UW- Madison Geoscience 777

Electron probe microanalysis -

Scanning Electron Microscopy
EPMA - SEM

Preface:
Whats EPMA and SEM all
about?
How does Geology 777 work?
What can you learn? Updated 1/16/13
UW- Madison Geology 777

Why?
You are taking this class because you need to be able to
intelligently use one or both of the Departments electron
beam instruments -- the Cameca SX51 electron microprobe
in Weeks 306 or the Hitachi S3400 SEM in Weeks 308.
Both instruments work on the same physical principles, but
have differences.
Traditionally this class has focused primarily upon the
electron microprobe, but over the past few years more
material has been added to address specific issues with
increased usage of the SEM. It is a work in progress
UW- Madison Geology 777

EPMA - what is it?

EPMA is a tool to get precise
and accurate quantitative
chemical analyses of micron-
size domains of our samples.
A focused beam (spot) of
high energy electrons interact
with the atoms in the sample,
yielding X-rays (and other
signals), which we quantify
and compare with counts from
standards. It is nominally non-
destructive.
UW- Madison Geology 777

SEM - what is it?

SEM is a tool to produce
images -- pictures -- of our
samples. A rastered
(scanned) beam of high
energy electrons sweeps
across the surface, interacting
with the atoms in the sample,
yielding backscattered
electrons, secondary electrons,
auger electrons, and in some
cases photons in the visible
light range (CL). It is
nominally non-destructive.
UW- Madison Geology 777

EPMA - is it for me?

This technique has its own characteristics, strengths, weaknesses. It pays
to consider whether it is the best technique to get the information you
need.
1) It is a micro-technique, and for multiphase samples provides discrete
compositions, not the bulk composition.
2) Under normal operataing conditions, it samples volumes (widths-
depths) on the order of ~1-3 um, limiting its usefulness for smaller
inclusions or thin films.
3) It provides major and minor element quantification, and has limited
capacity for trace element analysis. (What do you mean by trace?)
4) Despite being non-destructive, samples need to be mounted and
polished; they can be reanalyzed many times.
5) It is relatively inexpensive and accessible
6) Some degree of complexity; there can be a sharp learning curve
UW- Madison Geology 777

SEM - is it for me?

1) This technique is rather simple and one can learn the essentials in a
short time.
2) It provides images easily, though one needs to understand the various
parameters (e.g. working distance, resolution, etc) to not make
mistakes compromising image quality.
3) Samples may be imaged with little or no preparation (coating,
mounting+polishing), though this may complicate detailed
examination.
4) It is very easy to make mistakes using the easy EDS software,
especially for attempts to get chemistry of small particles.
UW- Madison Geology 777

Goal of this course

The goal is to provide useful background information to make
SEM and EPMA less a black box for you and to help you
make better decisions about how to analyze your samples,
and to understand when data is good and when it is not.
This class will provide the basic instructions for the use of our
Hitachi SEM and Thermo-Fisher EDS. It will point out errors
that can occur with EDS spectral interpretation.
This course provides some directed exercises with our
Cameca SX51. The electron probe is much more complicated
than the SEM and experience has shown that individualized
training is the best way to go. Which means this happens only
when the student has his/her samples ready to analyze do we
set up a 4-8 hour appointment.
UW- Madison Geology 777

How this course is structured

Weekly class meetings: ~1.5 hours, discussion of
assigned materials (PPT presentations, readings);
students will be responsible for many of the readings
Weekly quiz: at start of each class, on the assigned
material
Weekly labs: ~2 hours. Complete lab report and turn in
following week
Weekly assignments: Calculations and computer
exercises.
Each student will present an assigned published paper
UW- Madison Geology 777

Use for
Reference--In
Library on
Reserve
Goldstein et al,
3rd Edition.
2003 New:$75
UW- Madison Geology 777

Also On Reserve in Geo Library

Reed (1996) 201 pages Reed (1993)

Paper: New:$36 Paper: New:$55 Used:$35?
Hard:New: $95 Used $80 Hard:New ~$95
UW- Madison Geology 777

EPMA - ideal case

Simple assumptions: We have stuck our sample in
epoxy, cut and polished it (or made a thin section
epoxied to a glass slide and polished it). There are
standards, either user-supplied, or in the probe lab. We
sign up on the schedule, get some on the job training,
and analyze our samples. We return to our office with
the data we need ready to show our advisor.
UW- Madison Geology 777

The devil in the details

Optimal case for easy EPMA: The samples are flat,
well polished, conductive, non-porous, infinitely thick
(to e- beam), homogeneous, clean. Standards exist and
have the same 5 features. Materials are oriented at 90
to the electron beam (not tilted). Background positions
well chosen with no peak or background interferences
(in both unknown and standard). Detector pulse
distribution well centered. Constants for matrix
correction (e.g. mass absorption coefficients) well
known. Sample is not able to be altered by beam.
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EPMA real case details

Possible complications: The actual materials being
probed are scratched or etched, insulators, porous,
multiphase (eutectic) assemblages, with polishing oil in
pores. 1 round has surface that is not normal to walls,
resulting in tilted surface to electron beam. Background
and peak positions have interferences. Detector pulse
distribution on standard depressed (cut off) on low end.
Mass absorption coefficients poorly known. Specimen
is a particle -- or a thin film. Specimen is hydrous or
sensitive to alteration or damage by the beam electrons.
A main goal of this course is for you to understand
when the optimal conditions are met -- and when they
are not -- and if there is a way to make this thing work!
UW- Madison Geology 777

EPMA - so what to do?

How to trust the results?: Evaluate secondary
standards. Should get 100 wt% totals (98.5-101).
Evaluate stoichometry if able to.
How to get the best results: Get the sample preparation
right. Have multiple standards for difficult samples.
Take some time at the start: Dont be in a hurry with a
new sample/suite of elements. Do wavescans first to
consider peak and background interferences.