Scanning Electron Microscopy (SEM) Electron Probe Microanalysis (EPMA)

Analytical Methods in Materials Science 2009

Per Eklund
(based on original lecture by Hans Hgberg)

Outline

Practical aspects Basic principle Imaging with SEM Determination of elemental composition (EMPA/EDS/WDS)

Overview SEM is easy to use Routinely used in both research and industry And not just in materials science geology, archaeology, forensics, biology, Image interpretation is intuitive and simple (unlike TEM) SEM (1950s) is a much younger technique than TEM (1930s)

Practical aspects SEM is easy to use, but to learn how to use it WELL you need: practice practice, and practice!!! But it doesnt hurt to know a bit about the theory as well

Principles of SEM
Sample information obtained from the interaction between a primary electron beam and a material. The better focusing and the smaller wavelength of electrons (compared to light) enables: Higher magnifications >100000x Better resolution 10 - 50 LOM 3000 Increased depth of field 2 m -1 mm LOM m
The ability of an optical device to keep out-of-plane features in relatively good focus.

Technique allows for sample imaging (morphology topography) determination of elemental composition, electronic properties (cathodoluminescence)..

Electron interaction with matter

The electron excitation results in ejection of electrons and photons, which can be collected, detected and evaluated. Auger electrons from the surface region <50 , carry elemental and chemical information (compare AES) Secondary electrons formed by excitation of the surface elements at 50 100 depth, EK<50 eV sensitive to topography Backscattered electrons generated in the whole volume, high energy 50 eV< EK>E E-beam, composition and crystallographic information Visible light (cathodoluminescence) electronical/optical properties, band gap

E-beam Surface
Auger e

Excitation volume

Secondary eBackscattered eCharacteristic X-rays Visible light

Instrumentation SEM
The specimen is scanned by an E-gun incident electron beam and the electrons and/or photons emitted Lens from the surface are collected, system detected and analysed. Scan coil The lenses in the microscope Final lens condenses and demagnfies the electron beam to form a focused spot on the surface. TV screen Probe sizes 30- 60 . Analysis requires high vacuum (HV) conditions. (Exception: environmental SEM, low-vacuum Specimen Detector Pumps SEM) Specimen must be electrically condutive. Schematic diagram of a
scanning electron microscope

Primary electron source

The performance of the electron source is important for the final result in SEM analysis
W-filament, common in old instruments, relatively low brightness, probe size 6 nm =4.5 eV, lifetime 50 h LaB6 crystal, much higher brightness, =2.7 eV, lifetime 300 h, more sensitive

FEI Company

Field emitter, in new instruments excellent brightness, probe size 3 nm, lifetime 100 h or more, UHV conditions

The source should exhbit: low energy spread minimise the chromatic aberration high brightness low workfunction resonable lifetime Electron beam generated by either: filament technique LaB6 crystal Field emission (cold or hot) most common today Electron gun operated at 0 to 30 keV (60 keV) acceleration voltage

Electromagnetic lenses SEM

The lenses in a SEM instrument use electrostatic or magnetic fields to influence the electron tragectories of the primary beam. (LOM refraction or reflection) Electrons are forced to move in the center of the lens to minimize rotation around the optical axis. spherical aberration The lens system aims to form a focused point on the specimen Spot size defines the resolution small spot yields high resolution Apertures to adjust beam divergence, i.e. the mutual repulsion between electrons moving together.

Electro-Magnetic lens

Lens system SEM

Electron gun

Condenser lens

y-pla es x-pla t

tes

Scan coil

Objective/ final lens

Sample

The condenser lens controls the beam size (amount of electrons in the column) Increasing the size of the beam yields a better signal to noise (S/N ratio), but the larger beam diameter results in a lower resolution. The objective lens focuses the beam into a spot on the sample. Necessary to have an image in proper focus The scan coils enables deflection of the beam by varying the potential between the plates. The beam can be scanned across the sample.

Specimen properties in SEM

Samples should be:
Vacuum compatible (low vapor pressure) solid material etc. organic/biological samples possible after pre-treatment Electrically condutive Charge-up effects on non-conductive samples compensated by: reduced probe current reduced acceleration voltage coating by a thin metal film (Au, Pt)

Image obtained from fly

Image obtained from carrot

Imaging modes in SEM

The electrons and photons generated in the excitation volume carry different types of information from the analysed specimen.
Secondary electrons Backscattered electrons Absorbed specimen current Cathodoluminescence

Topographic Voltage Magnetic and electric field

Topographic Crystallographic Composition

Topographic Composition

Electronic Optic

Imaging using secondary electrons

Secondary electrons are produced when the incident electrons from the beam interacts with the atoms in the surface region of specimen. The impact (collision cascade) causes a path change for the incident electron and an ionization of several specimen atoms. The ejected electrons leave the atom with a very small kinetic energy (<50eV)

Pictures from Arizona State University

LOM picture

SEM picture

High-resolution imaging of fine surface morphology (resolution about 3.5 nm). Sensitive to the orientation of different surface features (edges etc.) creates an image contrast ideal for evaluating the sample's surface topography. Three-dimensional appearance of the specimen image, due to the large depth of field and the scanning mode applied in SEM.

Secondary electron emission

Yield proportional to

i * ( ) e

[C (1 cos )]

Incident electron beam

High yield

No yield Low yield

Secondary electron emission

Secondary electron emission depends on topography topographic imaging

Depth of field
Depth of field represents that distance along the microscope axis over which the specimen can be displayed without blurring the image.

Electron beam

d D tan = 2 2
Magnification Resolution
20 5 m 1 m 500 nm 100 nm 20 nm 10 nm

d D
Image plane

Depth of field SEM LOM

1 mm 200 m 100 m 20 m 4 m 2 m 5 m 2 m 0.7 m

100 200 1000 5000 10000

Depth of field
Magnification Resolution
20 100 200 1000 5000 10000 5 m 1 m 500 nm 100 nm 20 nm 10 nm

Depth of field SEM LOM

1 mm 200 m 100 m 20 m 4 m 2 m 5 m 2 m 0.7 m

Depth of field in SEM >> depth of field in LOM

Imaging using backscattered electrons

Backscattered electrons (BSE) are high-energy electron produced by the elastic collision of the incident electron beam with the electron cone of the sample atoms. Backscattered electron imaging provides elemental composition variation, as well as surface topography. (resolution about 5.5 nm) Yield is proportional to the atomic number (Z contrast) and depends on the beam energy and incidence angle. The larger escape depth compared to secondary electrons results in less good surface topography in imaging. Mapping of individual elements Detectors for combining topography and composition signals.

Polyphase garnets (Na, K, Al, Mg, Fe minerals), due to the Z contrast in the BSE image the Ferich compositions appear brighter.

Imaging using backscattered electrons

Backscattered electrons: topographic or compositional imaging

Cathodoluminescence in SEM
Cathodoluminescence (CL) is the light emission associated with the excitation of materials by an electron beam. Method usually applied to semiconductor materials, but also other classes of materials (e.g. in geology).
Courtesy Jens Birch, Thin Film Physics, LiU

SEM image of a pinhole defect in an AlN film grown on a 5kV 6H-SiC substrate 5 kV
CL

15 kV

In CL the focused electron beam is used and to excite a small region of the sample. (volume depends on the beam energy) The light emitted is evaluated and used to collect a spectrum. (element/compound specific emission lines) By changing the energy of the beam it is possible to perform depth profiling of the optical properties.

CL image =346 nm AlN emission line

CL image =496 nm 6H-SiC emission line

Other analysis modes in SEM

The SEM instrument can also be used to obtain information regarding the structural, magnetic and electrical properties of the specimen.

Additional techniques are:

Electron channelling (EC) crystalline materials symmetry, orientation and lattice information Electron Backscattered Diffraction (EBSD) comparable with EC, also called orientation imaging microscopy (OIM) Magnetic contrast imaging ferromagnetic materials Electric contrast imaging

Electron channelling pattern (ECP) from quartz

Detectors applied in SEM

Secondary electrons
E-T detector Secondary electrons ejected from the specimen are analysed by an Everhart-Thornley detector (E-T). The E-T detector consists of a Faraday cage in front of a scintillator, coupled to a light pipe leading to a photomultiplier tube The Faraday cage is held at a positive potential of a few hundred volts to collect the low energetic secondary electrons In the scintillator the electrons are accelerated to produce light upon impact. The photomultiplier produces an output signal related to the total number of electrons collected.

BSE detector

SEM chamber with E-T detector and BSE quadropole detector

Detectors applied in SEM

Backscattered electrons
The high-energy BSE are collected by a silicon diode (solid-state) detector. -Collisions with the semiconductor generates electron-hole pairs. -Number of pairs dependent on the electron energy. -Migration of the holes and electrons creates a potential, which produces a current dependent on the electron flux and the electron energy. Qudropole detectors are often used to individually mix topographic and composition information obtained from the BSE. A scintillator (modified E-T detector) can used as BSE detector. -No collection potential needed for bakscattered electrons -Collection yield related to scintillator size and specimen proximity

Silicon diode detector Polepiece

Backscattered electron detector assembly

Influence of acceleration voltage SEM

The acceleration voltage affects the size, shape and yield (ratio between backscattered and secondary electrons) of the excitation volume. High resolution Small probe size

High

Unclear surface structures More edge effects More charge-up More damage

Clear surface structures Less damage Less charge-up Less edge effects

Acceleration Voltage

Low resolution

Low

Larger probe size

Influence of probe current/diameter SEM

The achievable magnifications and resolutions for a SEM image are highly dependent on the probe diameter (size) and the probe current. Smooth image

Large

Deteriorated resolution More damage

High resolution obtainable Less damage

Probe current

Grainy image

Small

Influence of working distance SEM

The distance between the sample surface and the final/objective lens. Changed by raising or lowering the specimen. Distance typically between a few mm to 30-40 mm. High resolution

Small

Smaller depth of field

Low resolution

Working distance

Greater depth of field

Large

Influence of objective aperture SEM

The objective aperture lens regulates the amount of signal nesecessary for forming an image in SEM

Large current

Large

Low resolution Smaller depth of field

High resolution Greater depth of field

Aperture size

Grainy image

Small

Summary so far

Secondary electron imaging: topographic imaging only, high resolution Backscattered electrons: topographic or compositional imaging, modest resolution

Electron Probe Microanalysis (EPMA)

The electron beam specimen interaction also results in the emission of characteristic X-rays, which can be detected and analysed.
X-rays are produced in the whole excitation volume -characteristic X-rays (elastic) -bremsstrahlung (inelastic) -fluorescence from X-rays Yield/ratio depends on acceleration voltage and speciment composition Characteristic X-rays are used for -qualitative analysis -quantitative analysis Detection of the elements: -Wavelength Dispersive X-Ray Detector (WDS) -Energy Dispersive X-Ray Detector (EDS) -(Gas flow proportional counter)

Characteristic emission Bremsstrahlung

X-ray emission

Detectors in EPMA
Comparision between Energy Dispersive X-Ray Detector (EDS) and Wavelength Dispersive X-Ray Detector (WDS)
EDS
Solid-state detector Records X-ray energies Requires no focusing of X-rays Limited energy resolution (~100 eV) Light element analysis difficult Allows smaller electron probes, but poor accuracy at low concentrations Simple design Complete elemental spectrum displayed Operates at cryogenic temperatures (77 K) VERY EASY TO USE Not so easy to use WELL!

WDS
Crystal spectrometer Records X-ray wavelenghts Spatial separation of X-ray lines High resolution (~1 eV) Light element analysis with proper choice of crystal High sensitivity for trace elements Space consuming Analysis of one element at a time Peak and background measured separately Slow, complicated

WDS detector in EPMA

Principles of the of the Wavelength Dispersive spectrometer

X-ray diffraction separate the different X-ray energies wavelengths Requires a set of crystals with different lattice spacing to cover all the element in the peroidic chart Focusing requires moving detector and crystal use much more space than EDS detectors. WDS resolution is far superior to the EDS resolution applied in careful analytical work

Crystals applied in WDS

Crystal Lithium fluoride (LiF) Germanium (Ge) Sodium Chloride (NaCl) Ethylene diamine tartrate (EDT) Pentaerythriol (PET) Ammonia dihydrogen phosphate (ADP) Ortho-phtalate postassium hydrogen (KAP) Ortho-phtalate rubidium hydrogen (RAP) Gypsum Stearate (STE) Laurate (LAU) Cerotate (CER) W-Si multilayer Ni-C multilayer Wavelength Range (nm) 0.1-0.38 0.11-0.60 0.09-0.53 0.14-0.83 0.14-0.83 0.18-1.03 0.34-2.5 0.2-1.08 0.26-1.5 2.5-8.5 4.0-13.5 2.5-11.9 Atomic number range for K radiation 19-35 16-34 16-37 14-22 14-22 12-21 11-14 11-14 11-14 5-8 6-9 4-7 4-7 4-7

EDS detector in EPMA

Soild-state detector -semiconductor crystal Si(Li) -protected from contamination by a Be-window or thin polymer (Mylar) window -cooled in i LN2 to minimize the thermionic creation of charge carriers -front and back of crystal kept at high potential difference -X-rays generates electron-hole pairs -electron-hole pairs exhibit a characteristic creation energy - the total number of charge carriers created is proportional to the incident X-ray energy

EDS detector

Qualitative EDS analysis

EDS spectra contain the characteristic emissions (K, L, M) from all elements (Z>4) in the specimen Spectrum displayed as intensity as a function of energy Light elements difficult to detect if you have a Be window -mylar-window normal in modern systems -windowless analysis possible Spectrum treatment somewhat difficult -separation between characteristic peaks and bremsstrahlung -separation of diferent elements and emissions -light elements difficult to quantify

EDS spectrum with intensity as a function of energy

Quantitative analysis EPMA

The measured intensity (I) is converted to composition of each element (A) (weight or atomic percentage) Analysis technique use references of known composition Calculated from

IA = ( ZAF )CA I ' ( A)

Correction of the atomic number (Z)

due to different probabilities for backscattering (scales with the atomic number)

Correction of the absorption (A),

depends on the shape and size of the excitation volume (acceleration voltage and specimen composition)

Correction of the secondary fluorescence (F) small effect

depend on the acceleration voltage

Summary EMPA
Quantitative analysis with EDS difficult in many cases: -lack of suitable standards -element separation in spectrum -light elements difficult to quantify -secondary fluorescence strong for elements that are nearest neighbors (Z<21, e.g. Al and Si) or next nearest neighbors (Z>21) in the periodic table Quantitative anlysis works well for many normal materials, IF YOU HAVE SUITABLE STANDARDS!!! Superb method for qualitative analysis mapping are elements present or not, and where are they (mapping)

SEM picture and Ni and C elemental maps from a BCN film grown on Ni