Microscopy

(TEM, SEM, AFM, STM)

 Outline

Introduction
TEM
INTRODUCTION

Electron Microscopy
TEM: Transmission Electron Microscopy
SEM

SEM: Scanning Electron Microscopy

Scanning Probe Microscopy

AFM

AFM: Atomic Force Microscopy

STM: Scanning Tunneling Microscopy
STM
 INTRODUCTION
STM AFM SEM TEM
 10-2 m 1 cm
10 mm

1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
 Optical
Microscopy

Left: transmission
TEM
INTRODUCTION

~ TEM

Right: reflection
SEM

~ SEM

Scanning Probe
AFM

Microscopy

AFM
STM

STM
 Optical Resolution
10-2 m 1 cm
10 mm

1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
 Optical Resolution
10-2 m 1 cm
10 mm

1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

RAYLEIGH CRITERION
X-rays

10-10 m 0.1 nm
 Optical Resolution
10-2 m 1 cm
10 mm

1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
 Optical Resolution
10-2 m 1 cm Ernst Karl Abbe
10 mm

Resolution (Abbe):
1,000,000 nanometers =
10-3 m 1 milimeter (mm) 0.50 𝜆𝜆
𝑅𝑅 =
Microweves
𝑛𝑛 sin 𝛼𝛼
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm Diffraction limit (Rayleigh):

10 µm

0.61 𝜆𝜆
Infrared
SEM

𝑅𝑅 =
10-6 m
1,000 nanometers =
1 micrometer (µm) 𝑛𝑛 sin 𝛼𝛼
Visible

n: refractive index
10-7 m 0.1 µm
n sin α: numerical aperture
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
Resolution limit: ~ 200 nm
(λ violet)
Improve resolution
STM

10-9 m 1 nanometer (nm)

⇓ Lord Rayleigh
X-rays

10-10 m 0.1 nm Smaller wavelength

 TEM Resolution
10-2 m 1 cm
10 mm n = 1; consider first order
0.61 λ
1,000,000 nanometers = R= in TEM: - α << ⇒ sin α ≅ α
10-3 m 1 milimeter (mm) n sin α - α ≈ 0.01 rad
Microweves 𝐑𝐑 = 𝟔𝟔𝟔𝟔 𝛌𝛌
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
EE // keV
keV λrelat / Å R/Å
Infrared
SEM

1,000 nanometers =
50
50 0.0536 ~ 3.3
10-6 m 1 micrometer (µm)
200
200 0.0251 ~ 1.5
Visible

10-7 m 0.1 µm 400

400 0.0164 ~ 1.0
AFM

100 nm

1000
1000 0.0087 ~ 0.5
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
h h
λ= = (De Broglie)
p mv
STM

10-9 m 1 nanometer (nm)

2 −1⁄2
𝐸𝐸
X-rays

Relativistic correction 𝜆𝜆 = ℎ 2𝑚𝑚0 𝐸𝐸 + 2

10-10 m 0.1 nm
𝑐𝑐
 TEM Resolution
10-2 m 1 cm
10 mm

1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
INTRODUCTION

100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
TRANSMISSION ELECTRON MICROSCOPY Outline
INTRO

Introduction

Electron Microscopy
TEM: Transmission Electron Microscopy
SEM

SEM: Scanning Electron Microscopy

Scanning Probe Microscopy

AFM

AFM: Atomic Force Microscopy

STM: Scanning Tunneling Microscopy
STM
TRANSMISSION ELECTRON MICROSCOPY Schema of a TEM
INTRO
Ernst Ruska
(1908-88)
Nobel Prize 1986
SEM
AFM
STM

- worked in electron optics

- designed the first electron microscope
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Schema of a TEM
TRANSMISSION ELECTRON MICROSCOPY Electron Interactions
INTRO Electron beam
Characteristic X-rays
Secondary e–
Bremsstrahlung SEM
X-rays
Back
Auger e– scattered
SEM

Sample… can interacts with electrons

AFM

Scattered
Scattered (elastic) TEM
STM

(inelastic) Transmitted
unscattered e–
TRANSMISSION ELECTRON MICROSCOPY Image Formation
INTRO
SEM Contrast

Medium Low High

Absorption
Transmission
AFM
STM
TRANSMISSION ELECTRON MICROSCOPY Image Formation
INTRO
SEM Contrast

Medium Low High

Electrons
scattered
AFM
STM
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Image Formation
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Image Formation

1,1 nm

3,8 Å
TRANSMISSION ELECTRON MICROSCOPY
INTRO
START
ANIMATION
Incident beam 𝜃

Sample, showing
reflecting planes
𝜃

direct
SEM

Objetive lens
AFM

Back focal plane

(diffraction pattern)
STM

Image plane
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Image Formation
Bright and Dark Field
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO

Bright-Field
Dark-Field
TRANSMISSION ELECTRON MICROSCOPY TEM Images
INTRO MWCNT
Fe/LiF nanoparticles,
coated with graphite
SEM
AFM
STM
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
HREM Images
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Image Formation

1,1 nm

3,8 Å
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Electron Diffraction
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Electron Diffraction
TRANSMISSION ELECTRON MICROSCOPY Electron Diffraction Incident
INTRO
beam
θ
Bragg equation: λ = 2 dhkl sin θ

If λ <<, then also θ <<, and sin θ ≅ θ tan θ ≅ θ

Sample
for electrons 200 kV: λ = 0.025 Å
SEM

Cu Kα: λ = 1.542 Å

s s s
In the picture: tan(2θ) = 2θ = θ=
L L 2L L
AFM

Diffracted
θ
s
Bragg equation: λ = 2 dhkl beam
2L 2θ
STM

λL s
dhkl = λ � L = 𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
s
TRANSMISSION ELECTRON MICROSCOPY Electron Diffraction
INTRO
Electron Diffraction

focus on a nanoparticle: illuminate a large area:

Nano-Area Electron Diffraction Selected Area Electron Diffraction
NAED SAED
IN: IN:

~ 50 nm probe size Can observe a large area

SEM

Useful to study: - individual particles Useful to study: - thick films

- superlattices - bulk samples
- phase transformations
AFM

OUT: OUT:

Very weak beam Lower limit of area selection ~ 0.5 μm

Difficult to see and tilt the sample Difficult to record diffraction from:
STM

- individual nanoparticles
Complex alignment - thin films
TRANSMISSION ELECTRON MICROSCOPY Single Crystal Diffraction
INTRO

NiFe2O4

Spinel structure

Zone axis [1,1,0]

SEM
AFM
STM
TRANSMISSION ELECTRON MICROSCOPY Single Crystal Diffraction
INTRO
Tetragonal Sr2ScFeAsO3

Zone axis [1,0,0]

SEM
AFM
STM
TRANSMISSION ELECTRON MICROSCOPY Single Crystal Diffraction
INTRO

What information can be obtained?

- If the unit cell is known: Index the diffraction pattern

Orientation of the crystal
SEM

- If the basic structure is known: Unit cell parameters

Orientation of the crystal
AFM

- Determine the Bravais Lattice

STM

- Determine possible space groups

TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Powder Diffraction
Polycrystalline
material
TRANSMISSION ELECTRON MICROSCOPY
STM AFM SEM INTRO
Powder Diffraction

Polycrystalline ZnO
TRANSMISSION ELECTRON MICROSCOPY Powder Diffraction
INTRO Coating:

Ti, Cr solid solution

NaCl-type structure
SEM
AFM
STM
 Outline:
INTRO
SCANNING ELECTRON MICROSCOPY

Introduction
TEM

Electron Microscopy
TEM: Transmission Electron Microscopy
SEM: Scanning Electron Microscopy

Scanning Probe Microscopy

AFM

AFM: Atomic Force Microscopy

STM: Scanning Tunneling Microscopy
STM
 Schema of a SEM
INTRO
10-2 m 1 cm
10 mm
SCANNING ELECTRON MICROSCOPY
1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

Schema SEM
10-10 m 0.1 nm
 How SEM works
INTRO
SCANNING ELECTRON MICROSCOPY
How the Scanning Electron Microscope works
TEM
AFM
STM
SCANNING ELECTRON MICROSCOPY
STM AFM TEM INTRO
Interactions
 Interactions
INTRO
SCANNING ELECTRON MICROSCOPY
The incident beam produces various signals that can be detected and that
contain information about the sample's surface topography and composition
TEM

- Low energy e–
~ 50 eV
Secondary - From the surface
Electrons
- Image contrast
AFM

- High resolution
STM
 Interactions
INTRO
SCANNING ELECTRON MICROSCOPY
The electrons are scattered (elastic dispersion) by the sample
The image depends on the nature of the atoms
TEM

- High energy e–
~ incident beam
- Deeper e– (than S.E.)

Backscattered - Proportional to Z
AFM

Electrons
- Information about:
1. Surface
2. Composition
STM
SCANNING ELECTRON MICROSCOPY
STM AFM TEM INTRO
Topography and Contrast
 SE vs. BSE
INTRO
SCANNING ELECTRON MICROSCOPY
Texture and Contrast:
SE / BSE Comparison
TEM

Twisted pair of Ti wires

wrapped around a thicker Ni wire

Secondary electrons

Backscattered electrons
AFM
STM
 SE vs. BSE
INTRO
SCANNING ELECTRON MICROSCOPY
Texture and Contrast:
SE / BSE Comparison
TEM

BSE  contrast, composition

AFM

SE  texture, topography
STM
 SE vs. BSE
INTRO
SCANNING ELECTRON MICROSCOPY
TEM
AFM

Backscattered electrons
STM

Texture and Contrast:

Secondary electrons SE / BSE Comparison
 Incident Energy
INTRO
SCANNING ELECTRON MICROSCOPY
SEM images of vanadium oxide nanotubes
obtained at different electron energies (incident beam)
TEM
AFM
STM
 EDX
INTRO Characteristic radiations
SCANNING ELECTRON MICROSCOPY
Characteristic energy:
Kα, Kβ, Lα, etc Moseley’s law
2
Qualitative and Quantitative Analysis E = 𝐶𝐶1 𝑍𝑍 − 𝐶𝐶2
TEM

Intensity ratio

Kα : Kβ
10 : 1
Lα : Lβ1 : Lβ2 : Lγ
AFM

10 : 7 : 2 : 1

Characteristic Mα : Mβ
X-rays 10 : 6
STM

Detection: 0.1 %
 EDX
INTRO
SCANNING ELECTRON MICROSCOPY
Energy Dispersive Spectroscopy

allows to identify what those

TEM

particular elements are and

their relative proportions
AFM
STM
 EDX
INTRO
SCANNING ELECTRON MICROSCOPY
TEM
AFM

Mapping
previously defined
STM

elements over the

scanned area
 Outline:
INTRO
ATOMIC FORCE MICROSCOPY

Introduction
TEM

Electron Microscopy
TEM: Transmission Electron Microscopy
SEM

SEM: Scanning Electron Microscopy

Scanning Probe Microscopy

AFM: Atomic Force Microscopy
STM: Scanning Tunneling Microscopy
STM
 Schema of an AFM
INTRO
10-2 m 1 cm
10 mm
ATOMIC FORCE MICROSCOPY
1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
 Schema of an AFM
INTRO
10-2 m 1 cm
10 mm
ATOMIC FORCE MICROSCOPY
1,000,000 nanometers =
10-3 m 1 milimeter (mm)

Microweves
TEM

0.1 mm
10-4 m
100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm
STM

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
 Contact Mode
INTRO The tip is dragged across the surface of the sample
ATOMIC FORCE MICROSCOPY

and the contours of the surface are measured

TEM
SEM
STM
 Contact Mode
INTRO The tip is dragged across the surface of the sample
ATOMIC FORCE MICROSCOPY

and the contours of the surface are measured

TEM
SEM
STM
 Tapping Mode
INTRO The cantilever is driven to oscillate up and down at near its resonance
ATOMIC FORCE MICROSCOPY

frequency by a small piezoelectric element mounted in the AFM tip holder

TEM
SEM
STM
 Tapping Mode
INTRO The cantilever is driven to oscillate up and down at near its resonance
ATOMIC FORCE MICROSCOPY

frequency by a small piezoelectric element mounted in the AFM tip holder

TEM
SEM
STM
 Accuracy
INTRO
ATOMIC FORCE MICROSCOPY

The XY scan linearity affects the accuracy of the imaging results

TEM

40 μm
SEM
STM
 Accuracy and repeatability
INTRO
Accurate and Repeatable Surface Roughness Measurement
ATOMIC FORCE MICROSCOPY
TEM
SEM
STM
 ATOMIC FORCE MICROSCOPY
STM SEM TEM INTRO
Shape
Probe shape-hole
 ATOMIC FORCE MICROSCOPY
STM SEM TEM INTRO
Shape
Probe shape-bump
 ATOMIC FORCE MICROSCOPY
STM SEM TEM INTRO
Images
 Images
INTRO
ATOMIC FORCE MICROSCOPY

MgAl2O4
TEM

Spinel structure

Plane (111)
SEM
STM
 Images
INTRO
AFM Cálculo
ATOMIC FORCE MICROSCOPY

Identification of
TEM

Intermolecular
Hydrogen Bonds
SEM
STM
SCANNING TUNNELING MICROSCOPY Outline:
INTRO

Introduction
TEM

Electron Microscopy
TEM: Transmission Electron Microscopy
SEM

SEM: Scanning Electron Microscopy

Scanning Probe Microscopy

AFM

AFM: Atomic Force Microscopy

STM: Scanning Tunneling Microscopy
 SCANNING TUNNELING MICROSCOPY
AFM SEM TEM INTRO
Schema of a STM

Gerd Binnig
Heinrich Rohrer
SCANNING TUNNELING MICROSCOPY
AFM SEM TEM INTRO
Tunnel Effect
SCANNING TUNNELING MICROSCOPY Schema of a STM
INTRO
10-2 m 1 cm
10 mm

Resolution:
1,000,000 nanometers =
10-3 m 1 milimeter (mm)
Lateral ~ 1 Å
Microweves
Vertical ~ 0.1 Å
TEM

0.1 mm
10-4 m
100 µm
Microworld

10-5 m 0.01 mm
10 µm
Infrared
SEM

1,000 nanometers =
10-6 m 1 micrometer (µm)
Visible

10-7 m 0.1 µm
AFM

100 nm
Ultraviolet
Nanoworld

10-8 m 0.01 µm
10 nm

10-9 m 1 nanometer (nm)

X-rays

10-10 m 0.1 nm
SCANNING TUNNELING MICROSCOPY Images
INTRO
Surface of a Silicon cristal, (001)
Magnification ~ 10 millions
TEM
SEM
AFM
SCANNING TUNNELING MICROSCOPY Images Graphene layer Polymer
INTRO
TEM
SEM
AFM showing interferences BN support (+ molecular model)

1 nm
Ag H C
SCANNING TUNNELING MICROSCOPY Images
INTRO
Identification of Intermolecular Hydrogen Bonding

STM AFM Cálculo

TEM
SEM
AFM
SCANNING TUNNELING MICROSCOPY
AFM SEM TEM INTRO
Filled/Empty States
SCANNING TUNNELING MICROSCOPY
AFM SEM TEM INTRO
Filled/Empty States
SCANNING TUNNELING MICROSCOPY Filled/Empty States
INTRO
As dopant atoms in silicon: Si (100)
Filled-state image Empty-state image
TEM
SEM
AFM
SCANNING TUNNELING MICROSCOPY Filled/Empty States
INTRO
White:

Empty-states
NiO Ni

Filled- and Empty-state images

TEM

Ni-1 O Ni-2
SEM

Filled-states
AFM