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Materials Science on the Atomic

Scale with the 3-D Atom Probe:


Experiments and Modelling

George Smith

Department of Materials
Oxford University
Acknowledgements
• Alfred Cerezo, Professor, Oxford University
• Paul Warren, Gang Sha, Rohan Setna, Andrew Morley, Paul Bagot,
Terry Godfrey, Oxford University
• Kazuhiro Seto
– JFE Steel
• Shoichi Hirosawa
– Tokyo Institute of Technology
• David Larson
– Seagate Technology, USA (now at Imago Scientific Instruments)
• Funding:
– EPSRC, The Royal Society, Rolls-Royce, Oxford Nanoscience
Declaration of Interest
• In 1987, together with family and university
colleagues, I set up a small company, Kindbrisk Ltd
(subsequently renamed Oxford nanoScience)
• Oxford nanoScience became part of the Polaron Group
of companies, and is now owned by Imago Scientific
Instruments
• I and my family and colleagues are shareholders in
Polaron, which in turn is a stakeholder in Imago.
Outline of Talk
• Knowledge requirements for materials design: advantages of
combining experimental data with modelling studies

• Seeing atomic structure with the field ion microscope

• Studying 3-D atomic composition: atom probe analysis

• Modelling atomic processes by Kinetic Monte Carlo

• Case studies: examples from Cu, Al and Fe-based alloys

• Extension to thin films, catalysts and semiconductors


Field Ion Microscope Image of Pt
Field ion microscope
• Specimen in form of needle, 100nm end radius
• Voltage applied to specimen generates high field
• Gas ionised at apex generates image on screen

Channel plate
High voltage (d.c.) and phosphor screen
Field ionised
gas atoms

Needle-shaped
specimen (cooled)
Vacuum chamber
FIM image formation
Polarised Gas ion
+ gas atom
– Thermal
accommodation

Ionisation

Adsorption
Critical
surface

Specimen
Field ionisation
• Strong electric field Gas atom
distorts electron potential
of gas atom and allows
ionisation by electron
tunneling I
• Ionisation can only occur
when electron level in φ
atom lies above the Fermi e–
level in the metal
Metal
• This defines minimum or
critical distance, xc within
which ionisation cannot xc
occur
Ball model of FIM Specimen
Grain Boundary in Tungsten
Field evaporation
V(x)
• Electric field distorts the
potential curve for ion on
metal surface ∑I
n − nφ Ion
(no field)
• At very high field, ionic
and atomic curves cross
x
• Thermal activation can
produce ionisation - even Λ
Atom
at low temperatures −neFx
• Evaporation field depends
on sublimation energy Λ Ion
(in field)
(thus melting temperature)
Atom probe microanalysis
• Single atoms field evaporated from specimen and
identified by time–of–flight mass spectrometry.
• Local composition measured directly by counting atoms
• Spatial resolution is approx. 2nm laterally 0.2nm in depth.
High voltage Single-ion
FIM image
(d.c. + pulse) sensitive detector
screen

Field
evaporated
ions
Needle-shaped
specimen (cooled)

Vacuum chamber
Identifying single atoms
• Flight time t of ions removed from specimen is measured
over flight length d with (sub-)nanosecond resolution.
• By equating potential energy for ion at specimen and
kinetic energy after field evaporation, can calculate mass-
to-charge ratio:

Kinetic energy 1
2 mv2 = neV Potential energy

2 2
⎛ 1 ⎛
= 2eV ⎞ = 2 eV ⎞
m t
n ⎝ v⎠ ⎝d⎠
⎛ m⎞
Δ ( )
⎝ n ⎠ = ΔV + 2Δt
2
The 3-dimensional atom probe
• Single atoms removed from specimen and
identified
• Position sensing gives original position to sub-nm
• Continued removal gives 3-D atomic-scale map
Position-
High voltage
sensitive
(d.c. + pulse)
detector

Field
Specimen evaporated Flight time
(cooled) ions signal
3DAP Data Example: Stainless Steel
Mass Resolution: Log scale 24.5 to 33.5 amu

• FW1%M ~ 200
• All peaks resolved
• Cu2+ and Mo3+
species separated by
0.17 amu
Duplex Stainless Steel – Linear Scale
Duplex Stainless Steel – Linear Scale
3D atomic scale tomography
(x,y)
• At any point, 3DAP gives
analysis of the surface
z=0
elemental distribution
z=1
• Field evaporation leads to
z=2
atomic layer ‘slicing’
z=3
through the material
z=4
• Data allows reconstruction
z=5
of original 3–D
distribution of elements
3-dimensional atom probe (3DAP)
• 3DAP allows mapping of
element distributions with •Mg
•Si
atomic-scale resolution and in
3-dimensions
• Local compositions can be
measured directly
• Example:
– Mg and Si distributions
from 6000 series Al alloy
aged for 16hours at 180˚C
– Atom map clearly shows
(100) oriented precipitates

5nm
Data courtesy S. Pilcher, Oxford University
High resolution wide angle 3DAP
study of Cu precipitation process
High Ni steel aged for 50,000 hours at 330˚C

•Fe
•Cu

10nm

(only 10% of Fe atoms from analysis shown)


3-D Atomic Scale Computer
Simulation of Alloy Systems
• Accurate simulation of subtle solute effects
requires model which includes vacancy exchange
and vacancy-solute interactions
• Large number of parameters required, but these
are determined from independent sources:
– like atom-atom interactions (Eii) from cohesive
energies, corrected for different lattice parameters
– unlike interactions (Eij) from phase diagram
information
– vacancy-solute interactions (Eiv) from vacancy
formation energies in pure materials
Kinetic Monte Carlo model
• Alloy represented by atoms on fixed lattice: no strain
• Thermodynamics given by nearest neighbour interactions
• Diffusion modelled statistically
– Atomic diffusion steps modelled by vacancy migration
– Migration probability depends on energy change
– Realistic timescales calculated using residence time
algorithm
Vacancy exchange: parameters
E • Single vacancy used in
ΔEa ΔE model (conc. 10-6).
Model time is scaled
to take into account
x real vacancy
concentration:
• Activation barrier
given by: ΔE Cveq
ΔEa = ε 0 + t = model ∑ τ
2 Cv MCS

• where:ε 0 = Qidiffusion − ΔHvf


− [ΔHv (Fe) − Eiv ]
diffusion f
= Qi
b
Nucleation in copper-cobalt
• Cu-1at%Co solutionised and aged at 723K
(ΔT≈300K)
Data courtesy of R. Setna, University of Oxford
30 minutes 1 hour 24 hours

5nm
Model: nucleation in Cu-1at.%Co
• Simulation of ageing in Cu-1at.%Co at 723K

600 MCS 1200 MCS 29000 MCS


Hardness evolution of 7050 Al alloy
200
Ageing at 121˚C
190

180

170

160

150
1 10 100 1000 10000
Ageing time (min

• Alloy composition: 6.29 wt% Zn, 2.22 wt% Mg,


2.28 wt% Cu, 0.11 wt% Zr, 0.09 wt% Fe and 0.05
wt% Si
7050 Al alloy: 3DAP observations
AQ 30 min

60 min

240
min

1440 min
•Zn
5 •Mg
nm •Cu
Simulation of 7050 Al alloy
Development of precipitates during simulated ageing at 121˚C
25 mins 45 mins 810 mins 1500 mins

C’’
D D
C’
A’’ C’
D N A’
D A
B’

B
B’’

•Zn
•Mg
•Cu
Hardness for Cu-containing steel
250
240
Vickers hardness / HV
1.5%Ni-containing alloy
230
0.3%Ni-containing alloy
220
210
200
190
180
170
160
150
1x10 -1 Before 10 102 103 104 105
ageing
Ageing time at 365˚C / hrs

• Fe-0.5at.%Cu-Ni-1.5at.%Mn-0.75at%Si
• Higher Ni alloy shows a more pronounced
hardening
Analysis of steel aged at 365˚C
Before ageing 100hrs 1000hrs 3000hrs 10000hrs
1.5 at.% Ni
0.3 at.% Ni

10nm

• Higher density of Cu clusters are formed in higher


Ni alloy
Analysis of steel aged at 365˚C
• A shell of Ni, Mn and Si formed around Cu
clusters after ageing at 365˚C for 3000 hours
• Other solutes segregate weakly, or not at all

Cu Ni Mn Si 5nm
Interface segregation in high-Ni steel
Aged for 18620 hours at 330 ˚C Aged for 100 hours at 405 ˚C
20.0 20.0
Matrix Ppt. Si Matrix Ppt. Si
18.0 Mn 18.0 Mn
16.0 Ni 16.0 Ni
14.0 14.0

12.0 12.0

10.0 10.0

8.0 8.0

6.0 6.0

4.0 4.0

2.0 2.0

0.0 0.0
-0.3 0 0.3 0.6 -0.3 0 0.3 0.6
Distance from interface (nm Distance from interface (nm
Simulation of steel aged at
Before ageing
365˚C
~370hrs ~1860hrs ~9240hrs ~36720hrs
1.5 at.%Ni
0.3 at.%Ni

5nm

• Simulated microstructures are a good match with those


observed in 3DAP analysis of steels
Origin of interface segregation
Ni Ni Ni

Cu Fe Cu Fe Cu Fe

Eint=5(ΕCuCu+ΕFeCu+2ΕFeNi) Eint=5(ΕCuCu+ΕCuNi+ΕFeNi+ΕFeFe) Eint= 5(2ΕCuNi+ΕFeCu+ΕFeFe)


= 5 ×(-247.3) kJ/mol =5×(-254.6) kJ/mol =5×(-252.3) kJ/mol

• Energy parameters from model can be used to compare


internal energies of three different atom configurations
• Lowest energy configuration is for Ni at ppt. interface.
• Parameters for Mn and Si show similar tendency
3DAP Analysis of Multilayer Stack
•Co
•Cu
•Ni

<111>
growth
direction

5 nm 2 nm

Whole analysis (800k atoms) Selected volume 16×9×4 nm


MD Simulation of Deposition vs.
3DAP Data
3D Atom Probe Data Molecular Dynamics Model

•C
o
•C
u
•Ni
•Fe

2 nm

Modelling results from collaboration with X. Zhou and H. Wadley (Univ. of


Virginia)
Pulsed Laser Atom Probe
Unannealed TMR structure
Cap • Analysis of TMR
FM layer structure (similar to that
Barrier used in hard disks and
MRAM) with laser pulsed
FM layer
3DAP
• Laser pulsing makes
analysis of these complex
Seed structures more routine,
especially in the case
where insulating layers
2nm are present
Slice 4nm thick • Note atomic planes in
lower FM layer
Boron Dopant Atoms in Silicon
(specimen courtesy of D. Larson)
PLAP Spectrum from GaInAsP
Mass spectrum from GaN
N2+

69Ga+

71Ga+

69Ga+
N+
71Ga+
Field Evaporated Pt-Rh Surface
Pt-Rh after exposure to NO
Pt-Rh (111) surface exposed to
10 mbar NO at 573K
Pt-Rh (001) surface exposed to
10 mbar NO at 573 K
Molecular Adsorption Sites:
NO on Pt(012), 292K

• Molecular NO adsorption at step edges


Summary
• 3DAP is powerful technique for studying the
atomic-scale structure and composition of materials
• 3D experiments can be used to benchmark computer
models of materials behaviour
• 3-D atomic scale characterisation of processing of
metallic multilayer structures is now achieved
• Study of semiconductors and catalysts possible
• Foundation for atomic scale materials design – but
still a huge amount more work to do!
Questions & Answers