Energy Dispersive X-ray Spectroscopy

EDS, EDX, EDAX, etc.

Detect X-rays emitted by incident electrons Determine compositional information at high spatial resolution

Bremsstrahlung X-rays
Incident e- undergo Coulombic repulsion with charged atomic species in the sample, e- energy is lost
Conservation of energy and momentum requires that photons are produced X-ray photons due to braking (Bremsstrahlung) gives rise to an energy continuum

Eo E I continuum ( ) = i p Z E
Gives rise to background in EDS measurements, must be removed before quantification

Inelastic Scattering - X-ray emission

After the incoming e- beam excites inner shell e- in the sample, the excited e- decay back to a ground state In order to obey energy conservation, they emit an X-ray
The X-ray energy is dependent upon the elements present within the sample Can quantify composition by measuring these energies (EDX) May also emit an Auger e-

Most X-rays generated are re-absorbed by the sample (will discuss later in quantitative analysis) X-ray energies are labeled by the type of transition (see graph previous page):
decay of L to K shells: K decay of M to K shells: K decay of M to L shells: L etc. K1 = K to LII K3 = K to LI, but is not an allowed transition (see table in book CD)

Inelastic Scattering Characteristic X-ray Formation

Bohr model - electrons around an atom will equilibrate in certain energy levels around an atom Energy levels are dependent upon the nuclear mass and the number of electrons

More Characteristic X-rays

Excited e- decay time ~ 1ps The probability of a transition is given by:
Incident electron energy (in practice, we want an accelerating voltage 1.5x the energy of the highest X-ray peak) Critical Ionization Energy (Ec) a certain E is required in order to excite a characteristic X-ray (greater than X-ray E) in general, as Z decreases, Ec decreases - table of all Ec available in table on book CD Cross section for ionization

Q = 6.5110
Fluorescence Yield

20

ns bs log(csU ) 2 UEc

Ratio of X-rays produced to the number of shell ionizations Increases with Z, resets with each X-ray line (K, L, M)

X-ray Detection
How detect the energy dispersion of the emitted X-rays? Similar to the p-n BSE detector
X-rays hit a semiconductor, produce electron-hole pairs The number of pairs produced is proportional to the energy of the X-rays Si(Li) detector diffusion produced p-n junction that has intrinsic region ~mm range under reverse bias

Si(Li) detectors: must be kept cold (77K) to stop E field induced diffusion and reduce thermal noise Other detectors: HPGe, proportional counters, microcalorimeters, silicon drift detectors

X-ray detection
The number of e/ho pairs created equals the X-ray energy divided by the energy needed per charge (3.8eV/charge in Si(Li) detectors) ex: for a 5keV Xray, 1316 carriers are produced, which results in a charge of 2x10-16C for most detectors How do we measure such a small charge?

EDS Windows: block stray light, avoid oil and ice contamination, sometimes seal vacuum Window Materials: Be (old systems), polymer films (TW, UTW, SUTW, most common in new systems), windowless

X-ray detection
The charge is converted to voltage by the FET The voltage pulse is then shaped and processed by a set of amplifiers Problem: want to average out noise (need many pulses), but this must happen before another X-ray comes into the detector and charges pile up

X-ray pulse processing

Solution: use 2 amplifiers Fast amplifier determines when a pulse is coming in or not, and if there are 2 overlapping pulses discriminator and pile-up inspector decide whether to reject or accept the pulse Slow amplifier actually does the pulse shaping so the peak height can be converted into X-ray energy

Time Constants and Dead Time

Important stuff from all the pulse processing Time Constant - time allowed for the pulse processor to evaluate the magnitude of the pulse
short time constant, more counts per second, but with decreased energy resolution long time constant gives better resolution, but smaller cout rate

Dead Time - period of time between when a pulse is processed and the detector shuts off to when the detector can measure another pulse (closely related to the time constant)

EDS Spectra
Bremsstrahlung background Characteristic peaks illustrating the presence of individual elements

Analyzing EDS Data

What we know:
How X-rays are generated How the X-rays are measured in a detector How the pulse processor turns the detector signal into X-ray energies

What we can do with this info:

Analyze what elements are in the samples Quantify how much of each element is in the sample

Qualitative EDS
Qualitative EDS - find out what elements are present
pick highest peak intensity and highest energy first match each of the peak lines with the energies of the X-rays

Today - all systems are computerized

use software to scan through the element lists and determine what is present by which peaks line up with what is in your spectrum careful of SUM PEAKS! *ALL measurable peaks* (K, L, M) must match with the elements you think are there - just one line ID does not mean it is correct

Problems - many elements have peaks that overlap with other elements
Note: Dont forget what you coated your samples with! Au/Pd can overlap with many elements
Element Os Ti V Cr Line M K K K Interferes with Al, P, S, Cl Sr V Cr Mn Line K K K K K

Si Escape Peaks
It is probable that an incoming X-ray will ionize the Si within the detector material, producing electron/hole pairs, Auger electrons, and characteristic Si X-rays Some of these characteristic Si K X-rays can escape from the detector This shows itself as an extra peak within the EDS spectra with an energy equal to the characteristic X-ray energy minus the Si K X-ray energy (1.74eV) The probability of forming escape peaks increases as the energy of the incoming Xray approaches 1.74eV (see graph) Si escape peaks will not occur for X-ray energies less than the Si K ionization energy (1.838ev)

Detector Resolution
Energy spread of the detector is dependent upon several factors:
natural line width of the characteristic X-rays electronic noise (cool with LN2) pulse processing abruptness of the p-i-n junction in the Si(Li)

Full width at half maximum (FWHM) is determined at optimal If the FWHM is known at one conditions and standardized for a energy, it can be determined at given composition (Mn), time other energies by: constant, and dead time 2 1/ 2 FWHM = [2.5( E E ) + FWHM ref ref ] Typical ideal resolutions ~137140eV

Quantitative Analysis
Following qualitative analysis (what elements are present), we may be able to quantitatively determine what composition is present What controls X-ray intensity?
Composition (number of X-rays at a certain energy being emitted from the sample) X-rays produced = (ionizations/e-)*(X-rays/ionization)*(atoms/mole) *(moles/g)(g/cm3)(cm) Detection process (how many X-rays emitted get measured) X-rays detected = (X-rays/ionization)*(fraction emitted towards detector)*(detector efficiency)*(dead time)*(signal processing efficiency) etc..

More Quantitative Analysis

Best way to elminate all of those efficiency factors, etc. is to do Standards Based analyses
take a sample of known composition (preferrably close to one that you are trying to measure) and collect spectra using good collection statistics (30% dead time, long collection times, etc.) and standard beam conditions (the same gun bias, spot size, collection area, etc. you are going to use on your sample) calculate the composition of your sample from:

Ci ZAF ( Ii ) Cst ZAF ( Ist )

ZAF = correction for Z (atomic #), A (absorption) and F (fluorescence)

ZAF Correction Factors

Z - larger atoms, more BSE (with relation to standard) A - X-rays must escape the surface without being reabsorbed
dependent upon the (z) distribution of x-ray production with depth into sample

F - fluorescence - X-ray energy from one element is enough to fluoresce an X-ray from a neighboring atom, typically zero for <5keV, larger if the X-ray energies are close together

More ZAF
(z) distribution is dependent upon accelerating voltage!

Special Topics - Quant EDS of Thin Films

Thin Film Correction
Model with Monte Carlo Need to know substrate comp. Errors large if thickness of film unknown High spatial resolution if no substrate (STEM)

Can also use back to bulk analysis - use low kV such that interaction volume is similar to film thickness

Special Topics - Quant EDS of Particles

Particle Analyses
Particle size vs. interaction volume Alters take off angles Measure many particles to look for inhomogeneities / irregularities in spectra

Special Topics - Quant EDS

Surface Roughness Artifacts
Minimize by tilting sample towards detector

Low Z Analyses
Use lowest possible U to avoid large A factors and deal with detection efficiency problems Use windowless detectors (can make results suspect) z corrections important Quantitative analysis very difficult

EDS Summary
Measure composition qualitatively using software, making sure all lines match up Measure standard composition and ZAF correction factors Measure sample, quantitatively determine composition using correction factors Quantitative musts:
choose standards and conditions carefully be aware of ZAF corrections - if ZAF moves significantly away from 1, bad data

Good things about EDS

Fast spectra collection Easy to operate Small, low cost system

Bad things about EDS

Spectral artifacts Poor resolution

WDS Intro
Wavelength Dispersive Spectroscopy (WDS) Used in electron probe microanalysis (EPMA)
Use crystal of known crystallography and take advantage of Braggs law to increase resolution

WDS Analysis System

WDS Crystals

WDS Analysis
Advantages
High resolution if take off angle remains same Low Z analysis Lower background

Disadvantages
Slow (need many counts) Large detector can limit imaging resolution Mechanical movements needed

EDS / WDS Sampling

How determine composition of your sample?
BSE imaging can illustrate possible compositional changes in the specimen Composition from a specific position: spot mode Composition from set of specific positions: multipoint spectrum collection Composition from an area: area scan mode Composition from a boundary: line scan mode Composition from an array of specific positions: mapping (spectral imaging, dot mapping, X-ray mapping, etc) Allows for determination of phase distributions Allows for determination of minor phases Quantitative mapping possible

EDS Mapping - Setup

Qualitative mapping
Max count rate using high beam currents, analytical WD, tilt sample towards detector Small time constant, low dwell times at each pixel Ex: 1000cps, 512 x 512 bitmap, 30% deadtime 1 sec dwell time: 375,000 sec, 6240 min, 104 hours! Better solutions: decrease dwell time (lower total counts) or use smaller energy range for analysis Ex: 0.02sec dwell time: 7,500 sec, 125 min, 2 hours Long scan times: need drift correction

Quantitative mapping
Need sufficient counts and energy resolution to do background subtraction, ZAF corrections Usually sacrifice spatial resolution to prevent long scans

Data Recall (all images courtesy EDAX)

Recall EDS data from each pixel (voxel)

Produce element maps Produce line profiles from spectral images

EDS Mapping
Digital Dot Mapping (spectra at each pixel)
Window around energy region of interest Displaying data: Grayscale - intensity of peaks given grayscale value (need for scaling the data) Color - intensity again scaled to give bright / dark areas, different colors given to different elements Modern EDS systems allow for determination and display of composition at each pixel or along line profiles

Quant Map - ZAF Corrected

BSE SK S K ZAF

Pb L ZAF

Pb M

Pb M ZAF

Live Spectral Mapping

Frame averaging gives gradually better EDS data at each pixel, displays live maps either elementally or as overlay

Electron Energy Loss Spectroscopy

EELS
Typically used in the TEM / STEM Can be done in parallel and serial modes Measures the amount of energy lost by an electron after it passes through a sample of some thickness

EELS
Bend electron beam around hemispherical analyzer to separate e- of different energies in space Can also select a certain window of e- energies to image with (energy filtered TEM, EFTEM or GIF)
Make maps of composition without STEM

EELS
Information gathered from EELS
Characteristic energy loss gives elemental composition, complementary to EDS Zero loss peak intensity gives sample thickness if mean free path length is known Plasmon losses give information about majority carrier mobility Ability to map electronic conductivities, etc. At high energy resolution, can get information about bandgap Need specialized electron source

FIB
Focused Ion Beam
Controlled milling / machining using ion beams

Ion - Solid Interactions

Elastic / Inelastic collisions Sputtering: Elastic collisions, momentum transferred from incident ions into the target atoms, forming secondary ions (SI)
aka backsputtering SIs can be measured by its own plate detector, gives rise to different contrast than SEs, similar to BSE

Inelastic scattering: produces SE, phonons, plasmons, etc.

Nuclear Electronic

Ion - Solid Interaction Ranges

R = range Rp = projected range Xs = projected range along a vector normal to the surface Rr = radial range

Collision Cascades
Collision cascade: moving sea of particles within a solid under ion bombardment 3 regimes:
I. Single knock-on (M1<<M2 or Eo is low) Recoil atoms do not receive enough E to generate a cascade and sputtering is minimal II. Linear cascade (M1 ~ M2, moderate Eo) Recoil atoms receive enough energy to generate a cascade, but the density of moving atoms is dilute enough to disregard multiple collisions and collisions between moving atoms Normally operate FIB in regime II III. Spike regime (M1>>M2, Eo is high) Majority of atoms within the spike volume move during the collision cascade

More Ion - Solid Interactions

Modeling energy loss in amorphous solids
Universal screening function leads to the stopping power of the target material Take into account both conservation of momentum and the interatomic potential Best for MSE scientists to model with SRIM calculations (Monte Carlo, www.srim.org)

Ion Implantation
Flux - time rate of flow of energy (ions / cm2 / s) Fluence - number of particles incident on a specific area (ions / cm2) during a certain time interval Dose - quantity of ions absorbed by a medium (ions / cm2) Beam Current / Current Density - time rate of flow (Amps (C/s) or Amps / cm2)

More Ion - Solid Interactions

Sputtering - sputtering yield = # ejected particles per incident ion
Depends on target, incident energy, angle of incidence In FIB, sputter yield varies between 0.1 and 100 Ejected ion energies typically between 2-5eV

Sputter yield tables

Nova 200 Nanolab

Dual beam: FEGSEM FIB EDS Omniprobe EBSD Mounted directly under FIB column

The FIB Instrument

Similar to SEM optically Accelerate ions into a solid sample - but why? Attachments:
GIS Liftout / manipulator Dual Beam EDS, EBSD

FIB Column
Optically similar to SEM
Consists of: Gun (next slide) Condenser Lens Beam defining aperture (changes spot size and beam current alone, no real change in condenser setup) Beam blanker - Faraday cage which brings beam out of optic axis and into bulk material Objective lens - changes focal length Scan coils Stigmators

FIB Sources
Liquid Metal Ion System (LMIS)
heat Ga metal above melting temperature Ga flows to a W tip with radius ~2-5m use field emission to form 2-5nm Ga tip (Taylor cone) extract Ga+ ions and accelerate them down the column Ga flow continuously replenishes source

FIB Imaging
SE detection
same as SEM (E-T detector) spatial resolution limited by large interaction volume, aberrations (large energy spread for incident beam)

SI detection
can image insulators!!! - as long as charging is not too severe similar to BSE - only line of sight ions hit the detector

Topographical contrast
surface roughness introduces contrast into the electron image

Channeling contrast
ion channeling into individual grains at different orientations gives different backscatter yields, thus contrast

FIB Ion Column Channeling Contrast

FIB Imaging - Problems

Ion beam can damage / alter the surface you are trying to image
Sputtering can take the surface of interest away Beam induced grain growth Secondary Ga phase formation

FIB Milling
Effects of Z, crystal orientation, incidence angle Damage (amorphization, theatre curtain)
effects of accelerating voltage, beam current, angle of incidence

Redeposition Grain Growth Ga secondary phase formation

FIB Milling - Theatre Curtain Effect

FIB Milling - Redeposition

FIB Milling - Effects of Orientation

FIB Milling - Parameters

Can mill using patterns
Rectangle - mill top to bottom, reverse, or side to side Cross section (swimming pool) Cleaning cross section (one line at a time progressively towards endpoint) Circle or donut (mill top to bottom, reverse, side to side, or annular)

Can also mill using bitmap (24-bit RGB)

R: not used G: 0 - 255 (0 = blanking, 255 = no blanking) B: dwell time (0 = 100ns, 255 = determined by user) Only works in 100ns steps If user defines 500ns dwell time, only 5 milling levels allowed If user defines 500s dwell time, 5000 levels allowed (better depth control Can ultimately define depth by changing the number of passes

More FIB Milling Parameters

Computer analyzes milling data pixel by pixel
Max number of points = 1Million Pitch (x,y) = size of mill set in UI / #pixels in image Pattern resolution = HFW / pixels in length Overlap = resolution / spot size (given by selected beam current aperture)

Decreasing overlap (necessary at low beam currents) changes milling rate and possibly structure

FIB TEM Specimen Preparation

Geometries
H bar or Swimming Pools Wedge polishing / FIB finishing Omniprobe Wedge FIB and total liftout technique Plan-view

In-situ and Ex-situ liftout Artifacts

Ga implantation / contamination - reduce with low kV cleaning Theatre curtain / Amorphization - prevent with Pt Spotting

FIB TEM Specimen Prep

In-situ Liftout

Dual Beam FIB

Allows for 3-D reconstructions from serial sections
IMOD (U. Colorado software) AMIRA (Mercury software, tgs.com) EDS - TEM prep EBSD - TEM prep

Courtesy: IMOD

X-C SEM preparation FIB SIMS FIB Auger

Other Ion Systems in the FIB

Gas Injection Systems (GIS), i.e., Deposition (e-beam, i-beam) Allow for deposition / etching of structures using gases other than the Ga beam precursor chemical is heated and injected into the beam path of the electrons / ions via a long needle precursor is converted into metallic species Methylcyclopentadienyl Pt trimethyl - (CH3)3(CH3C5H4)Pt Tungsten Hexacarbonyl, W(CO)6 Trimethylamine Alane, (CH3)3NAlH3 TEOS, TMOS + H2O - SiO2 Phenanthrene, pyrene, napthalene for C deposition On roadmap: Au, Pd, Co, Fe Enhanced Etching chemistries gaseous chemical is injected into the Ga beam path, enhances the etch rate by reacting with the target material Halogens used most often (XeF2, Cl2, Br2, I2) for Si, SiO2, Al, W also H2O for PMMA and polyimide Delineation etch (2,2,2-trifluroroacetamide) removes insulator, leaving Si intact CuRx - reduces Cu channeling / preferential sputtering Selective C mill - removes organics and plastics, leaving inorganics intact

GIS Deposition with e- and ions

Ion Beam Deposition 1. High dep rate 2. Ga contamination 3. Residual surface damage 4. Effects of beam tail limit minimum feature size e- beam deposition 1. Lower dep rate (~0.2) 2. No Ga contamination 3. No surface damage 4. C and porosity content increased 5. Smaller structures possible

3-D Nanofabrication
Use GIS deposition to produce nanoscale 3-D structures Usefulness:
connect lines in IC devices lithography mask repair MEMS Milling cap layers

3-D Nanofabrication

3-D Etches
Useful for variable etching rate materials and devices

FIBIX
X-ray spectroscopy induced by Ga beam
No Bremsstrahlung X-rays, greatly reduced background and higher resolution at low Es Very sensitive at low Es No high E X-rays detectable Need nA to get decent spectra Sample will not last long in spot mode at these high beam currents