there is no change in the position of ion beam impact on the sample when
the sample holder is tilted. A combination of sample holder rotation and translation is
used to position the area of interest. Sample alignment is also aided by an optical
video camera system which is fitted with a zoom microscope lens allowing visual
selection of the area of interest. External lighting via fibre optics is used to illuminate
the sample. The image of the area of interest can be observed on a monochrome
monitor.

56
3.1.3 Primary ion gun
The system is equipped with two ion guns. One ion gun is equipped with a
duoplasmatron source for oxygen or argon and another is fitted with a thermal
ionisation source for cesium. Typically, an ion gun comprises an ion source and a
series of lenses to extract ions from the source and focus the beam onto the sample.
To force ions to move from the source to the sample, a potential difference is applied
between the source and the sample. The sample is normally grounded or held at a
small bias and the source region is floated to the accelerating voltage. X-Y deflection
plates are used to raster scan. A mass energy filter (Wien filter) is used to remove
contaminant ions and other multiple charged ions of the main beam. Only ions of the
required mass and energy are allowed through whilst other unwanted species are
deflected away from the beam. Neutral particles that are not affected are removed
through a slight bend further down the ion column.

3.1.3.1 O
2
+
source
The source comprises a cathode, an anode and an intermediate electrode. The
intermediate electrode is mounted between the anode and cathode to create two
discrete plasma chambers. A schematic of the source is shown in figure 3.4. A leak
valve is used to introduce oxygen into the source chamber. The high current density in
the cathode region ionises the gas efficiently producing dense plasma. The gas
pressure in the source is usually greater than 2 x 10
-6
mbar. The intermediate electrode
compresses the discharged plasma magnetically. The dense plasma is then allowed to
expand into an expansion cup through a small orifice in the anode which completes

57

Figure 3.4 Schematic of duoplasmatron ion source.

the magnetic circuit. Ions are then extracted from the plasma surface by an electrical
field between the anode and extraction electrode facing the plasma.

3.1.3.2 Cs
+
source
The cesium source is of the surface ionisation type. The schematics are shown
in figure 3.5. Cesium contained in the reservoir is evaporated by the reservoir heater
into the ioniser. At the end of the ioniser feed tube is an apertured porous frit made of
tungsten, a high work function metal. The tungsten frit is heated by passing a constant
current to the frit heater. After diffusing through the frit, the cesium atom leaves
behind an electron and becomes ionised. However, this ionisation process is known to
fail if too much cesium collects on the tungsten substrate, hence the amount of cesium
evaporated need to be carefully controlled. The whole source is floated at high voltage
which determines the ion energy. A high extraction field is maintained to prevent a
Gas (O
2
)
Cathode
& holder
magnet anode
Extraction
electrode
(ground)
Intermediate
electrode
O
2+
, O
-

58
Figure 3.5 Schematic of cesium surface ionisation source

build up of ions at the surface of the ioniser. The rate at which the cesium atoms
arrive at the surface of the ioniser is determined by the vapour pressure of the cesium
in the reservoir and the porosity of the frit. The cesium vapour pressure depends on
the temperature of the reservoir which can be controlled.

3.1.3.3 FLIG
The FLIG (Floating Low energy Ion Gun) is designed to produce low energy
ion beams with high beam currents. It is self-aligning on assembly and the main
optical elements are a compound accelerating immersion lens for ion extraction from
source (lens 1), a variable intermediate aperture and a compound retarding immersion
lens (lens 2) as the objective.
Ions are extracted and transported at high energy along the column at high
voltage (up to 5 kV). A float voltage will allow a deceleration at the final lens for a
low energy impact on the sample. Despite the deceleration, the design of the optics is
reservoir
heater
cesium
reservoir
porous
tungsten
frit
frit
heater
feed tube accelerator
electrode
focus
electrode
Cs
Cs
+

59

Figure 3.6 Schematics of the FLIG
9

such that a good beam current is maintained. A schematic of the FLIG is shown in
figure 3.6.
The extractor and lens 1 is mounted at the opposite end of the source flange.
Immediately after lens 1 is the Wien filter and the first alignment unit. These
assemblies are in the manifold housing where there is a differential pumping port.
Source
anode
aperture
Differential
pumping port
Extractor
& lens 1
Mini
gate
valve
Wien mass
filter & x-
align plates
Main
isolator
ceramic
ring
Pressure
step
aperture
10-pin
feedthrough
port
Stigmator
plates
Scan
plates
Neutral dump
with x- & y-
alignment
plates
Lens 2
Micrometer
drive with
aperture strip
60
This whole section of the ion gun floats at the float voltage (0-5 kV) when in
operation. A mini gate valve is positioned to isolate the lower column from the
extractor and source which is necessary for source replacement or maintenance. It
also serves to block the beam when it is not in use. An adjustable aperture mechanism
with six apertures is also available to control beam current and spot size.
The lower section of the gun is designed with a 2
o
bend to reject neutrals. The
stigmators and a second alignment unit are mounted in the first segment after the bend
and the retarding lens (lens 2) in the second segment. The lower column assembly
floats at the float voltage. Lens 2 focuses and decelerates the beam. After lens 2 is a
set of X and Y raster plates for high precision scanning.

3.1.4 Secondary ion optics
The secondary ion optics (SIO) is designed to collect as many ions from the
defined sputtered region and transfer to the mass analyzer. It also limits the energy of
these ions, thus enhancing the mass resolution of the quadrupole. Unlike magnetic
sector instruments, the ultralow extraction potential at the SIO does not influence the
settings on the primary ion beam, especially the incident angle.

3.1.5 Quadrupole mass spectrometer
The quadrupole mass spectrometer (QMS) is positioned at the exit of the
secondary ion optics. Ion species that enter the QMS are channelled through to the ion
detector sequentially on the basis of their mass-to-charge (m/e) ratio.
The QMS is constructed of four electrically conducting round electrodes
(rods) held in a square array and parallel to each other as shown in figure 3.7.
61

Figure 3.7 Schematic of the quadrupole mass spectrometer connections

Opposite electrodes are connected together electrically giving a two-dimensional (x-
y) quadrupole field. During operation, one pair (x-z plane) is connected to a positive
DC voltage and a sinusoidal RF voltage is superimposed. Similarly, the other pair of
electrodes (y-z plane) is connected to a negative DC voltage with a sinusoidal RF
voltage superimposed, but 180
o
out of phase with the RF voltage to the first pair. The
potentials applied are represented by the following expression:
)] cos( [ ) ( t V U t e o + = ,
where U is the DC voltage, V is the amplitude of the RF voltage applied to either pair
of rods and e is the angular frequency (2tf) of the RF. Under these circumstances, the
62
equipotential surfaces are symmetric hyperbolic cylinders and the potential on the z-
axis is zero.
If an ion is injected at the end of this assembly with motion generally parallel
to the z-axis, the RF and DC fields perpendicular to the z-axis will cause it to undergo
transverse motion. Light ions (low m/e ratio) will be able to follow the alternating
component of the field. In the x-direction, ions are in phase with the RF drive and
gain energy from the field, oscillating with increasingly large amplitudes until they
collide with one of the rods and are discharged. Therefore, the x-direction acts as a
high-pass mass filter i.e. only high masses will be transmitted to the other end of the
quadrupole without striking the x-electrodes.
On the other hand, heavy ions will be unstable in the y-direction, because of
the defocusing effect of the DC component. However, lighter ions will be stabilized
by the alternating component provided that its magnitude and amplitude are such as to
correct the trajectory whenever its amplitude tends to increase. Therefore, the y-
direction can be considered as a low-pass mass filter, i.e. only low masses will be
transmitted to the opposite end of the quadrupole without striking the y-electrodes.
Thus with proper selection of RF/DC ratio, the two directions together can be
made to discriminate against both high and low mass ions. The RF magnitude and
frequency determine the mass of the ions that can undergo stable trajectories through
the quadrupole in the z-axis. As the RF amplitude increases, heavier ions begin to
oscillate in phase with the RF and collide with the rods. The RF/DC ratio determines
the mass filter selectivity, i.e. the mass resolution.
4

Quadrupole mass spectrometers cannot differentiate ion species that have
similar masses, unlike magnetic sector instruments which have better mass resolution.
63
However, molecular ion interference can be removed by setting the ion energy filter
to accept only higher energy ions which are predominantly atomic ions.

3.1.6 Secondary ion detection
Ions emerging from the quadrupole mass analyser are detected with a channel
electron multiplier (channeltron). This is a horn-shaped glass tube coated with a
resistive material on the inside wall which acts as the secondary electron emitting
surface. The large opening provides a higher probability for an incident ion to be
captured. When a potential is applied between the ends of the tube, the resistive
surface forms a continuous dynode. Electrons produced are multiplied down the
curved channel and pulses are counted via the electronics in counts per second. The
pulse count is proportional to the number of ions detected.

3.1.7 Data acquisition and electronics
There are several electronic modules, each controlling a specific part of the
SIMS operations. A programmable logic controller (PLC) is also available to ensure
safety as well as to control the vacuum interlocks. A computer system is used for data
acquisition and data analysis.

64
3.2 Atomic Force Microscopy
3.2.1 Principles
Atomic force microscopy (AFM) is widely used for surface topography
imaging down to atomic resolution and for a wide variety of fundamental surface
science applications.
10-12
Unlike scanning tunnelling microscopy (STM) which is
limited to semiconductors and conductive materials, AFM can be used with insulators
too as it does not work on the phenomenon of electron tunneling.
13
In the atomic force
microscope, an atomically sharp tip typically made of silicon nitride (Si
3
N
4
) or single
crystalline silicon (Si), located at the free end of a cantilever, is scanned over the
surface of the sample.
12,13
As the tip moves over the sample (or the sample traverses
under the tip), forces between the tip and the surface cause the cantilever to bend or
deflect depending on the contour of the surface.
A laser and/or a position sensitive detector measure the deflection of the
cantilever and feedback to a control system. The signals received enable the control
system to maintain either a constant force or a constant height above the sample as
well as generating a map of the surface topography.
12

Several forces are involved in the deflection of the cantilever, the most
common being the van der Waals force. The dependence of the van der Waals force
upon the distance of the tip from the sample is described in figure 3.8.
As the tip moves closer to the surface, the atoms between the tip and the
surface weakly attract each other by the long range attractive force. This is the
distance in which the AFM operates in the non-contact regime. The attraction
increases until the atoms are in close proximity where their electron clouds will repel
65

Figure 3.8 Interatomic force vs. distance curve.
11

each other electrostatically. The electron-electron electrostatic repulsion progressively
weakens the attractive force as the interatomic distance decreases. This force goes to
zero when the interatomic distance is a few angstroms, about the length of a chemical
bond. When the van der Waals force becomes positive (repulsive), the atoms are in
contact. The AFM now operates in the contact mode. When a vibrating tip approaches
the sample, they come into intermittent contact. The atoms between the tip and
sample, alternate between being repelled by the short range repulsive force and
attracted by the attractive force. This mode is also known as the tapping or
(intermittent-contact) mode. These modes are described further in the following.

Force
Distance
(tip-to-sample separation)
contact
non-contact
intermittent-
contact
attractive force
repulsive force
66
3.2.2 Contact mode
In this mode, the tip is held less than a few angstroms from the sample surface,
and the resultant interatomic force between the cantilever and the surface is repulsive.
The repulsive van der Waals force will counter any force acting against it. This
translates into the bending of the cantilever as the atoms at the tip are close to the
atoms on the sample surface. Other than the van der Waals force and the force exerted
by the cantilever, a capillary force exerted by the presence of a thin film of water is
also present. This capillary force (~ 10
-8
N) arises when water around the tip holds the
tip in contact with the surface. This force is constant as long as the tip is in contact
with the surface. Hence, the total force exerted on the sample is the variable cantilever
force plus the constant capillary force which will be countered by the repulsive van
der Waals force. The deflection of the cantilever is sensed and the voltage that the
feedback amplifier applies to the piezoelectric device to maintain constant-height or
constant-force is translated to topographical information. Since the repulsive force is
not unique to any material surface, AFM is applicable to conducting as well as
insulating materials.
However, in the contact mode, the sample surface may be damaged due to
interaction of the hard tip with the surface. This mode is therefore not suitable for soft
or elastic samples.

3.2.3 Non-contact mode
In the non-contact mode, the cantilever is vibrated near the surface of the
sample (~ 50-150). Since the distance between the atom at the tip and the surface is
greater, the attractive forces are weaker. To overcome this, a stiff cantilever is
67
oscillated near its resonant frequency by means of a piezo oscillator with an amplitude
of a few tens to hundreds of angstroms. The control system then detects the changes
in the frequency, phase or vibration amplitude in response to the force gradients as the
tip comes near the sample surface. The changes are monitored and the feedback
system will maintain the resonant frequency or amplitude thus keeping the average
tip-to-sample distance constant. A combination of this feedback and the scanning
motion is used to generate the topographical image.
Non-contact AFM is preferred for measuring soft samples. However, if a few
layers of condensed water are on the surface of the sample, then the AFM will image
the water layer instead.

3.2.4 Tapping mode
The tapping mode
14,15
or intermittent contact mode is similar to the non-contact mode
except that the vibrating cantilever is now closer to the surface of the sample, lightly
touching or tapping the surface. During scanning, the tapping takes place at a
frequency of between 50,000 to 500,000 Hz, corresponding to the resonant frequency
of the cantilever.
10
As the oscillating cantilever intermittently contacts the surface, the
oscillation will be reduced due to energy loss when contacting the surface. The
resultant reduction in oscillation amplitude is used to identify and measure the surface
features. This method gives high resolution images without inducing destructive
lateral forces (frictional or drag). Thus, scratching of the soft surface and removal of
loosely bound surface materials can be avoided. Issues with the fluid contamination
layer which affects the oscillating probe will also be eliminated. A schematic of the
AFM in tapping mode is shown in figure 3.9.
68

Figure 3.9 Schematic of an atomic force microscope in tapping mode.

3.3 Experimental
3.3.1 Sample
The sample used was a Ge delta-doped Si sample comprising ten Si
0.7
Ge
0.3

delta-layers of 0.4 nm thickness (nominally), grown by atmospheric pressure chemical
vapour deposition (APCVD) at 700
o
C. The first layer is at 12 nm and subsequent
nominal depths of the delta-layers are at multiples of 11 nm.
16
The surface of the
sample was smooth with an rms roughness ~ 0.15 nm obtained by measuring with an
AFM. The native oxide, estimated at about 1-2 nm based on the age of the sample,
was not removed prior to sputtering.
17
The sample was obtained from Z. X. Jiang,
Delft University of Technology, and the dimensions were not verified as there was
insufficient sample for Transmission Electron Microscope analysis.
laser
position
sensing
device computer
control
system oscillating
tip
sample

Piezoelectric scanner
Cantilever
with tip
positioning
device
69
Silicon substrate was chosen as it is of technological importance and is widely
used in the semiconductor industry. The delta-layers are used as depth markers for the
study of depth resolution. The Ge delta-layer system has also been noted not to induce
any beam-induced roughening in Si.
18

3.3.2 Analysis parameters with O
2
+
SIMS
The O
2
+
primary ion energies used were 1 keV, 500 eV and 250 eV at incident
angles from 0
o
(normal incidence) to 70
o
at 10
o
intervals. The corresponding beam
currents were 140 nA, 130 nA and 48 nA respectively. The beam diameters were
estimated from the ion image of the Cu aperture on the sample holder to be ~ 30 um
for E
p
~ 1 keV and 500eV, and 60 um for E
p
~ 250 eV. The beam was rastered over
an area of 200 x 200 um for E
p
~ 250 eV and E
p
~ 1 keV, and 180 x 180 um for E
p
~
500 eV. Crater edge effects were minimized by using 6% area electronic gating
positioned at the centre of the crater. The secondary ions monitored were
44
SiO
+
,
30
Si
+

and
70
Ge
+
. The matrix ions
44
SiO
+
and
30
Si
+
were monitored for the purpose of
evaluating surface transients.
19

30
Si
+
and
70
Ge
+
isotopes were monitored even though
their relative abundance are smaller, 3% for
30
Si and 20% for
70
Ge as the signal
intensity (cps) obtained were sufficiently high but below the saturation level of the
channeltron. These isotopes were also selected as they are free from mass interference
with other elements or molecular ions.

70
3.3.3 Analysis parameters with Cs
+
SIMS
The Cs
+
primary ion energies used were 1 keV, 500 eV and 320 eV at incident
angles from 0
o
(normal incidence) to 70
o
at 10
o
intervals. E
p
~ 320 eV was the
minimum primary ion energy possible on the SIMS instrument used. The
corresponding beam currents used were 77 nA, 40 nA and 40 nA respectively. The
beam diameters were estimated to be 50 um for E
p
~ 1 keV and 70 um for E
p
~ 500
eV and 320 eV. The values were estimated from the ion image of the Cu aperture on
the sample holder.
The beam was rastered over an area of 300 x 300 um for 1 keV and 400 x 400
um for 500 eV and 320 eV. Larger scan areas were selected compared to that used
with O
2
+
primary ion beam as the beam diameter is larger. A 6% area electronic
gating together with a sufficiently large scan area will minimise the crater edge
effects. The secondary ions monitored were
30
Si
-
,
59
Si
2-
and
98
SiGe
-
.
30
Si
-
and
59
Si
2
-
were chosen as matrix signals as these are the most probable states for Si secondary
ions and their signal intensities were not too high as to saturate the channeltron.
98
SiGe
-
molecular secondary ion was monitored instead of
70
Ge
-
as it was found to be
more sensitive.
The samples were analysed with the ATOMIKA 4500 SIMS Depth Profiler
described earlier. The profiles obtained were subsequently analysed and the results are
presented and findings discussed in the next few chapters. The surface topography of
several craters was determined using a Digital Instruments (Veeco) Nanoscope
Multimode D3000 series atomic force microscopy (AFM). All AFM images were
collected using the tapping mode.

71
3.3.4 Sputter rate determination
The crater depths at the completion of sputtering were not measured as the
depth of the delta-layers was used for sputter rate determination. The sputter rates
were calculated for each depth segment i.e. from the surface to the first delta-layer
and subsequently from one delta-layer to the next delta-layer. The depths were taken
at each
70
Ge
-
peak position and the sputter rate was assumed to be constant from one
delta-layer to the next.
The sputter rate for each depth segment is calculated as:

t
n n 1
=
o o
z nm min
-1

where o
n
is the peak position at the nth delta-layer and t is the time taken to sputter
from the position o
n-1
to o
n
.

References

1. E. Niehuis and T. Grehl, Secondary Ion Mass Spectrometry SIMS XII, edited by
A. Benninghoven, P. Bertrand, H. N. Migneon and H. W. Werner, (Amsterdam,
Elsevier, 2000), p. 49.
2. P. Steffens, E. Niehuis, T. Friese, D. Greifendorf, A. Benninghoven, Journal of
Vacuum Science & Technology A 3, 1322 (1985).
3. J. M. Chabala, Secondary Ion Mass Spectrometry SIMS X, edited by A.
Benninghoven, B. Hagenhoff, H. W. Werner, (Wiley, Chichester, 1997), p. 23.
4. A. R. Krauss and D. M. Gruen, Applied Physics 14, 89 (1977).
5. J. L. Maul and S. B. Patel, Secondary Ion Mass Spectrometry SIMS XI, edited by
G. Gillen, R. Lareau, J. Bennett, and F. Stevie, (Wiley, Chichester, 1998), p.
707.
6. M. G. Dowsett, N. S. Smith, R. Bridgeland, D. Richards, A. C. Lovejoy and P.
Pedrick, Secondary Ion Mass Spectrometry SIMS X, edited by A. Benninghoven,
B. Hagenhoff, H. W. Werner, (John Wiley, Chichester, 1997), p. 367.
72
7. C. W. Magee, W. L. Harrington, R. E. Honig, Review of Scientific Instruments
49, 477 (1978).
8. J. F. O'Hanlon, A User's Guide to Vacuum Technology, (Wiley-Interscience,
New Jersey, 2003), p. 14.
9. Atomika SIMS 4500 Operation Manual v. 3.8, (1998).
10. E. Meyer, H. J. Hug, R. Bannewitz, Scanning Probe Microscopy: The Lab on a
Tip, (Springer-Verlag, Berlin Heidelberg, 2004), pp. 45-95.
11. R. Howland and L. Benatar, A Practical Guide to Scanning Probe Microscopy,
(Park Scientific Instruments, 1996).
12. S. N. Margonov and M. H. Whangbo, Surface Analysis with STM and AFM,
(VCH, Weheim, 1996).
13. G. Binnig, C. F. Quate, Ch. Gerber, Physical Review Letters 56, 930 (1986).
14. Q. Zhong, D. Inniss, K. Kjoller, V. B. Elings, Surface Science Letters 290, L688
(1993).
15. P. K. Hansma et al., Applied Physics Letters 64, 1738 (1994).
(1999).
18. Z. X. Jiang and P. F. A. Alkemade, Journal of Vacuum Science & Technology B
16, 1971 (1998).

Chapter 4: O
2
+
SIMS and surface transient
73
Chapter Four
Effect of ultralow-energy O
2
+
SIMS on Si surface transient

4.1 Introduction
In this chapter, I present my study using ultralow-energy O
2
+
primary ion
beams. Three primary ion beam energies were selected and depth profiles were
obtained with a range of incident angles. Since the O
2
+
primary ion beam enhances the
secondary ion yield of electropositive elements, we focus our study only on positive
secondary ion profiles.
The Si
+
matrix profiles were evaluated and surface spikes were observed to
occur under certain conditions. Possible reasons for the existence of surface spikes are
discussed. The matrix secondary ions Si
+
and SiO
+
monitored were evaluated for
transient width as a function of incident angle. The z
tr
values obtained from both Si
+

and SiO
+
were compared to decide whether it is sufficient to determine the end of
surface transient based on a single matrix profile. From the available data on z
tr
, the
dependence of z
tr
on u and E
p
is discussed. The onset of surface roughening is
ascertained by observing the Si
+
matrix profile. The condition whereby this
phenomenon occurs is reported.
The sputter rates calculated show that at ultralow-energy, the maximum rates
are achievable at a lower u compared to that at higher energies greater than 1 keV.
1

Sputter rate variations with depth are also evaluated to determine the accuracy of
using average sputter rates for depth calibrations. Finally, the conditions under which
minimum z
tr
and accurate depth calibration can be achieved are recommended.
Chapter 4: O
2
+
74
4.2 Results and Discussion
4.2.1 Surface Transient
Figure 4.1 shows the depth profiles of
44
SiO
+
,
30
Si
+
and
70
Ge
+
using E
p
~ 250
eV at u ~ 20
o
. I
p
is the primary ion current profile, which was monitored throughout
the depth profile. Only profiles with constant current were considered in this study.
This is essential to ensure that there are no variations in sputtering yield with depth
due to the primary ion beam current. The Ge delta-layer peaks are used as depth
markers. The
30
Si
+
and
44
SiO
+
profiles were used in the determination of the surface
transient width. The
70
Ge
+
profile shows ten well-resolved peaks. However, some
degradation in the resolution sets in as the profile goes deeper. This phenomenon is
discussed in the next chapter on depth resolution. The dips in the intensity of the
30
Si
+

and
44
SiO
+
profiles correspond to the positions of the Ge delta-layers. Similar profiles
were obtained by varying E
p
and u as mentioned in Chapter 3 are shown in appendix
A.
Figure 4.1 Depth profile obtained with E
p
~ 250eV at u ~ 20
o
. The dips in the matrix
profiles and the peaks correspond to the positions of the Ge delta-layers.
70Ge
+
30Si
+
44SiO
+
I
p
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 4: O
2
+
75
4.2.1.1 Surface spikes and incomplete oxidation
Figure 4.2(a)-4.2(c) show the
30
Si
+
profiles at the near surface region for E
p
~
250 eV, E
p
~ 500 eV and E
p
~ 1 keV respectively, at different primary ion incident
angles. The apparent depth was calculated based on the assumption of a constant
erosion rate from the surface to the first delta-layer.
2
At E
p
~ 250 eV there is no
surface spike (yield enhancement) at all incident angles, as is normally observed at
higher energies.
3
At E
p
~ 500 eV the surface spikes begin to show from u ~ 50-60
o

upwards and at E
p
~ 1 keV, the surface spikes appear at u ~ 30-40
o
. This is somewhat
different from that observed by Dowsett et al.
4
, who reported surface spikes from E
p
~
900 eV onwards at u ~ 0
o
for Si surfaces with or without native oxides. They
suggested that the spikes cannot be entirely due to yield enhancement in native oxide,
otherwise it would prevail throughout all energy ranges. Based on our data, we expect
the surface spike to appear at incident angles closer to normal as the primary ion
energy is increased to > 1 keV.
4

Several explanations have been suggested for the presence or absence of
surface spikes.
4
The spikes are non-existent at low energies possibly because the
ionization probabilities of Si
+
and SiO
+
at these energies are low and independent of
oxygen concentration. The contribution from electronic stopping may not contribute
significantly to ionization at sub-keV O
2
+
primary ion energies.
4
At higher energies
(keV), around 10% of neutral sputtering is believed to be due to electronic energy
deposition rather than screened nuclear interaction.
5

Chapter 4: O
2
+
76

Figure 4.2
30
Si
+
profiles for (a) E
p
~250 eV (b) E
p
~500eV and (c) E
p
~1keV.
a) 250 eV
1.E+03
1.E+04
1.E+05
0 1 2 3 4 5
I
n
t
e
n
s
i
t
y

(
c
p
s
)
0 10 20 30
40 50 60 70
b) 500 eV
1.E+04
1.E+05
1.E+06
0 1 2 3 4 5
I
n
t
e
n
s
i
t
y

(
c
p
s
)
c) 1 keV
1.E+04
1.E+05
1.E+06
1.E+07
0 2 4 6 8 10
Apparent Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 4: O
2
+
77
To account for the spike followed by a dip before reaching equilibrium at
oblique incidence with E
p
~ 500 eV, the following explanation is proposed. At oblique
angles above u ~ 60
o
, the total energy loss at the near-surface is greater than that at
normal incidence.
6
The energy deposited at the immediate surface results in an
increase in the sputtering yield. At the same time, oxygen is being incorporated into
the surface, gradually forming an oxidized altered layer and thus effectively reducing
the sputter rate.
7
This effect must be greater than the increase in sputtering yield with
increase in u. resulting in a lowering of the Si
+
and SiO
+
intensities. After the initial
dip in intensity, further oxygen incorporation will gradually enhance the ionization
yield before reaching equilibrium when the fully altered layer is formed.
1,8
Hence, this
proposed mechanism accounts for the spike followed by a dip feature at oblique ion
incidence.
For E
p
~ 1 keV, the
30
Si
+
profiles at u < 40
o
show equilibrium signals at higher
intensities than the initial intensities, but at about u > 50
o
the signal intensities at
equilibrium are lower than the initial intensities [Fig. 4.2(c)]. A similar trend was
observed for E
p
~ 500 eV but the lower intensities at equilibrium were observed only
for angles at about u > 60
o
[Fig. 4.2(b)]. For E
p
~ 250 eV no such trend was observed,
i.e. the intensities at equilibrium are higher for all angles of incidence [Fig. 4.2(a)]. It
appears that at ultra low energies such as E
p
~ 250 eV the sputter rate is lower,
allowing sufficient oxygen mixing to form a saturated oxide-altered layer at all
incident angles, thereby increasing the ion yield at equilibrium. However, this is not
the case at higher angles for E
p
~ 500 eV and E
p
~ 1 keV.
For E
p
~ 500 eV and E
p
~ 1 keV, and at u ~ 50-60
o
, there is incomplete
oxidation and hence a lower ion yield. As the primary ion incident angle increases, the
Chapter 4: O
2
+
78
maximum oxygen concentration that can be achieved decreases.
9,10
There comes a
critical angle u
c
, where incomplete oxidation due to O
2
+
bombardment is observed.
From Figures 4.2(b) and 4.2(c), it can be ascertained that u
c
~ 50
o
at E
p
~ 1 keV and u
c
~ 60
o
at E
p
~ 500 eV. The incomplete oxidation could be due to a loss of implanted
oxygen caused by back-scattered incident primary atoms, because the reflection
coefficient increases with an increase in the incident angle.
11
This was also confirmed
by transport of ions in matter (TRIM) simulations.
12

These observations are consistent with XPS studies done by Tan et al. with 4
keV O
2
+
bombardment on silicon.
13
Figure 4.3 shows the Si 2p spectra of the surface
at steady state for silicon craters bombarded at various incident angles. At u ~ 0
o
sputtering, the XPS chemical state at equilibrium Si intensity shows that Si(IV)
dominates corresponding to a complete oxidation and higher
30
Si
+
equilibrium profile
than initially. At u ~ 45
o
sputtering, the concentration of Si(I) and Si(III) chemical
states are greater compared to Si(IV) giving rise to a mixed layer of sub-oxides and
SiO
2
. At u ~ 55
o
, Si(IV) is almost non-existent with Si(I) and Si(III) dominating, thus
forming the sub-oxides on the crater surface at steady state sputtering. This
corresponds to a lower
30
Si
+
profile at equilibrium than initially. This lead to the
conclusion that u
c
is at about 40
o
incident angle. At u > 40
o
, the formation of sub-
oxide is favoured.
The XPS data suggest that when the O
2
+
penetration depth is shallow as in E
p

~ 250 eV, Si(IV) dominates and thus a saturated oxide layer is formed corresponding
to a higher
30
Si
+
ion yield. Conversely, beyond u
c
, Si(I) and Si(III) dominates forming
sub-oxides. Hence, the reduced intensities are an indication of incomplete oxidation
of silicon.
Chapter 4: O
2
+
79

Figure 4.3 The XPS Si 2p spectra of the surface at steady state for 4 keV O
2
+

bombardment: (a) virgin Si(100) sample; (b) sputtering at 0; (c) sputtering at 15;
(d) sputtering at 30; (e) sputtering at 45; (f) sputtering at 55; (g) sputtering at 70.
13

4.2.1.2 Transient Width
Figure 4.4 shows the measured transient widths based on both
44
SiO
+
and
30
Si
+

profiles as a function of incident angle. The end of the surface transient was taken to
be at 95% of the equilibrium signal for
30
Si
+
(or
44
SiO
+
), consistent with the criterion
used by Jiang and Alkemade.
14
A marginal difference in z
tr
between
30
Si
+
and
44
SiO
+
is noted throughout all the E
p
monitored, except in the range 30
o
< u < 50
o
for E
p
~ 1
keV and 40
o
< u < 60
o
for E
p
~ 500 eV. With E
p
~ 1 keV and at u ~ 40
o
,
30
Si
+
intensity
Chapter 4: O
2
+
80
reaches equilibrium at a depth of 40 nm whereas
44
SiO
+
at 70 nm. With E
p
~ 500 eV
and at u ~ 50
o
,
30
Si
+
intensity reaches equilibrium at a depth of 9 nm whereas
44
SiO
+

at 14 nm. There is a negligible difference observed at E
p
~ 250 eV, although at larger
incident angles (u > 60
o
) z
tr
is slightly larger for
44
SiO
+
. Previous reports
4,14
suggested
that both measured transient widths (Si
+
and SiO
+
) are not much different, but these
observations were limited to normal incidence at 300 eV < E
p
< 2.5 keV,
4
and at u ~
60
o
with E
p
~ 1 keV.
14
We note that the convenience of determining z
tr
using only Si
+

cannot be extended to all incident angles.
We observe that the variation in z
tr
values using
44
SiO
+
and
30
Si
+
yields (Fig.
4.4) is greatest at incident angles where the surface transient coincides with the onset
of surface roughening or ripple formation. A sign of the onset of roughening is when
the matrix profile does not reach a steady state but instead rises gradually.
15-17
At 1
keV, this occurs at u ~ 40
o
, and at 500 eV, it occurs at u ~ 50
o
. It is known that at
oblique angles ripples are formed. The critical angle for ripple formation is the same
as, or marginally larger than the critical angle for complete bombardment-induced
oxidation.
18
Incomplete oxidation lead to the formation of sub-oxides
13
and
subsequently a heterogeneous oxide layer which is known to initiate surface
roughening.
17
SiO
+
is a sensitive indicator of oxygen concentration at the sputtered
surface.
19
Therefore in the region of u
c
, oxidation of the silicon is incomplete; thus it
takes a longer time (hence, deeper) for the SiO
+
signal to stabilize.
Chapter 4: O
2
+
81

Figure 4.4 Measured transient width based on both
44
SiO
+
and
30
Si
+
.

Figure 4.4 also shows that the transient width is lowest at near-normal
incidence and increases to near the critical angle where the surface transient and the
onset of roughening overlap; thereafter, it decreases to z
tr
values that are larger than at
normal incidence. It is also interesting to note that this overlap between the surface
transient and onset of roughening occurs at lower u for higher E
p
, i.e. u ~ 40
o
for E
p
~
1 keV and u ~ 50
o
for E
p
~ 500 eV. It appears that at higher primary ion energy, the
sputtering process is more dominant than the ion incorporation process at a lower
incident angle than at lower primary ion energy, resulting in incomplete oxidation and
the onset of roughening.
We obtained very low z
tr
values of < 1 nm at E
p
~ 250 eV over the range of
angles 0
o
< u < 50
o
. The lowest z
tr
achieved with E
p
~ 250 eV was at u ~ 0-20
o
incidence with z
tr
~ 0.7 nm. For E
p
~ 500 eV z
tr
is also ~ 0.7 nm for u ~ 0-10
o
. For E
p

Si
+
(250 eV)
SiO
+
(250 eV)
Si
+
(500 eV)
SiO
+
(500 eV)
Si
+
(1 keV)

SiO
+
(1 keV)
Si
+
(560 eV)
ref.12
Si
+
(1 keV) ref 12
0
2
4
6
8
10
12
14
16
0 10 20 30 40 50 60 70 80 90
Angle of Incidence
T
r
a
n
s
i
e
n
t

W
i
d
t
h

(
n
m
)
Chapter 4: O
2
+
82
~ 1 keV, the z
tr
is about 1.5 nm for u ~ 0-10
o
. At low E
p
the sputter rate is lower as
there are fewer knock-on collisions. The lower sputtering yield allows a higher
concentration of oxygen to build up in the sample surface, forming SiO
2
over a wider
range of u. Further deposition of oxygen atoms results in a rapid outward growth of
ion-beam-synthesized SiO
2
similar to that observed at normal incidence.
20,21
Hence,
we conclude that the lowest z
tr
values are achievable over a larger range of incident
angles at lower impact energy, and not only at

normal incidence as previously
reported.
4,22

It is widely reported that z
tr
decreases with impact energy, but we observe that
at ultra low energies between E
p
~ 250 eV and 500 eV and u ~ 0-10
o
z
tr
does not differ
significantly. Although the sputtering yield difference is quite significant (see Fig.
4.5), this does not appear to affect the oxygen concentration on the surface. At such
low impact energies, the primary ion penetration is shallow, in the range of 2-3 nm.
This is in the range of the native oxide and thus explains the levelling-off in the z
tr
values even though the E
p
is reducing.

4.2.2 Sputter Rates
Figure 4.5 shows the sputter rates at various angles of incidence and primary
ion energies. Two plots are shown at each primary energy: one (labelled d1)
represents the average sputter rate at the near surface, i.e. the average sputter rate from
the surface to the first Ge delta-layer, ( i.e. top 12 nm); and the other is the average
sputter rate observed from the surface to the tenth Ge delta-layer. The sputter rate at
the near surface is known to vary because of the surface transients. Therefore, the
Chapter 4: O
2
+
83
comparison with the average sputter rate will be useful as the average sputter rate is
commonly used in depth profiling.
As expected, the sputter rate increases with incident angle, reaching a
maximum at u ~ 50
o
for E
p
~ 250 eV. The lowest sputter rate is about 20 nm min
-1

nA
-1
cm
2
and occurs at normal incidence for E
p
~ 250 eV. The maximum sputter rate
for both E
p
~ 500 eV and 1 keV occurs at u ~ 60
o
, which is consistent with that
observed at higher energies.
1

For all energies studied, the sputter rate is lowest at normal incidence. The
bombardment of silicon with oxygen ions at normal incidence and near-normal
incidence generates an altered layer of SiO
2
. Silicon has a strong affinity with oxygen

Figure 4.5 Sputter rates vs. angle of incidence. d1 shows the average sputter rate from
the surface to the first Ge delta-layer and the other is the average sputter rate observed
from the surface to the tenth Ge delta-layer.

0
1
2
3
0 20 40 60 80
250 eV d1
250 eV
d1
500 eV
d1
1 keV
0
5
10
15
20
25
30
35
40
0 20 40 60 80
Angle of Incidence
S
p
u
t
t
e
r

R
a
t
e

(
n
m
/
m
i
n
)
Chapter 4: O
2
+
84
to form SiO
2
, which sputters more slowly than Si. The oxidation of silicon also
reduces the sputtering yield.
6,23
As the incident angle increases, the effective range of
implanted oxygen decreases
12
and sputtering yield increases,
24
resulting in higher
sputter rates. At u > 60
o
there is little or no effect of implanted oxygen on sputtering
yield.
24

Figure 4.5 also shows that the near-surface sputter rate is higher than the
average sputter rates for all angles and energies except for u > 50
o
with E
p
~ 1 keV,
where the near-surface sputter rate is lower than the average sputter rate. This
anomaly can be explained by the fact that beyond u > 50
o
the matrix profiles do not
reach a steady state even at the tenth Ge delta-layer, implying that the onset of
roughening did not reach a steady state throughout the depth range measured. Hence,
the sputter rate remains high throughout and leads to a higher average sputter rate
comparable to that at the near-surface. For all energies up to u ~ 40
o
the difference in
the d1 sputter rate to that of the average sputter rate is quite constant (< 1 nm min
-1
);
beyond u ~ 40
o
the difference widens in the case of E
p
~ 250 eV and ~ 500 eV.
Figure 4.6(a)-4.6(c) show plots of relative sputter rates as a function of depth,
normalized to the sputter rate at the ninth to tenth Ge delta-layer. At E
p
~ 250 eV and
0
o
< u < 40
o
, sputtering is stable as a function of depth except at the surface. The
difference in sputter rate at the near-surface to the average sputter rate is about 7%.
For E
p
~ 500 eV and 0
o
< u < 40
o
the difference is 10%. At E
p
~ 1 keV and 0
o
< u <
20
o
the difference is about 11% and for u ~ 30
o
the difference is about 16%.

Chapter 4: O
2
+
85

Figure 4.6 Normalized sputter rates throughout the depth.

a) 250 eV
0.6
0.8
1.0
1.2
1.4
1.6
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
0 10 20 30
40 50 60 70
b) 500 eV
0.6
0.8
1.0
1.2
1.4
1.6
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
c) 1 keV
0.6
0.8
1.0
1.2
1.4
1.6
0 20 40 60 80 100 120
Depth (nm)
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
Chapter 4: O
2
+
86
We deduce that for E
p
~ 500 eV and E
p
~ 250 eV we may use the average
sputter rate for a reasonably accurate depth conversion at the near surface for 0
o
< u <
40
o
because the error will be in the range of 5 8% for E
p
~ 250 eV and 10% for E
p
~
500 eV. For E
p
~ 1 keV the error at 0
o
< u < 20
o
is about 11%. This finding expands
on the observation made by Wittmaack.
2
He reported that the difference in erosion
rate at the near surface to the average erosion rate is negligible for E
p
~ 500 eV at
normal incidence. The results of surface transient width, sputter rate and the onset of
roughening observed under ultralow-energy O
2
+
bombardment on silicon surface are
summarized in table 4.1.

Chapter 4: O
2
+
87
Table 4.1 Summary of surface transient width, sputter rate and the onset of
roughening observed for O
2
+
sputtering on silicon wafer.

250eV 500eV 1keV
Surface Spike Nil u > 50-60
o
u >30-40
o

Equilibrium signals
lower than initial
Nil u > 60
o
u > 50
o

u
c
(incomplete
oxidation) Nil u > 60
o
u > 50
o

Different z
tr
for SiO
+

and Si
+
u > 60
o
40
o
< u < 50
o
30
o
< u < 50
o

Onset of roughening Not obvious u ~ 50
o
u ~ 40
o

Range of u giving
lowest z
tr
u ~ 0-20
o
u ~ 010
o
u ~ 010
o

Lowest z
tr
0.7 nm 0.7 nm 1.5 nm
Sputter rate max. at u ~ 50
o
u ~ 60
o
u ~ 60
o

Sputter rate min. at u ~ 0
o
u ~ 0
o
u ~ 0
o
Stable erosion rate at 0
o
< u < 40
o
0
o
< u < 40
o
0
o
< u < 20
o

Difference in sputter rate
between near surface
and throughout depth for
u with stable erosion
rate ~ 7 ~ 10 ~ 11

Chapter 4: O
2
+
88
4.3 Summary
In this work, we confirm that it is sufficient to use either
30
Si
+
or
44
SiO
+

profiles to observe the surface transient width, but only in regions where the transient
width and the onset of roughening can be discriminated. We also observe that the
lowest transient width is obtainable at normal and near normal incidence. Although
the transient width decreases with the primary ion energy, there is no significant
improvement going from E
p
~ 500 eV to ~ 250 eV. However, we have a wider range
of incident angles at lower energies where z
tr
is minimum, i.e. 0
o
< u < 10
o
for E
p
~
500 eV and 0
o
< u < 20
o
for E
p
~ 250 eV.
The onset of roughening occurs at a smaller u at higher energy (u ~ 40
o
for E
p
~ 1 keV, u ~ 50
o
for E
p
~ 500 eV) and does not seem to appear at all at E
p
~ 250 eV
over the whole incident angle range studied. Higher matrix signals were observed
upon equilibrium at E
p
~ 250 eV for all angles. This is true only for 0
o
< u < 50
o
at
500 eV, and for 0
o
< u < 40
o
at 1 keV.
For all energies, the sputter rate is lowest at normal incidence, gradually
increasing to a maximum at about 50
o
< u < 60
o
. This is similar to that reported at
higher energies
4
. The sputter rate at the near surface does not differ much from the
sputter rates at other depths for E
p
~ 250 eV. However, this is only true at 0
o
< u < 40
o

for E
p
~ 500 eV and 0
o
< u < 20
o
for E
p
~ 1 keV. Within these incident angles, the
average sputter rate can be used reliably for depth conversion.
We conclude that the best working range to achieve a narrow transient width
and accurate depth calibration are at E
p
~ 250 eV, 0
o
< u < 20
o
and 500 eV, 0
o
< u <
10
o
where the z
tr
achievable is ~ 0.7 nm.
Chapter 4: O
2
+
89
References
3. W. Vandervorst and F. R. Shepherd, Applied Surface Science 21, 230 (1985).
4. M. G. Dowsett, T. J. Ormsby, G. A. Cooke, D. P. Chu, Journal of Vacuum
5. J. P. Biersack, Nuclear Instruments and Methods in Physics Research B 27, 21.
(1987).
6. T. Ishitani and R. Shimizu, Applied Physics 6, 241 (1975).
7. K. Wittmaack and S. F. Corcoran, Journal of Vacuum Science & Technology B
16, 272 (1998).
8. W. Reuter and K. Wittmaack, Applied Surface Science 5, 221 (1980).
9. J. L. Alay, Surface and Interface Analysis 19, 313 (2006).
11. W. Eckstein and J. P. Biersack, Z. Phys. B 63, 109 (1986).
12. J. F. Ziegler and J. P.Biersack, SRIM 2003, http://www.srim.org (2003).
13. S. K. Tan, K. L. Yeo, A. T. S. Wee, Surface and Interface Analysis 36, 640
(2004).
(1999).
17. C. M. Ng, A. T. S. Wee, C. H. A. Huan, A. See, Journal of Vacuum Science &
Technology B 19, 829 (2001).
20. W. Vandervorst, F. R. Shepherd, J. Newman, B. F. Philips, J. Remmerie,
Chapter 4: O
2
+
90
22. D. P. Chu, M. G. Dowsett, T. J. Ormsby, G. A. Cooke, Proceedings of
International Conference on Characterization & Metrology for ULSI
Technology (1998).
23. A. E. Morgan, H. A. M. de Grefte, N. Warmolts, H. W. Werner, H. J. Tolle,
Applied Surface Science 7, 372 (1981).

Chapter 5: O
2
+
SIMS and depth resolution
91
Chapter Five
Effect of ultralow-energy O
2
+
SIMS on depth resolution

5.1 Introduction
In this chapter, we focus on the influence of ultralow-energy O
2
+
primary ion
bombardment on depth resolution. The same set of profiles obtained for the study on
surface transients were used but only the
70
Ge
+
profiles were analysed. The profiles
from delta-layers are ideal for the study of depth resolution as the slopes and the peak-
broadening are indicative of the deviation from the ideal profile. The depth
resolutions at various E
p
and u combinations with depth were evaluated by calculating
the FWHM and
d
of the
70
Ge
+
peaks which represent the SIMS depth profiles of the
Si
0.7
Ge
0.3
delta-layers. We confirm that depth resolution can be improved by lowering
the primary ion impact energy at ultralow-energy. By varying the angle from 0
o
to
70
o
, we note that a better depth resolution is achievable not only at normal incidence
but over a wider range of incident angles as the probe energy is reduced. The dynamic
range for the detected secondary ions is also evaluated. Contributions from
roughening and atomic mixing to the depth resolution of delta-layers are discussed
using the mixing-roughness-information depth model.

Chapter 5: O
2
+
92

Figure 5.1 Profiles of
70
Ge
+
obtained with different E
p
(normalized to the first peak of
E
p
~ 250 eV) at a) u ~ 0
o
and b) u ~ 40
o
.

1keV
500eV
a)0
o
250eV
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
I
n
t
e
n
s
i
t
y

(
c
p
s
)
1keV
500eV
250eV
b) 40
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 20 40 60 80 100 120 140
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 5: O
2
+
93
5.2 Results and discussion
5.2.1 Depth resolution .
Figure 5.1(a) and 5.1(b) show the profiles of
70
Ge
+
normalized to the first peak
of the E
p
~ 250 eV profile, at u ~ 0
o
and 40
o
respectively using E
p
~ 1 keV, 500 eV
and 250 eV. We observe that at normal incidence, the depth resolution obtained when
using E
p
~ 500 eV is comparable to that at E
p
~ 250 eV. Clearly, the depth resolution
using E
p
< 500 eV is better than that at E
p
~ 1 keV. At normal incidence, the peak-to-
valley ratio (PVR) obtained when using E
p
~ 1 keV is smaller compared to that at E
p
~
250 eV and E
p
~ 500 eV at all depths, while the PVR observed at E
p
~ 500 eV and E
p

~ 250 eV are similar. At u ~ 40
o
, the deterioration in depth resolution with depth and
energy is obvious as E
p
is increased from 250 eV to 1 keV, i.e. the
70
Ge
+
peak
broadens. The PVR also decreases significantly from E
p
~ 250 eV to E
p
~ 1 keV.
Comparing the
70
Ge
+
profiles obtained using E
p
~ 1 keV at u ~ 0
o
and u ~ 40
o
,
it is clear that there is a broadening of the peaks, i.e. deterioration of depth resolution
due to the onset of roughening
1
as u is increased. At u ~ 40
o
, the depth resolution
deteriorates more severely than at u ~ 0
o
as E
p
is increased. The deterioration in depth
resolution observed as E
p
is increased for a particular u is the result of atomic mixing
due to increased ion penetration depth.
2
It is more severe at u ~ 40
o
due to a
combination of both factors of roughening and atomic mixing.

5.2.1.1 Depth resolution in terms of FWHM
Figure 5.2(a)-5.2(c) show the depth resolution measured in terms of FWHM of
the
70
Ge
+
peaks against the depth. To minimise errors in the determination of the
resolution parameters, large scan sizes were used to maximise the number of data
Chapter 5: O
2
+
94
points. Another source of error is the choice of baselines for the peaks in the
determination of FWHM. The errors were minimised by consistently using the same
method in determining the base of the peaks. The base of the peak was determined by
the valley-to-valley method i.e. by drawing a line from the valley before the peak to
the valley after the peak. The peak height was measured based on the vertical height
from the peak to the baseline.
At E
p
~ 250 eV, the depth resolution is constant with a mean FWHM of 1.5 nm
throughout the analysis depth of 115 nm, when u ~ 0-40
o
. The difference in depth
resolution from the first delta-layer to the last delta-layer is less than 15%. At u ~ 50
o
,
the depth resolution is constant at FWHM of 1.9 nm up to about 50 nm before
deteriorating further to 2.3 nm or by about 20%. At u ~ 60
o
and 70
o
, the FWHMs at
the first delta-layer are 2.4 nm and 3.3 nm respectively, but worsen with depth. The
FWHM increase from the first to the last delta-layer is 29% at u ~ 60
o
and 55% at u ~
70
o
. At all u investigated, the delta-layers are well resolved. Given the above
observations, a good depth resolution in the order of 1-2 nm can be obtained using u ~
0-40
o
with E
p
~ 250 eV, throughout the depth. Depth resolution degrades at u > 50
o
possibly coinciding with the onset of roughening but is not obvious as discussed
earlier in Chapter 4 (4.2.1.2).
1

Using E
p
~ 500 eV, the depth resolution is again constant throughout the depth
studied for u ~ 0-40
o
with a mean FWHM of 2.2 nm. At u ~ 50
o
, the depth resolution
degrades by about one and a half times, and worsens with depth after the fourth delta-
layer i.e. about 50 nm deep. A similar observation was reported by Liu et al.
3
using u
~ 56
o
where the onset of roughening was observed from a depth of 60 nm, and
Chapter 5: O
2
+
95

Figure 5.2 Depth resolution of Ge delta-layer as a function of profile depth, measured
by FWHM for a) E
p
~ 250 eV b) E
p
~ 500 eV c) E
p
~ 1 keV at various incident angles.
a) 250eV
0
o
-40
o
50
o
60
o
70
o
0
1
2
3
4
5
6
7
8
F
W
H
M

(
n
m
)
0 10 20 30
40 50 60 70
b) 500eV
0
o
-40
o
50
o
60
o
70
o
0
1
2
3
4
5
6
7
F
W
H
M

(
n
m
)
c) 1 KeV
0
o
-30
o
40
o
50
o
60
o
70
o
0
1
2
3
4
5
6
7
0 20 40 60 80 100 120 140
Depth (nm)
F
W
H
M

(
n
m
)
Chapter 5: O
2
+
96
consistent with our earlier finding discussed in Chapter 4 (4.2.1.2) that the onset of
roughening occurs at u ~ 50
o
.
1
Such degradation in depth resolution was also observed
by Ormsby et al.
2
at 500 eV and u ~ 50-60
o
. At u ~ 60-70
o
the FWHM at the first
delta-layer (d1) is about 2.4 nm, but deteriorates significantly beyond this depth.
Looking at the depth profiles of u ~ 60-70
o
(Appendix A, page 166), it can be deduced
that the degradation in resolution with depth was a result of erosion
inhomogeneity which has been attributed to a variation in sputter rate due to
rastering
4
and/or poor beam focus (instrument related factors) and not due to
sputtering induced surface roughness. The evidence of this observation is discussed
using Figures 5.3.
Using E
p
~ 1 keV, the depth resolution is constant at 3.5 nm as a function of
depth at u ~ 0-20
o
only. Unlike at lower energies, the depth resolution at E
p
~ 1 keV is
better at u ~ 60-70
o
to a depth of about 50 nm, but degrades thereafter. Good depth
resolution has previously been observed at E
p
~ 1 keV and u ~ 71
o
.
5
The poorer depth
resolution at u ~ 40-50
o
could be due to the onset of roughening which was observed
as described earlier in Chapter 4 (4.2.1.2)
1
at u ~ 40
o
. Wittmaack
6
also reported rapid
ripple growth at E
p
~ 1 keV and u ~ 38-62
o
. Jiang and Alkemade
7
observed the lowest
surface roughness using u ~ 55-70
o
at E
p
~ 1 keV in the range of u ~ 48-79
o
evaluated.
This is consistent with our observation of better resolution at u ~ 60-70
o
compared to
at u ~ 40-50
o
. Comparing across E
p
, we observe that a better depth resolution is
generally achieved at lower energy. Using E
p
~ 250 eV or 500 eV, the depth
resolution is good at normal to 40
o
incidence. At E
p
of 1 keV, the depth resolution is
better towards glancing angle, i.e. u ~ 60
o
onwards, but only down to a critical depth
Chapter 5: O
2
+
97
of about 50 nm; nevertheless constant depth resolution with depth at 1 keV is
achievable near normal incidence at u ~ 0-20
o
.
Figure 5.3(a)-5.3(c) show the ion intensity images of
70
Ge
+
at the depth where
the cursor positions are, respectively. The yellow squares are indicative of a high
concentration of
70
Ge
+
, while the black squares indicate the absence of
70
Ge
+
. Figure
5.3(b) shows that
70
Ge
+
was detected earlier on the right side of the crater confirming
that the crater base was not flat and parallel to the initial surface. At a shallower depth
as depicted in Figure 5.3(a), the
70
Ge
+
ion image shows an even breakthrough as the
crater was sputtered down the depth. Similarly, Figure 5.3(c) shows an even
70
Ge
+
ion
image at about the same depth as that in Figure 5.3(b). Looking at the depth profile, it
is obvious that the depth resolution is poor but this was not caused by an inclined
crater base (instrument related factors) as in the profile of E
p
~ 250 eV/ u ~ 70
o
but
rather by sputtering induced surface roughening (microtopography) as discussed
earlier.
Figure 5.4(a)-5.4(c) show the depth resolution (in terms of FWHM) of three
representative Ge delta-layers at the near surface d1 (12.2 nm), intermediate depth d5
(57.8 nm) and deepest at d10 (114.8 nm) for all three energies investigated. Figures
5.4(a)-5.4(c) show clearly that using E
p
~ 250 eV, a good resolution prevails at u ~ 0-
40
o
at all depths, before deteriorating at grazing angles. At E
p
~ 500 eV, good
resolution is maintained similarly at u ~ 0-40
o
. At 1 keV, the best depth resolution
obtained is at u ~ 60-70
o
, but only nearer the surface. The depth resolution is stable
with depth only at u ~ 0-20
o
.

Chapter 5: O
2
+
98

Figure 5.3 Ion image of
70
Ge
+
taken at the depth where the cursor position is. a) E
p
~
250 eV, u ~ 70
o
at the 2nd delta-layer b) E
p
~ 250 eV, u ~ 70
o
at the 4
th
delta-layer c)
E
p
~ 1 keV, u ~ 40
o
at the 4
th
delta-layer.
Chapter 5: O
2
+
99

Figure 5.4 Depth resolution of Ge delta-layer at various primary ion incident angles.
a) 250 eV
d1
d5
d10
0
1
2
3
4
5
6
F
W
H
M

(
n
m
)
d1 d5 d10
b) 500eV
d1
d5
d10
0
1
2
3
4
5
6
7
8
F
W
H
M

(
n
m
)
c) 1keV
d1
d5
d10
0
1
2
3
4
5
6
0 10 20 30 40 50 60 70
Angle of Incidence
F
W
H
M

(
n
m
)
Chapter 5: O
2
+
100
5.2.1.2 Depth resolution in terms of exponential decay
Figure 5.5 shows the overlay of profiles of the first Ge delta-layer obtained at
various u and E
p
normalized to the peak obtained at normal incidence. The trailing
edges at all three values of E
p
are always gentler than the leading edges due to ion
beam mixing effects. As E
p
increases, the leading edge slope becomes gentler. At
higher primary ion energy, the ion projected range is longer and hence the altered
layer is thicker, resulting in a gentler slope.
8
Similarly,
d
increases as E
p
increases for
the trailing edge due to an increased knock-on effect of Ge atoms. It can be clearly
seen that using E
p
~ 250 eV, that the depth resolution is best at u ~ 40
o
[Fig. 5.5(a)];
this is not obvious in the FWHM results which only give resolution information at
mid-height of the peak. At E
p
~ 500 eV, the depth resolution is best at u ~ 0-30
o
[Fig
5.5(b)]; and at E
p
~ 1 keV, it is best at u ~ 0-20
o
.
Figure 5.6 shows the decay length for selected o-layers using E
p
~ 250 eV, 500
eV and 1 keV against u ~ 0-70
o
. The figure shows that
d
decreases as E
p
is lowered.
At lower E
p
,
d
is small over a greater range of u. For E
p
~ 250 eV,
d
is lowest at u ~
0-50
o
; for E
p
~ 500 eV, it is at u ~ 0-30
o
and for E
p
~ 1 keV, it is at u ~ 0-20
o
. Using
E
p
~ 250 eV,
d
decreases from 0.9 nm to 0.6 nm as u increases from 0
o
to 50
o
. Even
though
d
at u ~ 50
o
is the smallest, the FWHM is higher, i.e. the peak is broader,
resulting in a poorer depth resolution than at u ~ 0-40
o
. This is because
d
only gives
information about the trailing edge, and not the full peak. Using E
p
~ 500 eV and u ~
40
o
,
d
is larger even though the FWHM is comparable to u ~ 0-30
o
, thus giving an
overall depth resolution which is poorer than u ~ 0-30
o
. Using E
p
~ 1 keV, profiling at
u ~ 60-70
o
results in lower
d
than at near normal. However the depth resolution is
Chapter 5: O
2
+
101
Figure 5.5 Comparison of the normalized
70
Ge
+
various E
p
.

40
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 10 20
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
40
50
a) 250 eV
40
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
I
n
t
e
n
s
i
t
y

(
c
p
s
)
0
10
20
30
40
b) 500 eV
40
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
I
n
t
e
n
s
i
t
y

(
c
p
s
)
c) 1 keV
30
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 5 10 15 20
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 5: O
2
+
102

Figure 5.6 Plot of decay length (
d
) versus incident angle (u).
a) 250eV
d1
d5
d10
0
1
2
3
D
e
c
a
y

L
e
n
g
t
h

(
n
m
/
e
)
d1 d5 d10
b) 500eV
d1
d5
d10
0
2
4
6
8
D
e
c
a
y

L
e
n
g
t
h

(
n
m
/
e
)
c) 1 keV
d1
d5
d10
0
1
2
3
4
5
0 10 20 30 40 50 60 70
Angle of Incidence
D
e
c
a
y

l
e
n
g
t
h

(
n
m
/
e
)
Chapter 5: O
2
+
103
better than near normal only to a depth of 50 nm, as the FWHM beyond the 50 nm is
larger, thus giving a poorer depth resolution beyond that depth.

5.2.1.3 MRI model and evaluation
Lau et al.
9
have successfully demonstrated with a similar SiGe o-doped
sample that the surface roughening behaviour during ion sputtering can be accounted
for by the Mixing-Roughness-Information depth (MRI) model proposed by
Hoffman.
10
The model considers the contributions of three fundamental parameters
namely, atomic mixing, roughness and information depth towards depth resolution.
Atomic mixing is described by an exponential function, with a characteristic mixing
length w, as shown in equation 5.1. Roughness is represented by a Gaussian term with
standard deviation o which corresponds to the root mean square surface roughness, as
in equation 5.2; and information depth is represented by an exponential term with
characteristic information depth . as in equation 5.3. z is the sputtered depth and z
o
is
the running depth parameter for which the composition is defined. For example, each
monoatomic layer at a location z
o
gives a normalised contribution at a sputtered depth
z that is described by
11

Atomic mixing: ] / ) ( exp[
1
w w z z
w
g
o w
+ = , (5.1)
Roughness: ]
2
) (
exp[
2
1
2
2
o
to
o
o
z z
g

= , (5.2)
Information depth: ] / ) ( exp[
1
o
z z g = . (5.3)

Chapter 5: O
2
+
104
In the atomic mixing parameter, mixing is assumed to be instantaneous,
12

complete, and it extends to a depth w. Therefore, roughness and atomic mixing are
assumed to be independent of each other. The information depth parameter can be
neglected as it is about one to two monolayers based on the secondary-ion escape
depth in low energy SIMS.
10
The roughness parameter consists of three components:
the original interface roughness (o
i
), sputtering induced surface roughness (o
s
) and
straggling of the mixing length (o
w
).
10
The total o parameter in the model is
( )
2
1
2 2 2
i w s
o o o o + + = . (5.4)
Interface roughness can be neglected as the sample is assumed to have high quality
interfaces. The contribution from mixing length straggling
13
can be significant
compared to the contribution of the original interface roughness and sputtering
induced surface roughness but is difficult to determine. The rms value of o
s
can be
obtained from AFM measurements.
Figure 5.7 shows the projected ion range of O
2
+
primary ions at ultralow-
energies from u ~ 0-70
o
using TRIM calculations. In Figure 5.1, we observe that as E
p

is increased, the depth resolution becomes poorer. At u ~ 0
o
and with increasing E
p
,
the primary ion range and hence the atomic mixing length also increases (see Fig.
5.7). Hence, the dominant contribution to depth resolution is atomic mixing. When
peak broadening occurs as u is increased from 0
o
to 40
o
for E
p
~ 500 eV and 1 keV,
the major contribution to the peak shape is from roughening since the effective ion
range is decreasing (by a cos u factor). Another observation is the increase in peak
broadening as the sputtered depth increases, and this must be due to sputter-induced
Chapter 5: O
2
+
105

Figure 5.7 The projected ion range of O
2
+
primary ion beam at various incident
angles calculated from TRIM
8

roughening. We can conclude that as the peak broadens with depth, the overall crater
morphology becomes progressively rougher.
10

At E
p
~ 250 eV, the FWHM and
d
values are constant for u ~ 0-40
o
and the
profiles are Gaussian, indicating that there is no significant onset of roughening.
However, at u ~ 50
o
, the onset of roughening is apparent as the FWHM values are
distinctively higher than that at u ~ 0-40
o
, since the contribution from atomic mixing
does not change very much. The observation is similar for u ~ 60
o
and 70
o
.
From Fig. 5.5 we infer that based on MRI modelling, the onset of roughening
at u ~ 50
o
for E
p
~ 250 eV, u ~ 40
o
for E
p
~ 500 eV and u ~ 30
o
for E
p
~ 1 keV is
consistent with Chapter 4 where the onset of roughening was determined by the less
250 eV
500 eV
1 keV
0
1
2
3
4
5
0 10 20 30 40 50 60 70 80 90
Angle of Incidence
I
o
n

R
a
n
g
e

(
n
m
)

250eV 500eV 1keV
Chapter 5: O
2
+
106
sensitive indicator of using the increase in
30
Si
+
profile which was not obvious for E
p

~ 250 eV, u ~ 50
o
for E
p
~ 500 eV and u ~ 40
o
for E
p
~ 1 keV.
Figure 5.8 shows the profile resolution data (FWHM and
d
) from the first
delta-layer as a function of beam energy when bombarded at normal incident. The
data demonstrates effectively the improvement in depth resolution by the use of lower
E
p
. The y-intercept can be interpreted as extrapolation to zero-energy. The value of
the intercept for FWHM is 0.8 nm. This can be interpreted to be the sum of the
nominal width of the delta-layer and the information depth since the contribution from
atomic mixing and roughness is absent. The information depth for SIMS which is the
secondary ion escape depth, is about two to three atomic layers (0.3 0.4 nm). Hence,
the width of the delta-layer is about 0.4 nm as specified. The value of the y-intercept
for
d
is 0.6 nm. At zero-energy there is no atomic mixing, hence this value is the
limit which is due to the initial surface topography and also the information depth of
the technique.

Figure 5.8 Depth resolution parameters (FWHM and
d
o
.
y = 0.0029x + 0.845
y = 0.0013x + 0.6
0
1
2
3
4
0 250 500 750 1000 1250
R
e
s
o
l
u
t
i
o
n

P
a
r
a
m
e
t
e
r
s

(
n
m
)
Primary Ion Energy (eV)
FWHM
d
Chapter 5: O
2
+
107
5.2.2 Dynamic range
Figure 5.9 shows the dynamic range averaged over the first nine peaks. It
gives an indication of the range of concentrations that can be detected by SIMS. The
dynamic range was calculated based on the ratio of peak intensity to the background
intensity. The lower of the intensities before the first delta-layer or after the last-delta
layer was taken to be the background intensity. At higher E
p
and correspondingly
higher beam current, we observe a better dynamic range. For all three primary ion
energies studied, the dynamic range increases as u moves away from normal, reaching
a maximum before decreasing. For E
p
~ 1 keV, the maximum is at u ~ 30
o
; for E
p
~
500 eV, the maximum is at u ~ 30-40
o
; and for E
p
~ 250 eV, the maximum is at u ~
40-50
o
. The results of high depth resolution and best dynamic range are summarized
in Table 5.2.

Figure 5.9 Dynamic range averaged over the first nine Ge peaks vs incident angle.

250eV
500eV
1keV
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 10 20 30 40 50 60 70
Angle of Incidence
D
y
n
a
m
i
c

R
a
n
g
e

(
I
m
a
x
/
I
m
i
n
)
250eV 500eV 1keV
Chapter 5: O
2
+
108
Table 5.1 Summary of depth resolution and dynamic range observed with O
2
+

sputtering.

5.3 Summary
At E
p
~ 250 eV, a good depth resolution of about 1.5 nm FWHM and
d
of
less than 1 nm is obtained at u ~ 0-40
o
throughout the depth range studied. The best
depth resolution is seen at u ~ 40
o
. At E
p
~ 500 eV, we observe a good depth
resolution of about 2.2 nm FWHM and
d
averaged at 1.2 nm throughout the depth
evaluated at u ~ 0-30
o
. At E
p
~ 1keV, we obtained a good depth resolution of 3.5nm
FWHM and
d
of 1.8 nm at u ~ 0-20
o
throughout the depth evaluated. The best
dynamic range is achieved at u ~ 40-50
o
for E
p
~ 250 eV, u ~ 30-40
o
for E
p
~ 500 V,
250eV 500eV 1keV
Lowest FWHM 1.5nm 2.2nm 3.5nm
u with lowest FWHM
throughout depth
u ~ 0 - 40
o
u ~ 0 30
o
u ~ 0 20
o

u with lowest FWHM
to a limited depth (nm) Nil
u ~ 60 70
o

(12 nm)
u ~ 60 70
o
(50 nm)
Lowest
d
< 1nm ~ 1.2nm ~ 1.8nm
u with lowest
d

throughout depth u ~ 0 -50
o

u ~ 0 - 30
o
u ~ 60 -70
o

u ~ 0 - 20
o
u ~ 60 -70
o

u with best dynamic
range u ~ 50
o
u ~ 40
o
u ~ 30
o

Highest dynamic
range 6.8 x 10
3
8.9 x 10
3
2.3 x 10
4

Chapter 5: O
2
+
109
and u ~ 30
o
for E
p
~ 1 keV. We conclude that the best condition for high depth
resolution with a good dynamic range is at E
p
~ 250 eV and u ~ 40
o
.
From our analysis using the MRI model, we confirmed that depth resolution
can be improved by lowering the primary ion impact energy which effectively reduces
atomic mixing. We also note that at ultralow-energy, a better depth resolution is
achievable not only at normal incidence but also over a wider range of incident angle
as E
p
is decreased. Over this u range, there is complete oxidation resulting in no onset
of roughening.
14
As u is increased, surface roughening sets in, resulting in a poorer
depth resolution.
From the
70
Ge
+
profiles, we can distinguish between contributions from
roughening and atomic mixing to the depth resolution of delta-layers. The Gaussian
broadening is due mainly to the roughening component, and the trailing edge
broadening, i.e. increases in
d
, is due primarily to the atomic mixing component.
Based on MRI modelling, the onset of roughening is detected earlier as compared to
observing an increase in the
30
Si
+
profile
1
suggesting that the MRI model is a more
sensitive indicator of the onset of roughening.

Chapter 5: O
2
+
110
References

1. A. R. Chanbasha and A. T. S. Wee, Surface and Interface Analysis 37, 628
(2005).
4. M. Meuris, P. Debisschop, J. F. Leclair, W. Vandervorst, Surface and Interface
Analysis 14, 739 (1989).
5. Z. X. Jiang, P. F. A. Alkemade, E. Algra, S. Radelaar, Surface and Interface
Analysis 25, 285 (1997).
9. G. S. Lau, E. S. Tok, R. Liu, A. T. S. Wee, J. Zhang, Nuclear Instruments &
Methods in Physics Research Section B 215, 76 (2004).
10. S. Hofmann, Surface and Interface Analysis 27, 825 (1999).
11. S. Hofmann, Surface and Interface Analysis 30, 228 (2000).
12. Z. L. Liau, B. Y. Tsaur, J. W. Mayer, Journal of Vacuum Science & Technology
B 16, 121 (1979).
13. A. Rar, D. W. Kojima, D. W. Moon, S. Hofmann, Thin Solid Films 355, 390
(1999).

Chapter 6: Cs
+
111
Chapter Six
Effect of ultralow-energy Cs
+
SIMS on Si surface transient

6.1 Introduction
Another widely used primary ion beam in SIMS is Cs
+
. It complements O
2
+

SIMS as it is sensitive to electronegative elements. The presence of Cs
+
enhances the
negative secondary ion yield. In this chapter, we will study the dependence of
transient width and sputter rate as a function of Cs
+
primary ion energy (E
p
~ 320 eV,
500 eV, 1 keV) and incident angles between 0-70
o
.
The matrix profiles (
30
Si
-
) were monitored and evaluated for transient width
determination. An extended transient width was observed and the width was
compared to the penetration depth of the incident Cs
+
ion. The influence of Cs on the
intensity and shape of the profile is also discussed.
The sputter rates were calculated and showed similar behaviour as that
observed with ultralow-energy O
2
+
SIMS. It is known that the transient width is
reduced when the primary ion energy is reduced. However, we find that at ultralow-
energies, reducing E
p
does not have a significant effect in reducing the transient
width. From the equilibrium intensity of the
30
Si
-
profile, we draw conclusions on the
detection sensitivity with respect to the incident angle used.

Chapter 6: Cs
+
112
6.2.1 Surface transients
Figure 6.1 shows the depth profiles of
30
Si
-
,
59
Si
2
-
and
98
SiGe
-
using E
p
~ 320
eV at u ~ 50
o
. I
p
is the primary ion current profile, which was monitored throughout
the depth profile. Only profiles with constant current, monitored as a horizontal line
(I
p
), were used in our study. The peaks (maximum intensity) are taken to be located at
the centre of the Ge delta-layers and are used as depth markers. However, we note
that the peak shape is asymmetrical depending on the primary beam energy and angle
of incidence. Hence, there may be a slight deviation of the peak from the actual centre
of the Ge delta-layer. The
30
Si
-
profiles were used in the determination of the surface
transient width. The
98
SiGe
-
profile shows ten well-resolved peaks and is used to
determine the depth resolution. The depth resolution is observed to deteriorate
progressively with depth. The dips in the intensities of the
30
Si
-
and
59
Si
2
-
profiles
correspond to the positions of the Ge delta-layer. Similar profiles were obtained for all
three energies and angles of incidence specified earlier are presented in appendix B.

Figure 6.1 Depth profile obtained using E
p
~320eV at u ~50
o
.
30
Si
-
59
Si
2-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
I
p
Chapter 6: Cs
+
113
6.2.1.1
30
Si
-
profiles
Figure 6.2(a)-6.2(c) show the
30
Si
-
profiles (intensity vs apparent depth)
recorded at the near surface region for E
p
~ 320 eV, E
p
~ 500 eV and E
p
~ 1 keV
respectively, at different primary ion incident angles. The apparent depth was
calculated based on the assumption of a constant erosion rate from the surface to the
first delta-layer.
1

For E
p
~ 320 eV, the
30
Si
-
surface transient

profiles obtained at various u can
be grouped according to three distinct profile trends:
(i)
30
Si
-
intensity rises abruptly with depth before reaching a steady state. This
is observed at u ~ 30-50
o
.
(ii)
30
Si
-
intensity rises abruptly but midway before arriving at steady state
intensity, it develops a shoulder. This is observed at u ~ 0-20
o
.
(iii)
30
Si
-
intensity rises less abruptly, develops a peak before reaching the
steady state intensity. This is observed with profiles from u ~ 60-70
o
.
When E
p
~ 500 eV,
30
Si
-
surface transient profiles from u ~ 30-40
o
rise
abruptly with no peaks or shoulders. Profiles from u ~ 0-20
o
do not develop a
shoulder but instead increase gradually to the steady state intensity. Profiles from u ~
50-70
o
develop a peak prior to reaching steady state intensity.
When E
p
~ 1 keV,
30
Si
-
surface transient profiles from u ~ 20-30
o
rise abruptly
with no peaks or shoulders. Similar to E
p
~ 500 eV, profiles from u ~ 0-10
o
, do not
develop a shoulder but rise gradually. Finally, the last group of profiles from u ~ 40-
70
o
, develop a peak prior to reaching the steady state intensity.

Chapter 6: Cs
+
114

Figure 6.2
30
Si
-
profiles for (a) E
p
~320 eV (b) E
p
~500 eV and (c) E
p
~1 keV.
a) 320eV
1.E+03
1.E+04
1.E+05
1.E+06
I
n
t
e
n
s
i
t
y

(
c
p
s
)
0 10 20 30
40 50 60 70
b) 500eV
1.E+03
1.E+04
1.E+05
1.E+06
I
n
t
e
n
s
i
t
y

(
c
p
s
)
c) 1keV
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0 2 4 6 8 10
Apparent Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 6: Cs
+
115
In the optimal profiles i.e. abrupt rise to steady state and therefore with the
shallowest transient (E
p
~ 320 eV/ u ~ 30-50
o
; E
p
~ 500 eV/ u ~ 30-40
o
; E
p
~ 1 keV/ u
~ 20-30
o
), the rapid increase in the
30
Si
-
intensity corresponds to a progressive build-
up of Cs concentration at the initial stages of bombardment. This causes a rapid
increase in
30
Si
-
ionization
2
resulting in a yield enhancement effect.
3
As the Cs
intensity rises, the work function decreases proportionally, thus enhancing the yield of
negative ions.
4
Subsequently, the Cs concentration stabilizes and the
30
Si
-
intensity
reaches a steady state. This equilibrium is achieved when the amount of Cs implanted
is equal to the amount of Cs sputtered. At this stage, the work function also
stabilizes.
5

It is interesting to note that profiles with the shoulder appear only at the
ultralow-energy of 320 eV (u ~ 0-20
o
) but not at 500 eV and 1 keV. If we compare
this to Si
+
profiles from O
2
+
bombardment,
6
this profile is indicative of the onset of
roughening. However, ripple formation has been reported to occur only beyond u ~
50
o
with E
p
~ 250 eV.
7
This is also supported by our
98
SiGe
-
profiles which show little
or no loss in depth resolution with depth implying the absence of roughening effects.
Further investigations were done with AFM. Figure 6.3 shows the AFM images of
1um x 1 um scans done at the crater bottom from u ~ 0
o
, 10
o
, 20
o
and 60
o
samples at a
depth of 2-3 nm. The bright features are very likely to be dust particles. The rms
roughness observed in the areas without the surface particles are ~ 0.18 nm for u ~ 0
o
,
10
o
, 20
o
and ~ 0.27 nm for u ~ 60
o
, where the onset of roughening is more obvious.
The change in the gradient of the profiles at the point of inflexion, where the
shoulder begins, is at an apparent depth of 0.5 nm. This is typically in the vicinity of
the native oxide layer (estimated at ~ 1-2 nm). The sputter rate at E
p
~ 320 eV / u ~ 0-
Chapter 6: Cs
+
116
Figure 6.3 AFM images of crater bottoms resulting from E
p
~ 320 eV a) u ~ 0
o
, b) u
~ 10
o
, c) u ~ 20
o
and d) u ~ 60
o
taken at 2-3 nm depth. The rms roughness values for
craters from u ~ 0
o
, 10
o
and 20
o
are ~ 0.18 nm and for u ~ 60
o
is ~ 0.27 nm, where the
onset of roughening is noted.

20
o
is the lowest (cf. Fig. 6.6) compared to other incident angles, corresponding to a
greater implanted Cs build-up on the surface.
8
The Cs concentration has also been
reported to be higher at the SiO
2
/Si interface,
9
owing to possibly the difference in
stopping power
10
or the strong cesium-oxygen bonding
11,12
as Cs
2
O which hinders the
out-diffusion of Cs
+
.
9
Therefore, as the
30
Si
-
intensity rises, the presence of oxygen
quenches the Cs-induced enhancement effect
13
on Si
-
culminating in the point of
inflexion, possibly in the region of the SiO
2
/Si interface. On further bombardment
across the interface, the oxygen concentration will diminish and the interaction with
Cs will be negligible resulting in the subsequent gradual increase in the
30
Si
profile.
This does not happen at higher energies with similar u, as the deeper Cs
+
penetration
Chapter 6: Cs
+
117
depth and higher sputter rate may have negated the cesium-oxygen interaction. This is
particularly significant for E
p
~ 1 keV where

the ion penetration depth is ~ 1.3 nm.
14

Similarly, the development of peaks in the profiles all occur at an apparent
depth of less than 1nm, which is possibly at the SiO
2
/Si interface. The Cs
concentration at the surface builds up rather slowly as the Cs accumulates at the
SiO
2
/Si interface coupled with a higher sputtering rate at u ~ 40-70
o
(cf. fig. 6.6).
11,12

The peak corresponds to the high Cs concentration at the SiO
2
/Si interface. Beyond
the interface, the profile intensity decreases gradually as the oxygen diminishes and
the Cs builds up again with depth. The gradual rise in the
30
Si
-
intensity stabilizes only
after a considerable depth giving rise to a wider z
tr
, which will be discussed in Section
6.2.1.2. It is noted that the critical angle at which a transient peak occurs increases as
the primary ion energy is lowered: At E
p
~ 320 eV, u
c
is 60
o
; at E
p
~ 500 eV, u
c
is 50
o
;
and at E
p
~ 1 keV, u
c
is 40
o
.

6.2.1.2 Transient width
Figure 6.4 shows the measured transient width based on
30
Si
-
profiles as a
function of incident angle. The end of the surface transient was taken to be at 95% of
the equilibrium signal for
30
Si
-
, consistent with the criterion used by Jiang and
Alkemade
12
for O
2
+
bombardment. We have also included plots of 2R
norm
of Cs
+
for
each E
p
and u since it is expected that z
tr
~ 2-2.5R
norm
where there is no
roughening.
13,15
The values are from TRIM calculations.
14

Chapter 6: Cs
+
118

Figure 6.4 Measured transient width based on
30
Si
-
profiles for E
p
~320 eV, 500 eV
and 1 keV. The plot of R
norm
of Cs
+
primary ion at various E
p
is also shown. For
conditions where extended transient effects is not observed, the z
tr
< 2R
norm

We noted that the
30
Si
-
profiles reach equilibrium in the shortest time, giving
the narrowest z
tr
in the range of 1.4 nm to 2.7 nm. Using primary ion energy of 320
eV and 500 eV, the minimum z
tr
is observed at u ~ 40
o
, with z
tr
~ 2.0 nm and z
tr
~ 1.4
nm respectively. At E
p
~ 1 keV, the minimum z
tr
~ 1.5 nm is observed at u ~ 30
o
. The
range where the narrowest z
tr
is observed is greater, i.e. u ~ 30-50
o
for E
p
~ 320 eV
and 500 eV, but is limited to u ~ 20-30
o
for E
p
~ 1 keV. The z
tr
at 1 keV/ u ~ 40-50
o
is
about 3.7 nm. Beyond u ~ 50
o
for all E
p
studied, the transient width broadens by 7-8
times compared to the narrowest z
tr
achievable. This broadening has been referred to
as the enhanced transient effect.
10
This is an important observation, as u ~ 60
o
is
widely used with Cs
+
bombardment for dopant profiling in SIMS since the beam
30Si
-
(320eV)
30Si
-
(500eV)

30Si
-
(1KeV)
2R
norm
320 eV
2R
norm
500 eV
2R
norm
1 keV
0
5
10
15
20
25
0 10 20 30 40 50 60 70 80 90
Angle of Incidence
T
r
a
n
s
i
e
n
t

W
i
d
t
h

(
n
m
)
Chapter 6: Cs
+
119
induced broadening effects was found to be a minimum
16-18
and also due to the
limited incident angle range available in magnetic sector instruments.
19-23
However,
with z
tr
~ 20 nm, it is obvious that u ~ 60
o
is not suitable for ultrashallow dopant
profiling. We also noted that z
tr
increases even though E
p
decreases when profiled at u
~ 60
o
. Under the conditions where extended z
tr
is not observed, z
tr
< 2R
norm
for E
p
~
320 eV and 500eV, while for E
p
~ 1 keV, z
tr
< 1.5R
norm
. At minimum z
tr
, E
p
~ 320 eV
/ u ~ 30-50
o
, z
tr
~ 1-1.4R
norm
; E
p
~ 500 eV / u ~ 30-50
o
, z
tr
~ 0.7-1.4R
norm
; E
p
~ 1 keV
/u ~ 20-30
o
, z
tr
~ 0.5-0.8R
norm
. This implies that the Cs concentration must have
stabilized in the region of where the majority of Cs
+
ions come to rest.

6.2.1.3 Steady-state intensity of
30
Si
-
profiles
Figure 6.5 shows the steady state intensity (sputter yield + ion yield) of
30
Si
-
at
various u and E
p
. At all three primary ion energies investigated, the
30
Si
-
intensity at
steady state increases from when u ~ 0
o
to a maximum when u ~ 30
o
, then decreases
to a lower level than at u ~ 0
o
as u is increased from 40
o
to 70
o
at 10
o
intervals. This
is consistent with earlier work using E
p
~ 1 keV where the Cs concentration was
found to decrease as u increases from 30-80
o
.
24
However, this trend differs from that
at higher energy
25
where there is no change in the
30
Si
-
intensity for u ~ 0-20
o
. Since
the sputter rate is lowest at u ~ 0
o
, intuitively the steady state Cs concentration, and
hence
30
Si
-
intensity, should be highest. However, this is not the case. At normal and
near normal incidence, Cs accumulates at the surface and hence less Si is sputtered as
compared to at u ~ 30
o
. Beyond u ~ 70
o
, the high sputter rate together with an
increasing backscattered primary ion yield with u, results in a lower Cs surface
Chapter 6: Cs
+
120
Figure 6.5
30
Si
-
intensity at steady state for various E
p
and u. Si
-
intensity from high
energy of E
p
~ 8 keV is also shown.
25

concentration which is too small to produce a significant enhancement of negative ion
yield.
25

6.2.2 Sputter rates
Figure 6.6 shows the sputter rates at various angles of incidence and primary ion
energies. Two plots are shown for each primary energy, one (labelled d1) represents
the average sputter rate at the near surface, i.e. the average sputter rate from the
surface to the first Ge delta-layer (top 12 nm), and the other is the average sputter rate
observed from the surface to the 10
th
Ge delta-layer.
As expected, the sputter rate increases with the incident angle, reaching a
maximum at u ~ 60
o
in the case of both E
p
~ 500 eV and 1 keV, consistent with that
observed at higher energies. The maximum sputter rate for E
p
~ 320 eV occurs at u ~
320eV
500eV
1keV
8keV
1.E+04
1.E+05
1.E+06
0 10 20 30 40 50 60 70 80
Angle of Incidence
I
n
t
e
n
s
i
t
y

(
c
p
s
)
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
I
n
t
e
n
s
i
t
y

(
c
o
u
n
t
s
/
n
C
)
Chapter 6: Cs
+
121
Figure 6.6 Sputter rates vs angle of incidence. For each E
p
, d1 represents the average
sputter rate from the surface to the first delta-layer and the other is the average sputter
rate from the surface to the tenth delta-layer.

50
o
. This is similar to that observed with ultralow-energy O
2
+
SIMS discussed earlier
in Chapter 4 (4.2.2).
26
The lowest sputter rate is about 9.3 nm min
-1
nA
-1
cm
2
and
occurs at normal and near normal incidence with E
p
~ 320 eV. For all energies
studied, the sputter rate is lowest at normal incidence. This is partly due to the
accumulation of Cs at the surface. As the incident angle increases, the penetration
depth of implanted Cs
+
decreases
14
and the sputtering yield increases, resulting in a
higher sputter rate. Beyond u ~ 60
o
, backscattering of the primary ions increases
leading to a subsequent decrease in the sputter rate.
14

Figure 6.6 also shows that the near surface sputter rate is higher than the
average sputter rates for all u and E
p
. For all E
p
up to u ~ 50
o
, the difference in the d1
sputter rate to that of the average sputter rate is quite constant; beyond u ~ 50
o
the
difference widens. This is indicative of a greater transient effect or the onset of
roughening.
500eV
d1
d1
320eV
1keV
0
2
4
6
8
10
12
14
16
0 20 40 60 80
Angle of Incidence
S
p
u
t
t
e
r

R
a
t
e

(
n
m
/
m
i
n
)
0
1
2
0 20 40 60 80
320eV
d1
Chapter 6: Cs
+
122

Figure 6.7 Normalized sputter rates to the last delta-layer throughout the depth.
a) 320eV
0.6
0.8
1.0
1.2
1.4
1.6
1.8
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
0 10 20 30
40 50 60 70
b) 500eV
0.6
0.8
1.0
1.2
1.4
1.6
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
c) 1keV
0.6
0.8
1.0
1.2
1.4
1.6
0 20 40 60 80 100 120
Depth (nm)
R
e
l
a
t
i
v
e

S
p
u
t
t
e
r

R
a
t
e
Chapter 6: Cs
+
123
The increase in the sputter rates is not proportional to E
p
. The variance is
greatest at oblique incidence. The sputter rates when E
p
~ 500 eV compared to when
E
p
~ 320 eV, increases by about 1.3 to 1.5 times at u ~ 0-50
o
to double at oblique
incidence. The sputter rate when E
p
~ 1 keV is much higher compared to E
p
~ 320 eV,
about 6-9 times at u ~ 0-50
o
and 13 times at oblique angles.
Figure 6.7 shows plots of relative sputter rates as a function of depth,
normalized to the sputter rate at the 9
th
to 10
th
Ge delta-layer. Using E
p
~ 320 eV and
u ~ 0-10
o
, the sputter rate is stable as a function of depth. The difference in sputter
rate at the near surface to the average sputtering rate is about 3%. At u ~ 20-50
o
the
difference is about 10-15%. When E
p
~ 500 eV and u ~ 0-30
o
, the difference between
transient and steady-state sputter rates is higher at 20%; but at u ~ 40-50
o
, the
difference is reduced to about 14%. When E
p
~ 1 keV, the difference is 25% at u ~
10-30
o
, and 15% at u ~ 50-60
o
. From these observations, we can infer that the
variance in the surface sputter rates to the average sputter rate increases with E
p
.
Hence, only at very low energies of E
p
~ 320 eV and u ~ 0-10
o
, may we use
the average sputter rate for a reasonably accurate depth conversion at the near surface.
For other combinations reported above, the error in the depth will be about 15%. The
results of the effect of ultralow-energy Cs
+
on transient width and sputter rate of Si are
summarized in table 6.1.

Chapter 6: Cs
+
124

Table 6.1 Summary of results from this work using ultralow-energy Cs
+
sputtering.

320eV 500eV 1keV
30
Si
-
profile with no
peaks & no shoulders)
u ~ 30-50
o
u ~ 30-40
o

u ~ 20-30
o
u ~ 0-10
o

(gradual rise)

30
Si
-
profiles with
shoulders
u ~ 0 - 20
o
Nil Nil
30
Si
-
profiles with peak u ~ 60-70
o
u ~ 50-70
o
u ~ 40-70
o

Enhanced transient
width
11

u > 57
o

(250 eV)
u > 60
o
u > 65
o

Equilibrium signals
maximum intensity at
u ~ 30
o
u ~ 30
o
u ~ 20-30
o

u
c
roughening (evaluated
at 25um)
27

u ~ 50
o

(250eV) u ~ 55
o
u ~ 60
o

Range of u giving
lowest z
tr
u ~ 30-50
o
u ~ 30-50
o
u ~ 20-30
o

Lowest z
tr
2.0 nm 1.4 nm 1.5 nm
Sputter rate max. at u ~ 50
o
u ~ 60
o
u ~ 60
o

Sputter rate min. at u ~ 0
o
, 70
o
u ~ 0
o
u ~ 0
o
Stable erosion rate
(surface cf depth) at
(i) u ~ 0-10
o

(ii) u ~ 20-50
o
u ~ 40-50
o
u ~ 50-60
o

Difference in sputter rate
between near surface
and throughout depth for
u with stable erosion
rate
(i) ~ 3%
(ii) ~ 15% ~ 15% ~ 15%

Chapter 6: Cs
+
125

6.3 Summary
The lowest transient width observed with ultralow-energy Cs
+
ion bombardment is
at an apparent depth of between 1.4 to 2.0 nm, observed under the following
conditions: E
p
~ 320, 500 eV / u ~ 30-50
o
and E
p
~ 1 keV /u ~ 20-30
o
. To the best of
our knowledge, this is the lowest z
tr
that has been reported with Cs
+
primary beams.
We postulate that the onset of roughening occurs in the profiles with peaks and
shoulders since the profiles take a longer time to reach equilibrium. For u > 50
o
,
extended transient effects are observed. For conditions where this effect is not
observed, z
tr
< 1.5-2R
norm
. Under the conditions where minimum z
tr
is achieved, z
tr
~
R
norm
, implying that the Cs concentration stabilizes in the vicinity of R
norm
.
The detection sensitivity is best when profiled at u ~ 30
o
for all energies used. The
sputter rate is lowest at normal incidence, gradually increasing to a maximum at about
u ~ 50-60
o
. This is similar to that reported for O
2
+
bombardment at ultralow-energy.
Only for E
p
~ 320 eV / u ~ 0-10
o
can we use the average sputter rate. For other
conditions such as for E
p
~ 320 eV / u ~ 20-50
o
, E
p
~ 500 eV / u ~ 40-50
o
and E
p
~ 1
keV / u ~ 50-60
o
, the error in the apparent depth at the top 12 nm to the average
sputter rate is better than 15%.
As reducing E
p
is not significant in reducing z
tr
at ultralow-energies, we
conclude that the optimum condition for ultrashallow SIMS profiling is at u ~ 30
o
for
all ultralow-energies (E
p
< 1 keV) as it gives the lowest z
tr
, highest detection
sensitivity and good sputter rate. Transient width and sensitivity in sputter profiling
with Cs
+
at ultralow-energy can thus be optimized simultaneously. Another important
characteristic of depth profiling is the depth resolution, which will be presented in the
Chapter 6: Cs
+
126
next chapter. Profiling at u ~ 60
o
as is commonly done is less sensitive, has larger
transient width and also roughening effects. Hence although u ~ 60
o
is widely used for
dopant profiling with good depth resolution, it is not suitable for ultrashallow
profiling where the bulk of the implant profile lies in the transient region.

References
4. M. L. Yu, Nuclear Instruments & Methods in Physics Research Section B-Beam
Interactions with Materials and Atoms 15, 151 (1986).
7. Y. Kataoka, K. Yamazaki, M. Shigeno, Y. Tada, K. Wittmaack, Applied Surface
Science 203, 43 (2003).
8. P. A. W. van der Heide, M. S. Lim, S. S. Perry, J. Bennett, Applied Surface
Science 203, 156 (2003).
9. M. Anderle and C. M. Loxton, Nuclear Instruments & Methods in Physics
Research B 15, 186 (1986).
10. P. Williams and J. E. Baker, Applied Physics Letters 36, 842 (1980).
12. K. Wittmaack, Nuclear Instruments & Methods in Physics Research B 7-8, 750
(1985).
13. P. A. W. van der Heide, M. S. Lim, S. S. Perry, J. W. Rabalais, Journal of
Chemical Physics 113, 10344 (2000).
Chapter 6: Cs
+
127
15. P. A. W. van der Heide, M. S. Lim, S. S. Perry, J. Bennett, Nuclear Instruments
and Methods in Physics Research B 201, 413 (2003).
16. C. W. Magee, S. A. Cohen, D. E. Voss, D. K. Brice, Nuclear Instruments &
Methods 168, 383 (1980).
17. C. W. Magee and R. E. Honig, Surface and Interface Analysis 4, 35 (1982).
18. J. J. Lee et al., Journal of Vacuum Science & Technology A 8, 2287 (1990).
19. J. Bennett, Surface and Interface Analysis 25, 454 (1997).
20. T. H. Buyuklimanli, J. W. Marino, S. W. Novak, Applied Surface Science 231-
232, 636 (2004).
21. T. Eto and K. Shibahara, Japanese Journal of Applied Physics 44, 2433 (2005).
22. G. R. Mount, C. J. Hitzman and S. P. Smith, Secondary Ion Mass Spectrometry
SIMS XI edited by G. Gillen, R. Lareau, J. Bennett, and F. Stevie, (Wiley
Chichester, 1998), p. 317.
23. M. H. Yang, G. Mount, I. Mowat, Journal of Vacuum Science & Technology B
24, 428 (2006).
24. P. A. W. van der Heide, C. Lupu, A. Kutana, J. W. Rabalais, Applied Surface
Science 231-2, 90 (2004).
26. A. R. Chanbasha and A. T. S. Wee, Surface and Interface Analysis 37, 628
(2005).
Science 203, 43 (2003).

Chapter 7: Cs
+
128
Chapter Seven
Effect of ultralow-energy Cs
+
SIMS on depth resolution

7.1 Introduction
It is known that depth resolution can be improved by lowering the primary ion
impact energy and/or increasing the incident angle up to a critical u, beyond which,
surface roughening ensues. However, a lower E
p
is accompanied by lower secondary
ion yield, and for an ultralow-energy Cs
+
primary beam, a poorly focused beam. In
this chapter, we investigate the effect of depth resolution with ultralow-energy (<1
keV) Cs
+
bombardment over a wide range of incident angles (u ~ 0-70
o
) with the aid
of Ge delta-layers in Si. The
98
SiGe
-
profiles were systematically evaluated by
calculating the FWHM and exponential decay to a depth of 120 nm. Based on the
results obtained, the optimum conditions demonstrating high depth resolution are
ascertained. It is established that the relationship between improvements in depth
resolution (FWHM) and increasing u is linear and gradual. The factors affecting depth
resolution are also examined with the use of the mixing-roughness-information model
(MRI). With this model, it is possible to differentiate the effect of atomic mixing and
surface roughness on the resolution of the o-layers. The impact of atomic mixing,
surface roughness and instrument conditions (poor focus) on depth resolution is also
discussed. Finally, the optimum conditions for high depth resolution with good
dynamic range are recommended.

Chapter 7: Cs
+
129
7.2.1 Depth resolution
Figure 7.1(a) shows typical depth profiles of
30
Si
-
,
59
Si
2
-
and
98
SiGe
-
using E
p
~
320 eV and u ~ 50
o
. The
98
SiGe
-
profile shows ten well-resolved o-layers. However,
before the trailing edge of the first peak reaches the background intensity level, the
leading edge of the next peak begins. This is a result of the atomic mixing depth being
comparable to the inter-o-layer spacing. We also noted tailing at the base of the
trailing edge, and the baseline appears to drift linearly upward with depth. Similar
profiles were done using different E
p
and u. and the results are further evaluated.
Figure 7.1(b) shows an example of
98
SiGe
-
profiles when E
p
is varied, using E
p

~ 320 eV, 500 eV and 1 keV at u ~ 60
o
, normalized to the first peak of E
p
~ 500eV
profile. The depth resolution is observed to be slightly better with lower E
p
at
shallower depths (< 23 nm); but the resolution deteriorates more quickly with depth as
compared to the profile at E
p
~ 1 keV. This can be seen from the rapidly decreasing
peak-to-valley ratio (PVR). The PVR is comparable at all E
p
at the first delta-layer but
becomes smaller with depth, the deterioration being more severe at lower E
p
.
Figure 7.1(c) shows typical
98
SiGe
-
profiles when u is varied, using E
p
~ 320
eV with u ~ 40-70
o
, and normalized to the first peak at u ~ 40
o
. We observe that the u
~ 50
o
profile has the narrowest peak, indicating the best depth resolution. The u ~ 40
o

profile has a gentler trailing edge whereas the u ~ 60
o
profile has a gentler leading
edge. Both u ~ 60
o
and u ~ 70
o
profiles show greater deterioration in depth resolution
with depth compared to u ~ 40
o
and u ~ 50
o
profiles.

Chapter 7: Cs
+
130

Figure 7.1 Typical depth profiles (a)
98
SiGe
-
profiles with
30
Si
-
and
59
Si
2-
(b)
98
SiGe
-

profiles with various E
p
at u ~ 60
o
(c)
98
SiGe
-
profiles with E
p
~ 320 eV at various u.
a) 320 eV / u ~ 50
o
30
Si
-
59
Si
2-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
320eV
500 eV
1 keV
b) 60
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
I
n
t
e
n
s
i
t
y

(
c
p
s
)
320eV 500eV 1keV
40
o
50
o
c) 320eV
60
o
70
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 20 40 60 80 100 120 140
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
40 50 60 70
Chapter 7: Cs
+
131
7.2.1.1 Depth Resolution in terms of FWHM
Figures 7.2(a)-7.2(c) show the depth resolution measured in terms of FWHM
of the
98
SiGe
-
peaks obtained at E
p
~ 320 eV, 500 eV and 1 keV and u ~ 0-70
o
against
depth. At E
p
~ 320 eV, good depth resolution is obtained at u ~ 30-50
o
with FWHM
of less than 2.4 nm throughout the analysis depth of 120 nm. The best depth
resolution is observed at u ~ 50
o
with a mean FWHM of 1.9 nm. The difference in
depth resolution from the first o-layer to the last o-layer is about 18%. At u ~ 60
o
, the
depth resolution is stable at FWHM of 2.6 nm up to a depth of 23 nm (second o-layer)
before deteriorating linearly to 5.7 nm at the last o-layer. The worst depth resolution is
at u ~ 70
o
, beginning with a FWHM of 3.4 nm that degrades with depth.
The trends in depth resolution are similar at E
p
~ 500 eV with good depth
resolution of less than 2.5 nm FWHM observed at u ~ 30-50
o
. The best depth
resolution is at u ~ 50
o
with a mean FWHM of 2.2 nm throughout the analysis depth.
The difference in depth resolution from the first o-layer to the last o-layer is about
17%. At u ~ 60
o
, the FWHM at the first o-layer (depth of 12 nm) is 2.3 nm; but it
deteriorates with depth to two and half times the initial FWHM at the last o-layer. The
depth resolution is worst at u ~ 70
o
, with a FWHM of 3.3 nm at the first o-layer and
degrading thereafter.
Using E
p
~ 1 keV, we observe a different trend compared to that at lower Cs
+

primary ion energy. The depth resolution deteriorates with depth when profiled at u ~
70
o
but not at u ~ 60
o
. The best depth resolution is observed when profiled at u ~ 60
o

with a mean FWHM of 2.5 nm up to a depth of about 80 nm (seventh o-layer) before
Chapter 7: Cs
+
132
Figure 7.2 Depth resolution of Ge delta-layers as a function of profile depth,
measured by FWHM for (a) E
p
~ 320 eV, (b) E
p
~ 500 eV and (c) E
p
~ 1 keV at
various incident angles.
a) 320eV
0-20
o
30-50
o
60
o
70
o
0
1
2
3
4
5
6
7
8
F
W
H
M

(
n
m
)
0 10 20 30
40 50 60 70
b) 500eV
0-20
o
30-50
o
60
o
70
o
0
1
2
3
4
5
6
7
F
W
H
M

(
n
m
)
c) 1 KeV
0-30
o
40-60
o
70
o
0
1
2
3
4
5
6
7
0 20 40 60 80 100 120 140
Depth (nm)
F
W
H
M

(
n
m
)
Chapter 7: Cs
+
133
it deteriorates gradually by 34% at the last delta-layer. At u ~ 50
o
, the mean FWHM
is 2.6 nm up to a depth of 103 nm (ninth delta-layer), which is slightly worse than at u
~ 60
o
but constant to a greater depth.
Given the above observations, a good depth resolution of about FWHM ~ 2
nm can be obtained at an ultralow energy of 320 500 eV with u ~ 50
o
throughout the
depth analysed. At higher primary ion energy of 1 keV, the best depth resolution is
achievable at a higher incident angle of u ~ 60
o
. These observations with Ge delta-
layers are similar to those made with Sb delta-layers and B delta-layers.
1,2
Beyond
these incident angles, the depth resolution deteriorates severely, consistent with the
data reported by Li et al.
3
Generally, good depth resolution is achievable across a ~
20
o
range of u; namely at u ~ 30-50
o
for E
p
~ 320 or 500 eV, and u ~ 40-60
o
for E
p
~ 1
keV.
Figures 7.3(a) 7.3(c) show the depth resolution (in terms of FWHM) of three
representative Ge delta-layers at the near surface d1 (12.2 nm), intermediate depth d5
(57.8 nm) and deepest at d10 (114.8 nm) for all three energies investigated at u ~ 0-
70
o
. Generally, the depth resolution improves gradually as u increases up to a critical
angle before worsening considerably. The critical angle is u ~ 50
o
at E
p
~ 320 eV and
E
p
~ 500 eV, and at u ~ 60
o
at E
p
~ 1 keV. Beyond the critical angles, the depth
resolution degradation is more severe with depth as can be seen from the increasing
slopes of d1, d5 and d10.

Chapter 7: Cs
+
134

Figure 7.3 Depth resolution of Ge delta-layers at various primary ion incident angles.
a) 320 eV
d1
d5
d10
0
1
2
3
4
5
6
7
8
F
W
H
M

(
n
m
)
d1 d5 d10
b) 500eV
d1
d5
d10
0
1
2
3
4
5
6
7
8
F
W
H
M

(
n
m
)
c) 1keV
d1
d5
d10
0
1
2
3
4
5
6
0 10 20 30 40 50 60 70
Incident Angle
F
W
H
M

(
n
m
)
Chapter 7: Cs
+
135
Figure 7.4(a) shows depth resolution in terms of FWHM of the first Ge delta-
layer peak for all three E
p
at u ~ 0-70
o
. It confirms that depth resolution improves with
decreasing E
p
provided that there is no surface roughening. However, the
improvement in depth resolution is marginal, about 1.3 times from 1 keV to 320 eV.
This improvement is not as significant as that observed when using O
2
+
where the
improvement in depth resolution was more than 2.5 times.
4

Figure 7.4(b) shows the plot of depth resolution in terms of FWHM (denoted
as dz) of the Ge delta-layer peak for d1, d5 and d10 against u up to the critical angle
for all three impact energies. At each impact energy, a linear relationship is observed
as follows:
For E
p
~ 320 eV dz = -0.019u + 3.0 (2)
For E
p
~ 500 eV dz = -0.019u + 3.2 (3)
For E
p
~ 1 keV dz = -0.019u + 3.8 (4)
The incremental improvement in depth resolution (decreasing FWHM) with
increasing u is linear, gradual and noticeably similar across all E
p
.

Chapter 7: Cs
+
136

Figure 7.4 (a) Depth resolution of the first Ge delta-layer peak at various E
p
. (b)
Linear relationship between depth resolution in terms of FWHM with u when no
surface roughening is present.
1 keV
a) d1
500 eV
320 eV
0
1
2
3
4
5
6
0 10 20 30 40 50 60 70
Incident Angle
F
W
H
M

(
n
m
)
1 keV 500 eV 320 eV
b)
y = -0.019x + 3.0
y = -0.019x + 3.2
y = -0.019x + 3.8
0
1
2
3
4
5
0 10 20 30 40 50 60 70
Incident Angle
F
W
H
M

(
n
m
)
320 eV 500 eV 1 keV
Chapter 7: Cs
+
137
7.2.1.2 Depth Resolution in terms of exponential decay
Figures 7.5(a)-7.5(c) show the decay length for selected delta-layers using E
p

~ 320 eV, 500 eV and 1 keV against u ~ 0-70
o
. Generally, for the first delta-layer, the
d
decreases as u increases, similar to that observed at higher energy (E
p
~ 8 keV).
5

For E
p
~ 320 eV, we observe
d
for the first delta-layer decreasing with increasing u
(u >10
o
) from 2.7 nm/e to a minimum at 1.1 nm/e at u ~ 50-70
o
.
d
values at the fifth
and tenth delta-layers are correspondingly higher, also decreasing as u increases
reaching a minimum at u ~ 50
o
. At E
p
~ 500 eV,
d
at the first delta-layer decreases
with increasing u from 2.5 nm/e to 1.1 nm/e at u ~ 60-70
o
; at 1 keV,
d
decreases with
increasing u from 3.8 nm/e to 1.5 nm/e at u ~ 70
o
.
Figure 7.5(d) compares the exponential decay of the first delta-layer against
depth for various E
p
. At E
p
~ 320 eV, increasing u beyond 50
o
does not improve
d

significantly. Similarly for E
p
~ 500eV, increasing u beyond 60
o
does not improve
d
.
However, an improvement is observed with E
p
~ 1 keV when u is increased beyond u
~ 60
o
but limited to the near surface regions ( ~ 12 nm) only, similar to that estimated
by Wittmaack
5
at E
p
~ 8 keV. This has been observed in the case of depth profiling of
75
As implants
6
where using E
p
~ 1 keV / u ~ 75
o
gives better depth resolution than at u
~ 60
o
, when only the trailing edge is evaluated. It is clear that
d
decreases with E
p
but
at ultralow energies (E
p
< 1 keV) improvements in
d
beyond u ~ 50-60
o
is negligible.

Chapter 7: Cs
+
138

Figure 7.5 (a) (c) Plot of decay length (
d
) against incident angle (u) for various E
p

at selected depth. (d) Comparison of
d
at the first delta-layer for various E
p
.
a) 320 eV
d1
d5
d10
0
1
2
3
4
E
x
p
o
n
e
n
t
i
a
l

D
e
c
a
y

(
n
m
/
e
)
d1 d5 d10
b) 500 eV
d1
d5
d10
0
1
2
3
4
E
x
p
o
n
e
n
t
i
a
l

D
e
c
a
y

(
n
m
/
e
)
c) 1 keV
d1
d5
d10
0
1
2
3
4
5
E
x
p
o
n
e
n
t
i
a
l

D
e
c
a
y

(
n
m
/
e
)
320 eV
500 eV
d) d1
1 keV
0
1
2
3
4
5
0 10 20 30 40 50 60 70
Incident Angle
E
x
p
o
n
e
n
t
i
a
l

D
e
c
a
y

(
n
m
/
e
)
320 eV 500 eV 1 keV
Chapter 7: Cs
+
139
Figures 7.6(a)7.6(c) show the overlay of profiles of the first Ge delta-layer
obtained at various u and E
p
normalized to the peak obtained at u ~ 30
o
. The trailing
edges at all three values of E
p
are always gentler than the leading edges due to knock-
on and ion beam mixing effects. It can be clearly seen that at E
p
~ 320 eV, the depth
resolution is best at u ~ 50
o
[Fig. 7.6(a)]. At E
p
~ 500 eV, the depth resolution is
marginally better at u ~ 50
o
compared to u ~ 60
o
[Fig. 7.6(b)]. Even though
d

obtained when using E
p
~ 500 eV / u ~ 60
o
is smaller than that at u ~ 50
o
, the depth
resolution at u ~ 50
o
is better as the FWHM is smaller, i.e. there is less ion
bombardment induced peak broadening. At E
p
~ 1 keV, it is best at u ~ 60
o
[Fig.
7.6(c)]. Therefore, based on FWHM and
d
data, we conclude that the best depth
resolution is achievable using E
p
~ 320 eV / u ~ 50
o
, E
p
~ 500 eV / u ~ 50
o
and E
p
~ 1
keV / u ~ 60
o
.

Chapter 7: Cs
+
140

Figure 7.6 Comparison of the normalized
98
SiGe
-
various E
p
.
30
o
40
o
50
o
a) 320 eV
60
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
I
n
t
e
n
s
i
t
y

(
c
p
s
)
30 40
50 60
30
o
40
o
50
o
b) 500 eV
60
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
I
n
t
e
n
s
i
t
y

(
c
p
s
)
c) 1 keV 30
o
40
o
50
o
60
o
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 5 10 15 20
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Chapter 7: Cs
+
141
7.2.1.3 Depth resolution evaluated with MRI model
Figure 7.7 shows the penetration depth of Cs
+
primary ions at ultralow-
energies from u ~ 0-70
o
using TRIM calculations.
7
In Figure 7.1(b), when E
p
is
increased at a constant incident angle u ~ 60
o
, we observe that the depth resolution of
the first delta-layer (at ~ 12 nm depth) is poorer at higher impact energy (E
p
~ 1 keV).
This is expected since E
p
scales with the penetration depth and therefore w. At the
same depth, there is no difference in
d
between the lower energies (E
p
~ 320 eV and
500 eV) suggesting that the small difference in penetration depth does not affect w
and therefore has little or insignificant impact on
d
. However, as the profile deepens,
lowering E
p
results in a worsening of the depth resolution as can be seen by the peak
broadening and a drop in the PVR. Since w decreases with E
p
and the penetration
depth cannot explain this worsening, sputter-induced roughening must be the
dominant factor in causing the degradation in the depth resolution. Surface
roughening as evidenced by AFM measurements has been shown to contribute to the
deterioration of depth resolution.
1,8,9
By analysing the u ~ 60
o
data in figure 7.2, we
deduce that the onset of roughening for E
p
~ 320 eV occurs after 23 nm (second delta-
layer), and that for E
p
~ 500 eV occurs after 12 nm (first delta-layer). These findings
complement the observations made by Kataoka et al.
1
where conclusions on surface
roughening were based on observations made at 35 nm.
In figure 7.1(c), where the impact energy is constant at E
p
~ 320eV and u is
varied, the depth resolution at u ~ 40
o
is worse than at u ~ 50
o
. The peak broadening,
however, is asymmetrical and occurs only at the trailing edge. This is obviously
caused by a larger w at u ~ 40
o
. When the incident angle is increased further to u~70
o
,
Chapter 7: Cs
+
142

Figure 7.7 Penetration depths of Cs
+
primary ions at various incident angles
calculated from TRIM.
7

the depth resolution does not improve but instead worsens when compared to that at u
~ 50
o
. Even though the penetration depth is shallower at such oblique angles, the
narrowing of the atomic mixing length (w) is insignificant when compared to the peak
broadening contributed by surface roughening. We infer that surface roughening
escalates beyond the second delta-layer as the depth resolution deteriorates at a faster
rate at u ~ 60
o
. We also notice that surface roughening corresponds to a drop in the
peak intensity as it reduces the sputter rate and hence the ion yield and intensity. On
the other hand, when the degradation in depth resolution is dominated by atomic
mixing as at u ~ 40
o
, it corresponds to an increase in
d
and no change in peak
intensity. In both cases a drop in PVR is noticeable.
0
1
2
3
4
5
0 10 20 30 40 50 60 70
Incident Angle
D
e
p
t
h

(
n
m
)
1 keV 500 eV 320 eV
Chapter 7: Cs
+
143
In figures 7.2 and 7.3, the increase in FWHM observed are a result of the onset
of roughening occurring at u ~ 60
o
for E
p
~ 320 eV and ~ 500 eV, and at u ~ 70
o
for
E
p
~ 1 keV. In figure 7.4(a), under conditions where surface roughening does not
occur, peak broadening is expected since the penetration depth increases with E
p

causing a wider w and
d
. This conclusion is also confirmed by analyzing figure 7.6.
In figure 7.5(d), the decrease in
d
near the surface ( ~ 12 nm) levels off when
u increases at u ~ 50
o
with E
p
~ 320 eV, u ~ 60
o
with E
p
~ 500 eV and E
p
~ 1 keV. We
propose two possibilities for this occurrence. As u increases, the primary ion
penetration depth becomes shallower thus reducing atomic mixing and
d
but as
surface roughening sets in, the decrease in
d
is offset by the peak broadening brought
about by ripple formation. Alternatively, the decrease in penetration depth at oblique
angles is not significant enough to cause a variation in
d
. Another observation is that
with E
p
~ 320 eV [Fig. 7.5(a)] and 500 eV [Fig. 7.5(b)],
d
deteriorates (increases)
with depth only at

u ~ 60-70
o
onwards, even though
d
is decreasing with increasing u
at the surface. We infer that the deterioration in
d
with depth is mainly attributed to
the onset of roughening which begins at a depth of 12-23 nm. Similarly, at E
p
~ 1 keV
[Fig. 7.5(c)], the onset of roughening is experienced at u ~ 70
o
. Figure 7.5(a) shows
that only at E
p
~ 320 eV, we observe a significant difference in
d
with depth
represented by d1, d5 and d10. At u ~ 0-50
o
where no surface roughening is present,
the wider
d
can be attributed to poor beam focus which is commonly experienced
using ultralow-energy Cs
+
beams. Poor beam focus has been reported to cause erosion
inhomogeneity.
10
We studied the profiles obtained at incident angles where surface
roughening does not occur and concluded that the effect of poor beam focus is
Chapter 7: Cs
+
144
characterized by a linear increase in baseline with depth but with no change in the
peak intensity [cf figure 7.1(a)]. We noted, however, that an increase in baseline also
occurs when there is surface roughening but it is always accompanied by peak
broadening and a decrease in peak intensity. In both situations, the PVR will decrease
but only in the case of surface roughening where a deterioration in depth resolution is
obvious. Hence, PVR is not a conclusive measure of depth resolution. The
deterioration in depth resolution caused by poor beam focus with depth is better
understood with the following relationship:
dz = M + Uz (9)
where the U term reflects instrumental problems (poor focus in this case) and the M
term represents the peak shape due to ion beam broadening, which like atomic mixing
is independent of depth.
11
While the drop in PVR with depth is obvious, the increase
in
d
with depth does not affect the FWHM significantly (cf Figure 7.2)
Table 7.1 shows the best depth resolution obtained with Cs
+
SIMS compared
to that from a similar work done with O
2
+
primary ion SIMS.
4
The penetration depth
based on TRIM calculations for the u with the best depth resolution is also tabled. We
find that with E
p
~ 1 keV Cs
+
SIMS gives better depth resolution than O
2
+
SIMS. This
is expected as a higher mass primary ion will give a shallower penetration depth and
hence narrower atomic mixing width. Penetration depth is determined by the rate of
energy loss along the path of the ion.
12
At constant energy, the bombarding ion with a
higher mass (larger atomic no.) will have a higher nuclear energy-loss rate in an
elastic binary collision due to its higher nuclear cross-section when penetrating the
target. However, at lower E
p
, the best depth resolutions are similar. This unexpected
behaviour can be explained by the contribution to depth resolution from a poorly
Chapter 7: Cs
+
145
Table 7.1 Primary ion penetration depth and FWHM at u with best depth resolution.

focused Cs
+
beam. The Cs
+
beam with a diameter larger than the O
2
+
beam is more
difficult to focus as it fills up the aperture as it enters the focusing lens in the ion gun
column. Moreover, at ultralow-energy, the beam is retarded as it enters the lens which
spontaneously expands the beam.
Figure 7.8 shows the profile resolution data (FWHM and
d
) from the first
delta-layer as a function of beam energy when bombarded at normal incident. Similar
to that observed with O
2
+
primary ion beam, the data demonstrates effectively the
improvement in depth resolution by the use of lower E
p
. A linear plot with
extrapolation to zero- energy has been done though the fit is not as good as that
compared to the data from O
2
+
primary ion beam. The value of the intercept for
FWHM is 2.2 nm and the corresponding value for
d
is 1.6 nm. Both values are
higher than that obtained with O
2
+
primary ion beam. As discussed earlier these limits
are influenced by the poorly focussed Cs
+
primary ion beam which caused an increase
in surface roughening due to inhomogeneous sputtering.

Penetration depth (nm) Depth resolution FWHM (nm)
E
p
O
2
+
Cs
+
O
2
+
Cs
+

250 eV 1.7 (u ~ 40
o
) - 1.5 -
320 eV - 1.7 (u ~ 50
o
) - 1.9
500 eV 2.8 (u ~ 30
o
) 1.9 (u ~ 50
o
) 2.2 2.2
1 keV 4.6 (u ~ 20
o
) 2.0 (u ~ 60
o
) 3.5 2.5
Chapter 7: Cs
+
146

Figure 7.8 Depth resolution parameters (FWHM and
d
) dependence on energy
for the first delta-layer profile at u ~ 0
o
.

7.2.2 Dynamic range
Figure 7.9 shows the dynamic range averaged over the first nine peaks. The
dynamic range gives an indication of the range of concentrations that can be detected
by SIMS. For all three primary ion energies studied, the dynamic range increases as u
moves away from normal. A good dynamic range of more than three decades is
obtained at u ~ 40-70
o
with all impact energies studied. The results are summarized in
table 7.2.

y = 0.0015x + 2.185
y = 0.0021x + 1.65
0
1
2
3
4
5
0 250 500 750 1000 1250
Primary Ion Energy (eV)
R
e
s
o
l
u
t
i
o
n

p
a
r
a
m
e
t
e
r
s
(
n
m
)
FWHM
d
Chapter 7: Cs
+
147

Figure 7.9 Dynamic range averaged over the first nine
98
SiGe
-
peaks vs incident
angle.

320eV
500eV
1keV
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
0 10 20 30 40 50 60 70
Incident Angle
D
y
n
a
m
i
c

R
a
n
g
e

(
I
m
a
x
/
I
m
i
n
)
320eV 500eV 1keV
Chapter 7: Cs
+
148
Table 7.2 Summary of results observed with ultralow-energy Cs
+
sputtering.

7.3 Summary
High depth resolution can be achieved with ultralow-energy Cs
+
SIMS. The
trends in depth resolution are quite similar when using E
p
~ 320 eV and E
p
~ 500 eV
with high depth resolution of less than 2.5 nm FWHM observed at u ~ 30-50
o
throughout the depth range studied. The best depth resolution of FWHM 1.9 nm is
observed at u ~ 50
o
with E
p
~ 320 eV and 2.2 nm with E
p
~ 500 eV. With E
p
~ 1 keV,
320 eV 500 eV 1 keV
Lowest FWHM 1.9nm 2.2nm 2.5nm
u with lowest FWHM
throughout depth
(120 nm)
u ~ 50
o
u ~ 50
o

u ~ 60
o
(up to 80 nm)
u with low FWHM to
a limited depth
u ~ 60
o

FWHM ~ 2.6 nm
(up to 23 nm)
u ~ 60
o

FWHM ~ 2.3 nm
(up to 12 nm)
u ~ 50
o

FWHM ~ 2.6 nm
(up to 103 nm)
u with good depth
resolution

u ~ 30-50
o
(< 2.4 nm)

u ~ 30-50
o
(< 2.5 nm)

u ~ 40-60
o
(< 3.0 nm)

Lowest
d
~ 1.1 nm/e ~ 1.1 nm/e ~ 1.5 nm/e
u with lowest
d

throughout depth u ~ 50-70
o
u ~ 60 -70
o
u ~ 70
o

u with best dynamic
range u ~ 60
o
u ~ 50
o
u ~ 70
o
Highest dynamic
range 1.1 x 10
3
3.0 x 10
3
2.8 x 10
3

Chapter 7: Cs
+
149
depth resolution of less than 3 nm FWHM is observed at u ~ 40-60
o
. The best is
observed at u ~ 60
o
with a mean FWHM of 2.6 nm.
By considering the MRI model, we confirm that depth resolution can be
improved by reducing atomic mixing and/or eliminating surface roughness. Atomic
mixing is reduced by lowering E
p
and/or by increasing u up to a critical incident angle
of u ~ 50
o
at E
p
~ 320 eV and ~ 500eV, and at u ~ 60
o
for E
p
~ 1 keV. Beyond the
critical angle, the depth resolution deteriorates severely with depth due to the onset of
surface roughening. However, a close examination reveals that the onset of surface
roughening is present with E
p
~ 320 eV / u ~ 60
o
only after 23 nm and with E
p
~
500eV / u ~ 60
o
after 12 nm. The relationship between depth resolution (decreasing
FWHM) and u is ascertained to be linear and gradual with all E
p
evaluated.
The decay length decreases as u is increased, with the narrowest
d
~ 1.1-1.5
nm/e obtained at oblique angles. We can extrapolate that a narrower
d
can be
achieved beyond u ~ 70
o
but only at the near surface. However, at this u, the FWHM
is broader. Hence smaller decay lengths do not necessary indicates a better resolution.
Under the conditions when
d
is narrow, it is useful for distinguishing interfaces.
d

also decreases with impact energy but does not decrease significantly at ultralow-
energy (E
p
< 1 keV). A small change in the penetration depth does not affect the
atomic mixing length and therefore has little or an insignificant impact on
d
.
Using the MRI model, we can establish whether the broadening is dominated
by surface roughening or atomic mixing. Surface roughening corresponds to a
decrease in peak intensity and peak broadening while atomic mixing corresponds to
an increase in the exponential decay of the trailing edge but not a reduction in peak
Chapter 7: Cs
+
150
intensity. Another phenomenon that is observed in Cs
+
SIMS is poor beam focus. This
is seen as a linear increase in profile baseline but without any change in peak intensity
provided there is no surface roughening.
Cs
+
SIMS gives better depth resolution than O
2
+
SIMS at higher impact energy
but not at lower energies below E
p
~ 500 eV due to the poor beam focus that causes
uneven erosion. We suspect that poor beam focus limits the improvement in depth
resolution at ultralow energy.

Chapter 7: Cs
+
151
References
Science 203, 43 (2003).
2. P. A. W. van der Heide, M. S. Lim, S. S. Perry, J. Bennett, Nuclear Instruments
and Methods in Physics Research B 201, 413 (2003).
3. Z. P. Li, T. Hoshi, R. Oiwa, Applied Surface Science 203, 323 (2003).
4. A. R. Chanbasha and A. T. S. Wee, Journal of Vacuum Science & Technology B
24, 547 (2006).
5. K. Wittmaack, Journal of Vacuum Science & Technology A-Vacuum Surfaces
and Films 3, 1350 (1985).
6. G. R. Mount, C. J. Hitzman and S. P. Smith, Secondary Ion Mass Spectrometry
SIMS XI, edited by G. Gillen, R. Lareau, J. Bennett, and F. Stevie (Wiley,
Chichester, 1998), p. 273.
7. J. F. Ziegler and J. P. Biersack, SRIM 2003, http://www.srim.org (2003).
8. C. M. Ng, A. T. S. Wee, C. H. A. Huan, A. See, Nuclear Instruments & Methods
in Physics Research B 179, 557 (2001).
9. G. S. Lau, E. S. Tok, R. Liu, A. T. S. Wee, J. Zhang, Nuclear Instruments &
Methods in Physics Research B 215, 76 (2004).
Spectrometry: Principles and Applications (Oxford University Press, New York,
1989).
1996), p. 88.

Conclusion
152
Chapter Eight
Conclusion

Ultralow-energy SIMS has been introduced for almost ten years now to meet
the increasing demands to reduce the transient width and to increase the depth
resolution possible for ultrashallow depth profiling and ultrathin films. However,
there are insufficient comprehensive studies done on the effects of ultralow-energy
O
2
+
and Cs
+
primary ion beams on surface transient and depth resolution over a wide
range of incident angles. Reducing the primary ion energy and increasing the incident
angle has positive effects on reducing the transient width and improving the depth
resolution. It is critical that the effects, the processes involved, the possibilities and
the limitations be understood so that methods can be developed towards achieving
more accurate SIMS depth profiling data to support the needs of the semiconductor
industry.

8.1 Surface transient
One of the motivations of this study is the need to qualitatively and
quantitatively profile ultrashallow junctions consistent with the demands of the
semiconductor industry. A significant part of the doped region in ultrashallow
junctions coincides with the surface transient region of the SIMS technique. The
surface transient cannot be avoided even with the introduction of ultralow-energy
SIMS as the dynamics of ion-surface interactions takes time to reach equilibrium.
Nevertheless, it is imperative that the inaccuracies owing to varying sputter rate and
Conclusion
153
secondary ion yield experienced during the surface transient should be limited to a
very shallow depth (narrow transient width).
Our study with an ultralow-energy O
2
+
primary ion beam shows that the
minimum transient width is achievable at normal and near normal incidence. To date,
only normal incidence has been reported. The lowest transient width achieved is ~ 0.7
nm (apparent depth) with primary ion energies of less than 500 eV. However, we
notice that at ultralow-energy, reducing the incident energy beyond 500 eV does not
result in a significant reduction in transient width. Nevertheless, the range of incident
angles to which the minimum transient width can be achieved is greater when the
incident energy is lowered. Equilibrium is achieved earlier as a result of complete
oxidation of silicon which is readily achieved at these incident angles. The complete
oxidation of silicon also prevents the onset of roughening with E
p
~ 250 eV.
When an ultralow Cs
+
primary ion beam is used, a minimum transient width of
1.4 nm to 2.0 nm (apparent depth) is achieved with E
p
~ 320 eV, 500 eV, u ~ 30-50
o

and E
p
~ 1 keV, u ~ 20-30
o
. This is the lowest transient width that has been reported.
Unlike O
2
+
sputtering, where the oxidation of silicon reduces the time taken to reach
equilibrium, Cs
+
sputtering proceeds with a gradual build up of Cs concentration on/in
the silicon substrate. Hence, the wider transient width as compared to that achieved
with O
2
+
sputtering. We have shown that the narrowest transient widths are achieved
when the Cs concentration stabilises in the vicinity of the Cs penetration depth
(R
norm
).
Beyond u ~ 50
o
for all energies studied, an extended transient effect has been
observed. This observation suggests that u ~ 60
o
which has been widely used for
Conclusion
154
depth profiling with Cs
+
, is not appropriate for profiling ultrashallow junctions i.e.
when narrow transient is essential.
There are techniques such as silicon capping and backside depth profiling that
have been developed and are successful in circumventing the surface transient effect.
Nevertheless, the sample preparation that is necessary prior to SIMS depth profiling
in both techniques are very tedious and are not suitable for routine analysis.

8.2 Sputter rate
In the ultralow-energy regime, the sputter yield decreases correspondingly.
This is an important consideration, as it affects the speed of analysis. For both primary
ion beam species used, the lowest sputter yield is experienced at normal incidence and
the highest at an incident angle of 50-60
o
which is similar to that at higher energy ion
sputtering. However, it is worthwhile to note that at E
p
~ 250 eV, the maximum
sputter rate is observed at u ~ 50
o
.
Another important consideration for sputter rate is the use of average sputter
rate for depth conversion. We confirmed that the intrinsic surface transient causes the
sputter rate at the near surface to be higher than the average sputter rate. As such, it is
prudent to have an idea of the error in depth scale when the average sputter rate is
used.
With a Cs
+
primary ion beam, the range of incident angle where the average
sputter rate can be reliably used is smaller compared to O
2
+
primary ion beam.

Conclusion
155
8.3 Depth resolution
Another motivation in this study is the need to achieve high depth resolution
with ultralow-energy O
2
+
and Cs
+
primary ion beam. A high depth resolution is
critical to be able to differentiate between thin adjacent layers as in gate oxides and
multi-quantum wells.
With ultralow-energy O
2
+
primary ion beams, the depth resolution improves as
the primary ion energy is lowered. It is also noted that the range of incident angles
where high depth resolution is achieved is greater with decreasing incident energy.
Thus, high depth resolution is achievable not only at normal incidence but over a
wider range of incidence angle as E
p
is reduced. The best depth resolution is observed
at u ~ 40
o
with E
p
~ 250 eV.
Similarly, depth resolution improves when the ultralow-energy Cs
+
primary
ion beam incident energy is lowered. The best depth resolution is achieved at u ~ 50-
60
o
. We established that at ultralow-energy the relationship between depth resolution
(decreasing FWHM) and incident angle is linear and gradual with u < 50-60
o
. We also
noticed that when E
p
decreases,
d
does not decrease significantly because the atomic
mixing length do not change very much with a small change in penetration depth
resulting from a decrease in E
p
at ultralow-energy. However, when the incident angle
is increased, the decrease in
d
is obvious. Hence, oblique angles are better at
profiling steeply varying profiles and interfaces. We predict that
d
may be smaller at
u > 70
o
but only at the near-surface.
Based on the MRI model, we are able to identify the factors that contribute to
poor depth resolution: surface roughening by observing a drop in the peak intensity
and Gaussian peak broadening, and atomic mixing by a broadening of the trailing
Conclusion
156
edge due to an increase in
d
but without a decrease in peak intensity. We also
confirmed that depth resolution (decrease in FWHM) can be improved by reducing
atomic mixing i.e. by reducing E
p
and/or increasing u up to 40-60
o
with Cs
+
primary
ion beam and up to 20-40
o
with O
2
+
primary ion beam. When E
p
decreases, it
corresponds to a reduction in atomic mixing. When u increases beyond a critical
angle, surface roughening will set in contributing to a poorer depth resolution.
The onset of roughening can also be detected earlier with the MRI model
compared with observing an increase in the matrix
30
Si
-
profile. Thus, the MRI model
is a more sensitive indicator of the onset of roughening.
A Cs
+
primary ion beam gives better depth resolution than O
2
+
primary ion
beam at higher E
p
but not at ultralow-energy of less than 500 eV due mainly to poor
beam focus. Therefore, poor beam focus is the limiting factor in the improvement of
depth resolution at ultralow energy.
Other methods such as oxygen flooding and sample rotation have been used to
suppress surface roughness and therefore sustain high depth resolution. Oxygen
flooding has been successful only with O
2
+
primary ion beam. These techniques,
however, have been developed mainly for use with instruments that can operate only
at oblique angles.

8.4 Dynamic range
With an ultralow-energy O
2
+
primary ion beam, the dynamic range increases
as u moves away from the normal with the highest dynamic range achieved at u ~ 30-
50
o
. The dynamic range is about three to four orders of magnitude. Beyond these
incident angles the dynamic range decreases.
Conclusion
157
With a Cs
+
primary ion beam, a dynamic range of three orders of magnitude is
possible when profiled at u ~ 40-70
o
.

8.5 Optimum conditions for analysis
From the observed effects of ultralow-energy O
2
+
and Cs
+
SIMS on silicon, we
recommend different sets of conditions for the analysis of ultrashallow implants and
thin films or multi-quantum well structures which are positioned deeper beneath the
surface. For the profiling of electropositive elements in ultrashallow implants, it is
best to operate with O
2
+
primary ion beam. To obtain a narrow transient width and
reliable depth conversion by using the average sputter rate, E
p
< 500 eV, u ~ 0-10
o
or
E
p
~ 250 eV, u ~ 0-20
o
are recommended.
For electronegative elements, profiling with a Cs
+
primary ion beam with E
p
<
500 eV, u ~ 30-50
o
and E
p
~ 1 keV, u ~ 20-30
o
is recommended for a narrow
transient. To achieve a narrow transient and the highest detection sensitivity, it is best
to profile at u ~ 30
o
for E
p
< 1 keV. With this combination, the transient width and
sensitivity can be optimized simultaneously.
For applications such as the profiling of multi-quantum well and thin films, a
high depth resolution is essential. Such requirements are best achieved when profiling
at u ~ 20
o
with E
p
~ 1 keV, u ~ 30
o
with E
p
~ 500 eV and u ~ 40
o
with E
p
~ 250 eV
O
2
+
primary ion beam. The dynamic range is almost the maximum achievable. With a
Cs
+
primary ion beam, u ~ 50
o
is recommended with E
p
< 500 eV and u ~ 60
o
with E
p

~ 1 keV without compromising on dynamic range.
Conclusion
158
When both a narrow transient width and a high depth resolution are required,
it is best achieved at u ~ 40
o
with E
p
~ 250 eV O
2
+
primary ion beam. The transient
width is marginally worse off than at normal and near normal incidence. This is also
possible with a Cs
+
primary ion beam at u ~ 50
o
with E
p
< 500 eV.

8.6 Proposed future work
In the sample used for this study, the first delta-layer is at a depth of 12 nm
and this is the first reference position for an accurate depth determination. The
transient width and sputter rate can be more accurately determined if the first delta-
layer can be nearer the surface. Further work with the first delta-layer nearer the
surface is necessary to determine a more accurate measure of the transient width.
Based on the recommended optimum operating conditions, it is useful to study
the percentage error in the quantification of dose of commonly used ultrashallow
implants such as B, P and As. The same set of samples can also be used to observe the
error in the junction depth compared to the use of alternative methods such as
spreading resistance profilometry (SRP) or carrier illumination method (CI).
Similar studies on other common substrates such as GaN, GaAs and InSb is
also beneficial to observe for similarities or differences when subjected to different
matrices.
The onset of roughening has a deleterious effect on both the surface transient
and depth resolution. More detailed scientific studies with in-situ XPS on ultralow-
energy SIMS will provide a better understanding on the process of surface roughening
especially with Cs
+
primary ion beam.

Appendix A
159
Appendix A

Depth profiles with O
2
+
primary on beam

b) 250 eV, 10
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
a) 250 eV, 0
o
70
Ge
+
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
I
p
Appendix A
160

d) 250 eV, 30
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
c) 250 eV, 20
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
161

e) 250 eV, 40
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
f) 250 eV, 50
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
162

70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
h) 250 eV, 70
o
g) 250 eV, 60
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
163

j) 500 eV, 10
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
i) 500eV, 0
o
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
164

k) 500 eV, 20
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
l) 500 eV, 30
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
165

m) 500 eV, 40
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
n) 500 eV, 50
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
166

o) 500 eV, 60
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200 250 300
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
p) 500 eV, 70
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200 250 300
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
167

q) 1 keV, 0
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
r) 1 keV, 10
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
168

s) 1 keV, 20
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
t) 1 keV, 30
o
70
Ge
+
Ip
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
169

u) 1 keV, 40
o
70Ge+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
v) 1 keV, 50
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix A
170

w) 1 keV, 60
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
x) 1 keV, 70
o
70
Ge
+
I
p
30
Si
+
44
SiO
+
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
171
Appendix B

Depth profiles with Cs
+
primary ion beam

a)320 eV, 0
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
b) 320 eV,10
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
172

c) 320 eV, 20
o
30Si-
Ip
59Si2-
98SiGe-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
d) 320 eV, 30
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
173

e) 320 eV, 40
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
f) 320 eV, 50
o
30
Si
-
I
p
59
Si
2
-
98SiGe-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
174

g) 320 eV, 60
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
h) 320 eV, 70
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
175

i) 500 eV, 0
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
j) 500 eV, 10
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
176

k) 500 eV, 20
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
l) 500 eV, 30
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
177

m) 500 eV, 40
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
i
n
t
e
n
s
i
t
y

(
c
p
s
)
n) 500 eV, 50
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
178

o) 500 eV, 60
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
p) 500 eV, 70
o
30
Si
-
I
p
59
Si
2
-
98SiGe-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
179

r) 1 keV, 10
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
q) 1 keV, 0
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
180

t) 1 keV, 30
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
s) 1 keV, 20
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
181

u) 1 keV, 40
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
v) 1 keV, 50
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
Appendix B
182

w) 1 keV, 60
o
30
Si
-
I
p
59
Si
2
-
98SiGe-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)
x) 1 keV, 70
o
30
Si
-
I
p
59
Si
2
-
98
SiGe
-
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0 50 100 150 200
Depth (nm)
I
n
t
e
n
s
i
t
y

(
c
p
s
)

Ultralow Energy SIMS

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A STUDY OF THE EFFECTS OF ULTRALOW-ENERGY

SECONDARY ION MASS SPECTROMETRY (SIMS) ON

Sputtered ion emission yield

, and molecular ions M

. Doubly charged ions are

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