Characterisation Tools for

Nano @ IITB

Ajit Kulkarni
I. I. T.-Bombay
 Why this talk here?
• Process may be based on a recipe – if it does not
work, what next?
• Or a new process is developed, how do you develop
an understanding of the process?
• Characterise the product, a material.
• What do we mean by characterisation?
• More difficult to define the question than to answer it
• So once again…what is Characterisation?
 Charcterisation of the
UNKNOWN……material
• Characterisation is the study of
structure (including microstructure)
and composition (including trace level).
• Charcterisation makes use of one or
more structure, composition-property
correlation previously established.
• Is it a catch-22 problem?
– Or is it the limitation
Characterisation of Materials - composition,
structure, microstructure, mapping

• Philosophy
– No characterisation is complete or absolute
– Characterisation is not a goal unto itself.
– Time, cost and need determine the methodology
of characterisation along with its limitations.
– One has to look for ‘IT’ to see it. One may see
‘IT’ if ‘IT is there. ‘IT’ can’t be seen if you don’t
look for ‘IT’ even if it is there. One may not see
‘IT’ even if ‘IT’ is there, because it depends on
how you look for ‘IT’.
Analysis - Probes and Signals

What can be learnt from these signals?

photons
EXCITATION EMISSION
• bonding geometry of molecules ions

electrons
• physical topography
• chemical composition
Interaction
• chemical structure with material

• atomic structure
• electronic state

TRANSMISSION
 Probes and volume of interaction
Volume of interaction depends on nature of probe (photon /
electrons / ion) and its penetrability), sample(density), the
way, the signal spreads laterally in the sample (scattering).

Ultimately, this determines, lateral resolution and depth

resolution for the analysis. Operating parameters of the
instrument (acceleration voltage) alters energy of electrons
and hence depth of interaction volume.

In a scanning electron microscope, spot size or cross

section of e-beam limits lateral resolution .

In transmission electron microscope, the wavelength and

the energy spread limits resolution.

Of course, the instrument may set an upper limit.

(aberrations)

In ESCA, the escape depth of electrons determines the

 Analytical Techniques – a comparison
Analytical Technique Signal Measured Elemental Range Depth Resolution Surface info.

IMS Secondary Ions H-U 5-30 Å Chemical composition

Chemical structure
OF-SIMS Secondary Ions H-U, Large Organic 2000 Å (Scanning Mode) Adsorbate bonding
Molecules / Cluster Ions
EM Transmitted Electrons X-Rays Na-U EDX N/A

E-SEM, EDX Backscattered or Na-U 1 - 5 micrometres

Secondary Electrons and X-Rays
SS Ions H- U monolayer atomic structure
on scattering spectroscopy) chemical composition
ES/SAM Auger Electrons Li-U 2-30nm chemical composition
uger electron spectroscopy, scanning Auger microscopy)
SCA/XPS Photoelectrons Li-U 5 - 30nm chemical composition
lectron spectroscopy for chemical analysis, X-ray photoelectron spectroscopy) chemical structure
AIRS IR photons organic, some inorganics monolayer Adsorbate bonding
eflection-absorption infra-red spectroscopy)
TM - solid surfaces upper most atoms physical topography
canning tunnelling microscopy)

Analytical Technique Signal Measured Elemental Range Depth Resolution surface info,
 Sample size, nature and
the need for standards
In TEM, ~3 mm diameter sample of a few hundred Å thick
is studied. Does it represent the ‘bulk’. What is the effect
of this sampling procedure?

Surface and bulk analysis ? What you see on the surface

need not represent bulk. ESCA / Auger looks at a few
nanometer thick layers only. EDAX may look at signal
averaged over a depth of one micron. Even exposure to
air may add / modify the surface.

Signal from one constituent may get altered by another

constituent – interference
Even microstructure can alter signal strength.
Matrix effects – make things difficult to quantify
Nearly identical standards are needed. Convenient for
quality control in a plant. How about an R&D lab?
Some times analysis of each sample is a research project.
 Some jargons to remember
Signal to noise ratio
Background correction
Spectral resolution (can be Mass resolution)
Sensitivity
Limit of detection
Range of measurements
Calibration
Interference and Matrix effect
Reference or standard

No single technique can offer a universal solution.

 Probe-material interaction –an
example… X- ray as a probe
X-rays in photoelectrons out

KE

Sample Surface Layer Ev

φ
Ef
valence
band BE
photon

core
levels
ding energy (eV) = photon energy - kinetic energy - work function
BE (eV) = hν - KE – Φ
asuring (signal) electron intensity and energy will give quantitative and
alitative information
 After Photoemission……

X-ray Fluorescence or Auger electron emission

XRF/ EDAX / WDS / Electron probe micro analyser/AE
Fluorescence yield
Analytical tools based on above fundaes

• Fluorescence X-rays (XRF)

• Diffracted X-rays (XRD)
• Emitted Electron (AES)
• Photoelectron (XPS)
X-ray Fluorescence Spectroscopy

Emitted X-rays can be used to analyse the

atom that is emitting
Qualitatively
and
Quantitatively
Triggering emission – signal it can be X-rays,
electrons, Ions
XRF
EDS / WDS in SEM / EPMA/ TEM / STEM
Ion probe microanalysis
In X-ray fluorescence measurements, intensity of
characteristic radiation emitted by analyte atom
is measured

Intensity of X-rays is a function of

incoming signal intensity

absorption cross section
Fluorescence yield
concentration of atoms in target
self absorption
Matrix effect

when it is measured the

Signal measured is a function of

Detector characteristics
Collection geometry
…Matrix effect
rface and Bulk Analysis – constraints

A sample with a surface of size 1 cm2 - this

will have ~ 1015 atoms in the surface layer. In
order to detect the presence of impurity
atoms present at the 1 % level, a technique
must be sensitive to ca. 1013 atoms. Contrast
this with a spectroscopic technique used to
analyse a 1 cm3 bulk liquid sample i.e. a
sample of ca. 1022 molecules. The detection of
1013 molecules in this sample would require 1
ppb (one part-per-billion) sensitivity - very
Surface Sensitivity of XPS

X-rays in Photoelectrons out

d
d = 3λ
Surface Sensitivity of XPS
• The average distance from the surface a photoelectron
can travel without energy loss is defined as the
inelastic mean free pathlength (IMFP), λ .
• Sampling depth, d, defined as the average distance
from the surface for which 95% of photoelectrons are
detected, d = 3λ .

‘universal curve’
X-ray Photoelectron spectroscopy is...

Surface sensitive - photoelectron

signal from first 1-10 layers of
atoms and molecules.
Quantitative.
Provides insight into the chemical
state of the element.
 Sensitive - detection limit ~0.1

atomic %.

Able to detect all elements except

H and He.
Depth Profile through a TiN/SiO2 thin film on Si.

Si 2p region as a function
of depth from the surface
• Si 2p region
shows
chemical
environment of
Si the Si atoms.
SiO2
TiN
 Tools for better vision-
microscopy
• Transmission Electron Microscope-
CM200
• FEGTEM-JEM2100F
• CryoTEM*-
• FEGSEM- J7600F
• ESEM*-
• IR microscope –
• Confocal Laser Scanning microscope*
 Sophisticated Analytical Instrument Facility

Instrument Details :
Make : PHILIPS
Model: CM200
Specification : Operating voltages : 20-200kv Resolution :
2.4 Å

Applications :
 Materials Science/Metallugy
 biological Science
 Nanotechnology
 Ceramics
 Pharmaceuticals
 Semiconductors
 Centre for Research in Nanotechnology & Science (CRNTS)

TEM images are formed using transmitted electrons (instead of the

visible light) which can produce magnification details up to 1,000,000x
with resolution better than 10 Å. Further more the analysis of the X-ray
produced by the interaction between the accelerated electrons with the
sample allows determining the elemental composition of the sample with

T high spatial resolution.

Electron beam can be raster scanned over the sample and any
signal generated can be measured as a function of beam position. ..
E Mapping of sample for Composition, morphology etc. (STEM)

M
On the anvil a new
HRTEM (JEM 2100F)
Field emission gun

Higher brightness,
100 times greater
than LaB6 gun
Higher coherency
Higher energy
resolution, 0.7 to
0.8eV
Higher resolution,
increased contrast –
lattice imaging
STEM mode, EDS,
2Kx2K camera 27
 JSM-7600F FEG SEM Scanning
electron Microscope
☆High resolution
☆High stability
☆High productivity
Features of JEOL JSM 7600F
• Designed for Nano sciences
• In-Lens FE GUN
• Aperture angle optimizing lens
• Gentle Beam mode
• Specimen Airlock
 Why you need low kV
20kV 5kV

15kV 3kV
Resolution of JSM-7600F
Specimen: Evaporated gold on carbon

15kV 1kV
Ultra High Resolution by JSM-7600F

Platinum catalyst on carbon 　　 15kV, x500,000

 Composition and mapping
X-ray Fluorescence Spectrometer – Philips 400W

Secondary Ion Mass Spectrometer- Phi-NanoTOF

Induction Coupled Plasma Atomic Emission Spectrometer-

Laser ablation-ICP Mass Spectrometer

EDS and WDS in electron microscopes (STEM, SEM)

ESCA*
PHI nanoTOF TOF-SIMS
Secondary Ion Trajectories in
TRIFT Analyzer
ESA 3 ESA 2

Cs+, C60 +
Energy Slit
Post- for
Spectrometer Metastable
SED Blanker Ion Rejection
Sampl

Pre-Spectrometer
Blanker Angular Acceptance ESA 1
Diaphragm
e

Detector

Ga+, Aun+ User selectable angular acceptance diaphragm

 Superior TRIFT Analyzer Imaging
LMIG FIB cut and TOF-SIMS Images

Total Secondary Ion Image Aluminum Ion Image Silicon Ion Image

Only a PHI TRIFT analyzer can collect ions from

the top surface and the perpendicular face of the
FIB cut
 representative of representative of
reflectron performance TRIFT performance
The TRIFT analyzer is
able to efficiently
collect the secondary
ions that are emitted at
oblique angles (i.e.
ions emitted more
parallel to the substrate
surface).

The ability to collect

obliquely-emitted
secondary ions results
in unequalled imaging
performance.
Oblique angular direction due
to extraction field lines curving
from the substrate over the In
particle.
TRIFT Adjustable Solid Angle of Acceptance
Wide Collection Angle for Superior Imaging Narrow Collection Angle for Best Mass Resolution

SiC Fiber

10µ m 10µ m

Tire Chord

100µ m 100µ m
“Turn Key” Charge Neutralization
 Patented dual beam charge
Low-energy
(A) Electron Beam compensation has been used for many
Analytical Ion Beam
Negative charge
surrounding
years on PHI XPS instruments.
analytical zone
repels electrons.
 The dual beam charge compensation
- - - - - - - - - - - - ++ - - - - - - - - - - -
Insulating Sample method has proven successful at “turn
Sample Platen
key” insulator analysis.

 The dual beam method allows electron

Low-energy
energies below 10eV to be used,
(B) Electron Beam reducing sample damage.
Low-energy
Analytical Ion Beam Ion Beam

 Inert gas ion energies (≤10eV) are below

the damage threshold.
Insulating Sample

Sample Platen
 Effective neutralization enables
insulator imaging at higher
magnifications.
“Turn Key” Charge Neutralization
Sample: bulk PET

Improper charge
100
neutralization.
Total Counts (0.0004 amu bin)

80
Ga+ dose = 2x1011 ions/cm2
raster size = 250 µ m
60 43 m/z of PET m/∆ m = 2,000
40

20

0
42.9 43.0 43.1 43.2

1200 Proper charge C3H7

Total Counts (0.0004 amu bin)

1000
neutralization.
Ga+ dose = 2x1011 ions/cm2
800
raster size = 250 µ m
m/∆ m > 9,000
600 43 m/z of PET C2H3O
400

200
CH3Si
0
42.9 43.0 43.1 43.2
m/z
“Turn Key” Charge Neutralization

3mm thick polypropylene (PP)

5000
100µ m x 100µ m raster area C2H5+
Total Counts (0.0002 amu bin)

10 minute acquisition
4000

3000

m/∆ m > 8,000 @ 29m/z

2000

1000

0
28.95 29.00 29.05 29.10
 Generation of 3D
Isosurfaces and Cross-
Section Images
Y

Si Si
Chemical and Biological tools
Nuclear Magnetic Resonance Spectrometer
Electron pin Resonance Spectrometer
FTIR spectrometer
Fluorescence Spectrometer
CHSN analyser

FACS Cell sorter

Fluorescence Microscope
Tissue culture laboratory
 Other Materials-
Characterisation tools

Thermogravimetry, Differential Thermal analyser

Differential Scanning calorimeter

Image analyser with Optical Microscope –polariser, DIC etc

Confocal Laser Raman Spectrometer – Photoluminescence Spectrometer

Dynamic Light scattering- particle size analyser

Zeta Potential measuring unit

 Centre for Research in Nanotechnology & Science (CRNTS)

Instrument Details :
Make : Thermo finnigan, Italy
Model : FLASH EA 1112 series
Specification : Estimation of CHN/CHNS/O in percentage level to high concentration level.

The CHNS(O) Analyzer find utility in determining the percentages

of Carbon, Hydrogen, Nitrogen, Sulphur and Oxygen of organic
compounds, based on the principle of "Dumas method" which
involves the complete and instantaneous oxidation of the sample by
"flash combustion". The combustion products are separated by a
chromatographic column and detected by the thermal conductivity
detector (T.C.D.), which gives an output signal proportional to the
concentration of the individual components of the mixture.
 Centre for Research in Nanotechnology & Science (CRNTS)

Instrument Details :
Make : VARIAN, USA
Model: E-112 ESR Spectrometer
Specification : X-band microwave frequency (9.5 GHz)

Electron Spin resonance spectroscopy is based on the absorption of microwave

radiation by an unpaired electron when it is exposed to a strong magnetic field. Species that
contain unpaired electrons (namely free radicals, odd-electron molecules, transition metal
complexes, rare earth ions, etc.) can therefore be detected by ESR.
Electron Spin Resonance, ESR, is a powerful non-destructive and non-intrusive analytical
method. ESR yields meaningful structural information even from ongoing chemical or physical
processes, without influencing the process itself. It is the ideal technique to complement other
analytical methods in a wide range of application areas.

Applications :
 Molecular structure  Relaxation properties
 Crystal structure  Electron transport
 Reaction kinetics  Crystal / ligand fields
 Valence electron wave functions  Reaction mechanisms etc.
 Molecular motion
 Centre for Research in Nanotechnology & Science (CRNTS)

Instrument Details :
Make : Nicolet Instruments Corporation, USA

Model: MAGNA 550

Specification : Range - 4000 cm-1 to 50 cm-1

Infrared Spectroscopy gives information on the vibrational and rotational modes of

motion of a molecule and hence an important technique for identification and
characterisation of a substance.. The Infrared spectrum of an organic compound provides
a unique fingerprint, which is readily distinguished from the absorption patterns of all
other compounds; only optical isomers absorb in exactly the same way. Hence FTIR is an
important technique for identification and characterization of a substance.
Applications :
 Chemistry & Chemical Engineering  Food Industries
 Polymer & Rubber Industries
 Agriculture
 Forensic Labs
 Pharmaceutical Labs  Petroleum

 Nanotechnology  Industries
 Sophisticated Analytical Instrument Facility

Instrument Details :
Make : VARIAN, USA
Model: Mercury Plus 300MHz NMR SPECTROMETER
Specification :
5mm Autoswitchable probe with PFG (1H/ 13C/ 31P/ 19F)
5mm Dual Broad Band probe with PFG for Multinuclear NMR
(13C, 15N, 27Al, 31P, 29Si, 77Se, 119Sn, 125Te, 199Hg, 51V, 7Li etc.)

Nuclei with non-zero spins, when placed in a strong magnetic field precess at specific
orientations with respect to the applied magnetic field. When appropriate energy is supplied in the
form of radio frequency, these nuclei flip to a higher energy state. The energy absorbed during this
transition is a function of nucleus type and its chemical environment in the molecule The excited
nuclei are allowed to precess freely and come back to their equilibrium positions. During this
process an electric signal is induced in a suitably placed RF coil. This signal which is monitored
with respect to time is called free induction decay (FID). The FID, which is in time domain gives its
equivalent frequency domain signal on Fourier transformation. A plot of the absorption frequency
versus the intensity of the absorption constitutes the NMR spectrum.
 Centre for Research in Nanotechnology & Science (CRNTS)

Instrument Details :
Make : PHILLIPS (now, PANAlytical, The Spectris Technology, The Netherlands)
Model: PW 2404
Specification: X-Ray tube with Rh target.

X-ray generator:
4 KW with 60 KV, 125 mA (in steps). The generator is solid state
based on 'Switch Mode Power Supply' design to respond fast the
changes sought in X - Ray tube power.