Specimen Preparation of

Metals and Alloys for

Atom Probe Tomography
by Electropolishing
R. Prakash Kolli, Ph.D., PE
July 24, 2016
1st Atom Probe Pre-meeting Congress
Organized by the MSA AP FIG

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 Atom Probe Tomography (APT)
•  Field evaporation technique that permits 3D atom-
by-atom reconstructions

• Specimens in the form of sharp needles or

microtips fabricated by electropolishing or by a
dual-beam focused ion beam (FIB) – scanning
electron microscope (SEM) instrument

•  106 – 107 nm3 analysis volume

•  10-10 – 10-11 torr UHV
•  20 – 100 K specimen temperature
•  ≤ 200 kHz voltage pulsing
•  ≤ 1,000 kHz laser pulsing
h"p://www.cameca.com/instruments-for-research/
leap-si.aspx
•  ~0.1 – 0.2 nm depth spatial resolution
•  ~0.2 – 0.5 nm lateral spatial resolution
•  Equally sensitive for all chemical species

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 Overview
•  Specimens in the shape of sharp needles
or microtips
•  Apply a positive DC voltage
•  Apply rapid AC voltage pulses or laser
pulses
•  Ions are field evaporated and detected
•  x- and y-position determined by
position sensitive detector
•  z-position given by pulse sequence
•  mass-to-charge state (m/n) ratio
determined by time-of-flight (TOF)
mass spectrometry 3
 Specimen Preparation Overview

•  APT requires a sufficiently high electric field at the specimen

tip of ~10 – 50 V nm-1
•  Sharp specimens with small radii can attain such a field
•  rtip ≤ ~50 nm
•  Shank half-angle ≤ ~10°
•  Specimen fabrication for APT is a combination of science and
art
•  Researcher skill is a significant factor in the rate of successful specimen
preparation
•  Successful specimen preparation leads to more successful data
acquisition and data analysis

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 Specimen Preparation Techniques

•  Electropolishing
•  Dual-beam Focused Ion Beam (FIB) – Scanning Electron
Microscope (SEM) instrument
•  Other fabrication techniques

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 Electropolishing

•  Conventional method that relies on conductivity of the

specimen to be analyzed
•  Electrochemical process that is often performed at room
temperature
•  Manual or Automated
•  Initial (Rough) Polishing, Final Polishing, Pulse Polishing
•  Electrolytes
•  Artifacts
•  Advantages and Disadvantages

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 Manual Electropolishing

•  A two-step electrochemical method that shapes

conductive specimen blanks into sharp needle-shaped
specimens for APT analysis
•  Specimen blanks are wire or small rectangles (0.5 × 0.5 x ~ 10 – 25 mm3)
taken from bulk material
•  Specimen blank acts as an electrode, requires a counter electrode, an
electrolyte, and a controllable DC voltage and current
•  Assisted by a low power optical microscope or steromicroscope

Electropolish
APT Needle-Shaped Specimen
Cut
Bulk
Schema9c courtesy of Mr. Richard Martens (U. Alabama)
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 Specimen Blanks
Blanks from a
thin ribbon or sheet
Miller and Smith (1989)

Wires or Whiskers

Larson, et al. (2013)

Blanks cut from the bulk by low-speed saw

Gault, et al. (2012)

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 Manual Electropolishing Station
Suspended
Light Source Specimen Blank
Stand
Fume Exhaust Vent

Counter
Electrode

CuveDe
w/ Electrolyte

VerFcal
TranslaFonal
Control

Stereomicroscope
Power Supply and Control

Images courtesy of Dr. Dieter Isheim (NUCAPT) 9

 Other Manual Electropolishing
Configurations

•  Manual ElectropointerTM by Simplex •  Standardized Configura9on

Scien9fic

Power Supply
and Control

Specimen Blank
and Loop Counter
Electrode

OpFcal
Microscope Adjustable
Actuators

Larson, et al. (2013)

http://www.simplexsci.com/EPMan.html

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 Manual Electropolishing Procedure

•  Initial or Rough Polishing – thin the wire or specimen

blank into a necked shape by using the meniscus of the
electrolyte that is in the cuvette while applying a DC
voltage
•  Final Polishing – continue thinning the necked wire or
specimen blank in a controllable manner until separation
by using a lower strength electrolyte and a lower DC
voltage
•  Pulse Polishing – uses a wire loop with a thin film of
electrolyte to resharpen a blunt or fractured needle and
short voltage pulses

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 Manual Electropolishing Method

Blank IniFal
Polish

Needle
Electrolyte

Final
Polish
Miller and Smith (1989)
Original schematic courtesy of Dr. Matt Bender (Northwestern)

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Manual Electropolishing Method
NUCu-140-1 Aged 1024 hours @ 500 oC

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 Automated Electropolishing Station

•  ElectropointerTM by Simplex Scientific

Automated Suspended
Computer Control TranslaFonal Specimen Blank
Monitor and Control Voltage Stepper Motor

Loop
Counter Electrode
Beaker
w/ Electrolyte

Images courtesy of Mr. Richard

Martens (U. Alabama)

Kostrna, et al. Microsc. Microanal. (2006)

http://www.simplexsci.com/ElectroPointer.html 14
 Electrolytes

•  Acids in solvents similar to those used in TEM specimen

preparation
•  These acids are often toxic, corrosive, and flammable –
check Material Safety Data Sheet (MSDS)
•  Different metals and alloys require different electrolytes
and voltages to produce controlled electropolishing
•  Too high a voltage for a particular electrolyte will cause pitting

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 Example Electrolytes

•  Steel & Nickel-Based Superalloys – ~2-10% perchloric

acid in acetic acid or butoxyethanol or methanol
•  Aluminum Alloys – ~20-30% nitric acid in methanol;
~2-10% perchloric acid in butoxyethanol or methanol
•  Copper – Phosphoric acid
•  Magnesium Alloys – 5% perchloric acid in butoxyethanol
•  Titanium Alloys – 6% perchloric acid in methanol
References
Miller and Smith (1989)
Miller, et al. (1996)
Gault, et al. (2012)
Larson, et al. (2013)
Miller and Forbes (2014)

Perchloric acid is hazardous and requires a dedicated and certified fume hood. 16
 Electropolishing Artifacts

•  Different phases can polish at different rates

Iron-based bulk metallic glass that

exhibits non-uniform cross-secFon and
mulFple phases

Miller and Russell Ultramicrosc. (2007)

•  Tip may bend during final polishing

•  Electrolyte residue
•  Pitting
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 Advantages

•  Inexpensive equipment
•  Can easily repolish and resharpen blunt or fractured
needles
•  Can rapidly make specimen blanks
•  Can rapidly make multiple needles
•  No Ga+ ion implantation
•  No embrittlement

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 Limitations

•  Limited to conductive metals and alloys

•  Only one to four needles per puck
•  Oxides can form on some metals such as titanium
•  Site-specific sample preparation is more difficult

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Questions?

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Backup Slides

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 Focused Ion Beam (FIB)
Instrument

•  Focused Ion Beam (FIB) instrument

•  Use a FIB instrument or dual-beam FIB instrument to fabricate needle-
shaped specimen tips for APT analysis
•  Dual-beam FIB instrument is more advantageous since one can alternate
between the gallium+ (Ga+) ion beam and the e-beam for milling and
imaging to check progress
•  Can fabricate conductive, semi-conductive, or insulator materials into tips
•  Permits site-specific specimen fabrication
•  Multi-step method that is derived from TEM specimen fabrication methods

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 Focused Ion Beam (FIB)
Instrument

•  In situ moat method – Material surrounding the region of interest (ROI) is

removed by Ga+ ion milling that is then annularly milled into a needle-
shaped post for APT analysis
•  In situ lift-out method – Material surrounding the ROI is milled and then
extracted using a micromanipulator and mounted on a pre-fabricated
post. It is then annularly milled into a needle-shaped post for APT
analysis

Image from Google Images.

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 Focused Ion Beam (FIB)
Instrument

•  In situ Moat Method

•  Circumferential milling
•  Annular milling

Miller and Russell (2007)

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 Focused Ion Beam (FIB)
Instrument

•  In situ Lift-Out Method

•  Milling of ROI

•  Creation of Specimen Blanks

•  Annular Milling

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Focused Ion Beam (FIB)
Instrument

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 Focused Ion Beam (FIB)
Instrument

•  Focused Ion Beam (FIB) Instrument

•  Works very well almost all materials including odd geometries, such as flakes,
powders, sheet, etc.
•  Easier to control location and final geometry
•  Ga+ ion implantation in specimen tip will affect mass spectrum
•  User skill is critical for fabricating successful specimens
•  References
•  M. K. Miller and G. D. W. Smith, “Atom Probe Microanalysis: Principles and Applications to
Materials Problems”, Materials Research Society, 1989.
•  M. K. Miller, “Atom Probe Tomography: Analysis at the Atomic Level”, Springer, 2000.
•  B. Gault, M. P. Moody, J. M. Cairney, S. P. Ringer, “Atom Probe Microscopy”, Springer 2012.

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 Focused Ion Beam (FIB)
Instrument

•  References
•  G. B. Thompson, M. K. Miller, and H. L Fraser, “Some aspects of atom probe specimen
preparation and analysis of thin films”, Ultramicroscopy, 100 (2004) 25 – 34.

•  M. K. Miller, K. F. Russell, and G. B. Thompson, “Strategies for fabricating atom probe

specimens with a dual beam FIB”, Ultramicroscopy, 105 (2005), 287 – 298.

•  K. Thompson, D. Lawrence, D. J. Larson, J. D. Olson, T. F. Kelly, and B. Gorman, “In situ

site-specific specimen preparation for atom probe tomography”, Ultramicroscopy, 107
(2007), 131 – 139.

•  M. K. Miller and K. F. Russell, “Atom-probe specimen preparation with a dual beam

SEM/FIB miller”, Ultramicroscopy, 107 (2007), 761 – 766.

•  Some pre-2004 references by Larson.

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 In situ Fabrication

•  In situ fabrication
•  Fabrication of tips through catalytic growth methods, e.g. nanowires

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