Lecture Module #14 Introduction to Electron Microscopy An overview What are electron microscopes? • Scientific instruments that use a focused beam of electrons to examine objects on a very fine scale. What is electron microscopy? • Electron microscopy is the science and technology of using an electron beam to form a magnified image. • Advantages: – The use of electrons rather than light provides a nearly 1000 fold increase in resolving power (i.e., ability to focus fine details) over light. • Disadvantages: – High cost – Time commitment – Small areas of analysis Magnification • Refers to how large an object can be made (and still resolved). magnification = size of image size of object • Advantages: – You get higher magnification with electron microscopes techniques than you can with light. – Smaller wavelength Æ higher resolving power. Resolution is: • The closest distance between two points that can clearly be resolved as separate entities through the microscope. Resolution is defined by: ↓ Intensity Consider light as EM energy transmitted as a wave motion. Abbe relationship d 0.61λ 0.61λ ro = 1 = = NA 2 n sin α λ = wavelength of illuminant α = semi-angle We can consider light as a series of ripples impinging upon an obstacle. ro Distance d1 n = index of refraction NA = numerical aperature B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) Depth of Field Important Terms • Depth of Field • A measure of how much of the object that we are looking at remains in focus at the same time. – Height above and below the plane of focus that an image remains sharp. – DOF is a function of magnification, α, and probe size • Advantages: BEAM α – You get higher depth of field with (many) electron microscopy techniques than you do with light. Scan Plane of focused image DOF – WHY? Region of image in focus SEM TEM Other instruments we have or are getting • DualBeam Focused Ion Beam (DB-FIB) – Nano-machining platform • X-ray photoelectron spectrometer / Auger (XPS/Auger) EPMA What do we get out of electron microscopes? • ??? Comparison of Selected Characteristics of Light and Electron Microscopes FEATURE • Topography – Surface features of an object. “How it looks.” • Morphology – Size and shape of particles making up object. • Composition – Relative amount of elements and compounds making up the object. • Structure – Crystallography. How atoms are arranged in the object Light Microscope SEM Uses Surface morphology and sections (1-40 µm) Surface morphology Source of Illumination Best resolution Magnification range Depth of field Visible light High-speed electrons 200 nm 10-1,000× 0.002-0.05 nm (NA=1.5) Glass On eye by lens 3-6 nm 20-150,000× 0.003-1 mm Lens type Image rayformation spot Information generated Limiting Factor Phases Reflectivity Wavelength of light Electromagnetic On CRT by scanning device Topography Composition Crystal orientation Brighness, signal/noise ratio, emission volume TEM Sections (40-150 nm) or small particles on thin membranes High-speed electrons 0.2 nm 500-500,000× 0.004-0.006 mm (NA=10-3) Electromagnetic On phosphorescent screen by lens Crystal structure Crystal orientation Defects Composition Lens quality Adapted from: Scanning and Transmission Electron Microscopy, S. L. Flegler, J.W. Heckman Jr., K.L. Klomparens, Oxford University Press, New York, 1993. All of this information is related to properties. History of electron microscopes • Developed due to limitations of light optical microscopes (LOMs) – LOM: ~1000x magnification; 0.2 µm (200 nm) resolution properties structure • Transmission Electron Microscope (TEM) was developed first. processing – M. Knoll and E. Ruska, 1931 – Patterned “exactly” like a LOM. Uses electrons rather than light. • Scanning Electron Microscope (SEM) performance – 1942 Mechanical, Physical, Thermal, Optical, Electrical, etc… Goodhew, Humphreys & Beanland Electron Microscopy and Microanalysis, 3rd Edition Taylor & Francis, London, 2001 70X How do electron microscopes work? • Form a stream of electrons in the electron source (thermionic emission) and accelerate them towards the specimen using a positive electrical potential. 300X Electron microscopy provides significant advantages over light optical microscopy in terms of resolution and depth of field • Use apertures and magnetic lenses to focus the stream into a thin focused monochromatic beam 1400X • Focus the beam onto the sample using another magnetic lens. 2800X • Interactions occur inside the irradiated area of the sample. Collect results of interactions in a suitable detector and transform them into an image (or whatever you are interested in). Electron Source (i.e., electron gun) The Electron Gun • The electron gun provides an intense beam of high energy electrons. • There are two main types of gun. The thermionic gun, which is the most commonly used, and the field emission gun. • Electrons are generated and emitted from a filament by thermionic emission (W or LaB6) or from a sharp tip by field emission (single crystal of W). Thermionic electron gun most widely used (~$70K-$150K) Electrons are emitted from a heated filament and accelerated towards an anode W Filament Bias resistor Wehnelt cap (negative potential) Space charge Electron Beam – 10-1000 kV + Crossover Anode Plate (positive potential) • The electrons are accelerated through a potential difference. Wehnelt A biased grid with a potential that is a few hundred volts different than the filament (cathode). This helps to accelerate the electrons and causes their paths to cross over. W Filament Wehnelt cap Crossover The effective source of illumination for the microscope. The size is critical for high resolution applications. (negative potential) Space charge Electron Beam Filament Made from a high Tmp material with a low work function (φ) in order to emit as many electrons as possible. The work function is the energy needed by an electron to overcome the barrier that prevents it from leaking out of the atom. φW = 4.5 eV, φLaB6 = 3.0 eV. Ground Operation of thermionic gun • Apply a positive electrical potential to the anode • Heat the cathode (filament) until a stream of electrons is produced Bias resistor – 10-1000 kV + Crossover Anode Plate – >2700 K for W • Apply a negative electric potential to the Wehnelt – electrons are repelled by the Wehnelt towards the optic axis • Electrons accumulate within the region between the filament tip and the Wehnelt. This is known as the space charge. • Electrons near the hole exit the gun and move down the column to the target (in this case the sample) for imaging. (positive potential) Ground Anode Positively charged metal plate at earth potential with a hole in it. It accelerates the electron beam to the high tension potential. Other Types of Electron Sources (i.e., electron guns) The function of the electron gun is: Lanthanum hexaboride (LaB6) Higher brightness than W. More $$$ (~$500K) Field emission source Highest brightness. Even more $$$ (~$750K) ADVANTAGES Provide higher current density → Higher brightness To provide an intense beam of high energy electrons There are two main types of gun. The thermionic gun, which is the most commonly used, and the field emission gun. Brightness, B, is the beam current density per unit solid angle. B = jcπβ2 jc = current density β = convergence angle http://www.matter.org.uk/tem/electron_gun/electron_sources.htm Beam-Specimen Interaction • This is what makes electron microscopy possible. • Electrons strike the sample leading to a variety of reactions. Interaction Volume • Represents the region penetrated by electrons – Signals must escape the sample to be detected Incident high kV beam of electrons Secondary e(SE) Backscattered e- (BSE) Auger e- Characteristic x-rays Incident electron beam Visible light Bulk (SEM) Absorbed e- e- - hole pairs Foil (TEM) Bremsstrahlung x-rays (noise) Interaction Volume Elastically scattered e- Inelastically scattered e- Direct (transmitted) beam • Use results of reactions to form image or generate other information. Secondary electrons Backscattered electrons X-rays Different signals come from different depths in the target (sample) INCIDENT BEAM Interaction Volume ~5–50 nm Secondary electrons ~50 nm TEM specimen thickness ~1 nm – Auger electrons • X-rays: – most escape – sampling volume ≈ interaction volume ~300 nm Backscattered electrons • Backscattered electrons: ~1.5 µm X-rays – originate further from the incident beam (some fraction of a µm) • Secondary electrons: ~1.0 µm X-ray resolution – escape from a region slightly larger than the incident beam (several µm) – yield the best spatial resolution Z = 29 (Cu), Accelerating voltage = 20kV Backscattered electrons (BSE) • Formation – Caused when incident electrons collide with an atom in a specimen that is nearly normal to the path of the incident beam. – Incident electron is scattered backward (“reflected”). • Use – – – – Imaging and diffraction analysis in the SEM. Production varies with atomic number (Z). Higher Z elements appear brighter than lower Z elements. Differentiate parts of specimen having different atomic number Backscattered electrons are not as numerous as others. However, they generally carry higher energies than other types of electrons. Secondary Electrons (SE) • Formation – Caused when an incident electron “knocks” and inner shell electron (e.g., k-shell) out of its site. – This causes a slight energy loss and path change in the incident electron and ionization of the electron in the specimen. – The ionized electron leaves the atom with a small kinetic energy (~5 eV) • Use – IMAGING! – Production is related to topography. Due to low energy, only SE near the surface can exit the sample. – Any change in topography that is larger than the sampling depth will change the yield of SE. More abundant than other types of electrons. They are electrons that escape the specimen with energies below ~50eV X-rays Auger Electrons (AE) • Formation – De-energization of the atom after a secondary electron is produced. – During SE production, an inner shell electron is emitted from the atom leaving a vacancy. – Higher energy electrons from the same atom can fall into the lower energy hole. This creates an energy surplus in the atom which is corrected by emission of an outer shell (low energy) electron • Use – AE have characteristic energies that are unique to each element from which they are emitted. – Collect and sort AE according to energy to determine composition. – AE have very low energy and are emitted from near surface regions. Transmitted electrons • Can be used to determine: – – – – – thickness crystallographic orientation atomic arrangements phases present etc. • Foundation for Transmission Electron Microscopy (TEM) • Formation – Same as AE. Difference is that the electron that fills the inner shell emits energy to balance the total energy of the atom. • Use – X-rays will have characteristic energies that are unique to the element(s) from which it originated. – Collect and sort signals according to energy to yield compositional information. – Energy Dispersive X-ray Spectroscopy (EDS) Foundation of XPS (X-ray photoelectron spectroscopy). XPS can be used to determine the “state” of an atom and to identify chemical compounds. Specimen Interaction Volume • Volume where electron beam - specimen interactions occur. • Depends upon: – Z of material being examined • higher Z materials absorb more electrons and have smaller interaction volume – Accelerating Voltage • higher voltages penetrate further into the specimen and generate larger interaction volumes – Angle of incidence of electron beam • larger angle leads to a smaller interaction volume INCIDENT BEAM ~5–50 nm Secondary electrons ~50 nm TEM specimen thickness INCIDENT BEAM ~100 Å Secondary electrons ~1 nm – Auger electrons ~50 nm TEM specimen thickness ~300 nm Backscattered electrons 10 Å - 30 Å – Auger electrons <1µm - 2µm Backscattered electrons ~1.5 µm X-rays ~5 µm X-rays ~1.0 µm X-ray resolution ??? X-ray resolution Z = 29 (Cu), Accelerating voltage = 20kV Z = 28 (Ni), Accelerating voltage = 20kV Increasing incident energy (E0) “Instruments of the trade” ~50 nm • Primary Instruments – Transmission Electron Microscope (TEM) – Scanning Electron Microscope (SEM) Z1 • Variants Z2 Z1 < Z2 < Z3 Z3 Increasing atomic number (Z) • Interaction volume is larger for materials that have lower atomic numbers and for higher incident beam energies! – – – – – – Electron Probe Microanalyzer (EPMA) Scanning Transmission Electron Microscope (STEM) Environmental SEM (ESEM) High Resolution TEM (HRTEM) High Voltage TEM (HVTEM) etc... The TEM is analogous to the transmission LOM TEM TEM LOM Electron gun • Patterned after transmission light optical microscopes Vacuum column Light source Condenser system Apertures z z y + Tilt & rotation • Yield Following Information: Source y Stage x x – Morphology Objective lens • Size shape and arrangement of particles, precipitates, etc. Final imaging system – Crystallographic information • Atomic arrangement Phosphor screen; film; digital recording system – Compositional Information Eyepiece or TV screen; film; digital recording system Observation and recording system • If proper detector is present 1 in 1020 electrons are collected Components of the TEM • Source – filament plus anode plates with applied accelerating voltage. Electron gun Vacuum column • Condenser Lenses – electromagnetic lenses adjusted by lens currents not position. z y + Tilt & rotation x • Specimen Stage – allows translations and tilts. • Objective Lens – usually <50X. • Imaging System – multiple electromagnetic lenses below the objective: set magnification, focal plane (image vs. diffraction pattern). • Observation – fluorescent screen, plate film, CCD camera. Phosphor screen; film; digital recording system 1 in 1020 electrons are collected Adapted from B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) <1 in 106 photons are collected Condensor Lenses OPTICAL LENS Light Source MAGNETIC LENS Electron Source ELECTROMAGNETIC lenses focus the electron beam to as small a spot as is possible. They are equivalent to convex lenses in optical lens systems. Soft Fe pole pieces Adapted from B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) Cu coils N N S S Electrons in Magnetic Fields Electron Lenses • Use electrostatic or electromagnetic fields to focus beams of charged electrons. • ELECTROMAGNETIC – Most lenses are of this type. Consist of Cu wire coils around soft Fe cores. Sometimes an Fe pole-piece is used to “shape” the field. A. Electrons moving through a perpendicular magnetic field experience perpendicular forces. B. Electrons moving parallel to a magnetic field are unaffected. C. Electrons moving nearly parallel to a magnetic field take a helical path around the magnetic field direction (i.e., the microscope axis). A B C Nearly aligned electron electron • ELECTROSTATIC – Unusual. Only common example is the Wehnelt aperture in the electron gun. Force on electron is out of plane unaffected Magnetic field No Force Electrons follow a helical path Adapted from B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) Beam Tilting and Translation Trajectories in Electromagnetic Lenses • When you adjust the magnification (and the focal length), you modify the lens strength by adjusting the current in the electromagnetic lens coils. • Since the magnetic field is changed, MAGNETIC LENS so are the helical trajectories. Electron Source • This ultimately leads to image Soft Fe pole rotation which must be corrected pieces for or calibrated. N N S Object S Cu coils Rotated image Image is inverted and rotated • The electron beam can be positioned for fine measurements (spot modes) or scanning (SEM, STEM) BEAM TILTING APPARENT ORIGIN Upper scan coil Lower scan coil BEAM TRANSLATION APPARENT ORIGIN Condenser Alignment • In TEM it is important to center the condenser aperture about the optical axis. • If the aperture is off center, the beam is displaced away from the axis when the condenser lens is focused. • You can try condenser alignment at: Condenser Astigmatism • Astigmatism in the condenser lenses distorts the beam to an elliptical shape either side of focus and prevents the beam being fully focused. It is corrected by applying two orthogonal correction fields in the x and y directions. • You can try stigmator adjustment at: http://www.matter.org.uk/tem/condenser_astigmatism.htm http://www.matter.org.uk/tem/condenser_alignment.htm Objective Aperture • Depending upon where you position the objective aperture and whether or not you tilt the beam, a bright field image, a dark field (i.e., scattered) image, or a diffraction pattern can be collected. • You can look at this in more detail at: http://www.matter.org.uk/tem/dark_field.htm B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) AND http://www.matter.org.uk/tem/stem_images.htm B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) BF TEM Micrograph and SADP NiAl-1.0Hf Grain structure Crystallographic information B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) [111] zone axis BF TEM Micrographs Defect Structures NiAl-1.0Hf β′ 250 nm 1hr NiAl-1.0Hf 100 nm 4hr Precipitate distribution Defect structures Dislocations imaged in NiAl-0.5Zr single crystals deformed at elevated temperatures. HAADF (Z-contrast imaging) analysis Nano-scale X-ray Analysis As-deposited Annealed 1000°C/1h 1 2 Hf rich region β′ Ni2AlHf β′ -NiAl EDX spectrum β′ -precipitate NiAl-1.0Hf 200 nm NiAl-1.0Hf 20 nm • Hf segregates to GB’s in as-deposited & annealed coatings. • Hf precipitates as β´-Ni2AlHf phase after annealing. How does a TEM work? Electron Beam • Pass a focussed beam of electrons through a thin foil Thin Foil < 500 nm thick • As beam passes through sample, it is scattered • Project the transmitted (scattered) beam onto a phosphor screen to form an enlarged image • Modes: – Bright Field/Dark Field modes for visualization of structure and defects – Selected Area Diffraction/Convergent Beam Diffraction for crystallographic information Schematic Representation of optics in a TEM Technical Details Electron Gun Anode Plate First Condenser Lens (C1) • Produce a stream of monochromatic electrons in the electron gun • Focus the stream into a small coherent beam using C1 and C2 – C1 determines the “spot size” (i.e., size of electron probe) – C2 changes intensity or brightness Second Condenser Lens (C2) Condenser Aperture Sample • Use condenser aperture to restrict the beam • Part of the beam is transmitted through the sample • Focus transmitted portion using the objective lens to form an image • Objective and selected area apertures are used to restrict the beam further Objective Lens Objective Aperture Selected Area Aperture First Intermediate Lens Second Intermediate Lens Projector Lens Phosphor Screen – allows examination of diffraction from specific atoms, crystals, features… – SAD, CBD Used to magnify image. • Enlarge image with intermediate and projector lenses TEM SEM SEM Electron gun Electron gun • Patterned after reflecting light optical microscopes Vacuum column • Yield Following Information: Condenser lens Condenser system z y – Topography Scan coils Stage Also tilts and rotates • Surface features of an object. Detectable features limited to a few nanometers depth. x Objective lens – Morphology Time base Probe lens z Signal amplifier y Final imaging system • Size shape and arrangement of particles, precipitates, etc Stage x Also tilts and rotates Detector and processing system Observation and recording system – Compositional Information • Elements and compounds the sample is composed of CRT – Crystallographic information • Possible using new techniques (OIM/BKD) In the SEM you use secondary signals to acquire images. Components of an SEM • Source: Schematic Representation of the optics in an SEM Electron gun – same as TEM but lower V Condenser lens • Condenser: Electron Gun Anode Plate First Condenser Lens (C1) Condenser Aperture Second Condenser Lens (C2) – same as TEM Scan coils • Scan Coils: Time base Objective Aperture – raster the probe Scan Coils Probe lens • Probe Lens: – lens that forms a spot at the specimen surface • Detector & Processing System: – collects signals such as X-rays and electrons as a function of time and position. – Provides digital images for real-time viewing, processing, and storage. z Signal amplifier y Stage x Also tilts and rotates Objective (probe) Lens Detector and processing system tor Detec CRT Sample SEM: Technical Details • Produce a stream of monochromatic electrons in the electron gun • Focus the stream using the first condenser lens – Coarse probe current knob • The beam is constricted by the condenser aperture (eliminates high-angle electrons) • Second condenser lens is used to form electrons into a thin, tight, coherent beam. – Use fine probe current knob • Use objective aperture to limit beam (i.e., eliminate high-angle electrons) • Scan coils raster the beam across the sample, dwelling on the points for a predetermined period of time (selected using scan speed) • Final objective lens focuses beam on desired region. • When beam strikes the sample, interactions occur. We detect what comes out of the sample. γ' Substrate 80 γ + γ' Ni 70 60 Ni-AD Ni-Annealed 50 Substrate IDZ 40 40 Coating Al Al-AD Al-Annealed 30 Secondary electron mode γ+γ′ γ γ′ γ+γ′ Composition (at%) 20 10 0 40 Pt Pt-AD Pt-Annealed 30 20 10 0 1.0 10 µm 0.8 Could get additional information in backscattered or mixed mode Hf Hf-AD Hf-Annealed 0.6 0.4 0.2 0.0 -15 -10 -5 0 5 10 15 20 Distance (µm) Figure 4.8. Composition profiles of the major elements measured by WDS in an EPMA. 25 X-ray Analysis in the SEM EDS or WDS Useful things to remember about SEM operation Al2O3 + ??? • Change magnification by changing the scan area • Focus by changing the objective lens current ??? Ni Al O Pt Hf O Hf Pt Al Ni • The probe current/spot size are controlled by the condenser lens current Elemental diffusion profile NiAlPtHf coatings on CMSX-4 substrates for a temperature of 1150°C and times from (a) 20 hrs and (b) 100 hrs. B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) Microanalysis in Electron Microscopy B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) WDS • Yields best discrimination of emitted X-ray signal • Characteristic X-rays are always generated by interactions between the incident electron beam and the sample. They constitute a fingerprint of the local chemistry. • Use a series of bent crystals to cover the range of wavelengths of interest • Collect X-ray signal to determine local chemistry • Scan wavelengths within each range by rotating the crystal and moving the detector while keeping the position of the crystal fixed. • Common Techniques: – Wavelength-Dispersive Spectrometry/Spectroscopy (WDS) – Energy-Dispersive Spectrometry/Spectroscopy (EDS) • X-rays are collected from the sample at a fixed angle. The angle at the collecting crystal will vary with 2θ and the diameter of the focusing circle will change WDS WDS continued Bent crystal Radius = 2R • All peaks are scanned sequentially. You cannot record more than one characteristic line at once unless there are multiple spectrometers available. Focusing Circle • EPMA! Specimen Receiving slits R X-ray Detector • Data is collected sequentially. Takes more time but the results are much more precise than EDS. EDS vs. WDS • Pulse height is recorded by the detector. It is related to the energy of the photon responsible for the pulse. • Solid-state detectors are generally used. • EDS is faster than WDS • Problems with EDS: Resolution of M lines in a WDS spectrum of a superalloy (Oxford Instruments) – Poor discrimination or energy resolution. WDS systems are much better, particularly when characteristic lines from different elements overlap. – Need a windowless or thin window detector to pick up light elements. – WDS is more quantitative Can use BSE signal in conjunction with SE signal to yield enhanced topographical information Images • Topography and atomic number influence signal. • Backscatter coefficient: – η = -0.254 + 0.016Z - 1.86x10-4Z2 + 8.3x10-7Z3 SE image Multiple elements of BSE detector “Overlapping shadows” Reduced resolution • Atomic number contrast: – C = (η1 - η2)/ η1 Single segment of BSE detector The BSE sampling volume is large which limits resolution TOPOGRAPHIC CONTRAST TOPOGRAPHIC CONTRAST Signals from 2 detectors B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005) B.D. Huey, MMAT322 Lecture Notes, University of Connecticut (2005)