PHY 6006 – Characterisation Techniques

(Module 7)
Characterization techniques
• Electrical studies – Dielectric and Four probe method
• Magnetic studies – VSM and SQUID
• Mechanical studies – Nanoindentation
• Optical studies – Photoluminesce and UV-VISIBLE spectroscopy
Electrical studies – Two and Four points probe
method
• The potential probe is most commonly employed method for
measuring the resistivity of samples with low resistance value
Conditions are required – Four probe method
• The material possesses uniform resistivity in the measurement area
• If minority carriers are injected in semiconductor via the current conducting
electrodes, much of these carriers recombine at the electrodes and they have
negligible influence on conductivity
• Surface to place the probes should be flat without any surface leakage
• The probes employed in measurement should touch the surface in straight line
• Diameter of contacts between the probes and semiconductor should be smaller
than the gap between the probes
• The material’s surface can be either conducting or non-conducting. The boundary
is conducting when a material having lower resistivity is deposited. Non-
conducting boundary results from plating the semiconductor surface insulator
Electrical studies – Four probe method
• As the current I is injected through the point
contacts placed on the sample(which is a
thin conducting film)having a uniform
resistivity ρ; the current spreads radially and
the current density around the contact

• The thin film approximation is valid only if

the inter spacing between the contacts is
much larger than the film thickness
Electrical studies – Four probe method
• For the ideal case of a 3D semi-infinite material with the four electrodes
equally spaced and aligned along a straight line (a 4P in-line array, the
material resistivity is given by,
𝑉
ρ =2 π 𝑠
I

• Electric field can be expressed as,

ρ 𝑉 𝑑𝑉 Miccoli et al., J. Phys.: Condens. Matter 27, 223201 (2015)
𝐸 ( 𝑟 ) =ρ 𝐽 = =−
2 π 𝑟𝑡 I dr
Electrical studies – Four probe method
• The volume or bulk resistivity (ρ) is
calculated as follows;

Where, V: the voltage measured

between probes
I: the magnitude of the source
current (amps)
t: the sample thickness
k: a correction factor based
Van der Pauw method – Four probe method
• Van der Pauw theorem for isotropic thin films of arbitrary shape
• Four probes must be located on the sample's periphery and are small
compared to the sample size
• Sample must be homogeneous, thin (i.e. t/s < 1/5: F1 = 1), isotropic
and singly connected
Van der Pauw method – Four probe method
• If IAB is the current flowing between contacts A and B, while VCD is the
voltage drop between contacts C and D, the resistance is given
by RAB, CD = VCD/IAB

• Van der Pauw has shown that these resistances satisfy the following
condition (ρ is the resistivity)

1
Van der Pauw method – Four probe method
• For samples provided with a plane of symmetry (where A, C are on the line
of symmetry while B, D are placed symmetrically with respect to this line),
reciprocity theorem gives,
RAB, CD = RBC, DA = R
• This gives resistivity as,
π 𝑡 𝑉
ρ=
ln 2 I

• For non-symmetric samples, the resistivity is generally expressed as;

f

where, f is now a function of the RAB, CD/RBC, DA ratio

Four probe method – Anisotropic crystals and
surfaces
• The evaluation of the electrical resistivity in the case of an anisotropic
solid is in general more complex and demanding

• for isotropic materials the I/V ratio measured with 4P probes along one
axis is directly proportional to the material resistivity

• Anisotropic materials where the I/V ratio measured along one arbitrary
axis simultaneously depends on other resistivity components
(e.g. ρx, ρy, ρz for orthorhombic crystals)
Four probe method – Anisotropic crystals and
surfaces
• Mapping procedure of an anisotropic cubic sample into an equivalent
isotropic parallelepiped
• Dielectric As Vx and Ix are preserved, the resistivity for isotropic
samples, is given by; 𝑉𝑥
ρ=2 π √ 𝜌 𝑥 /𝜌 𝑠 𝑥
I𝑥
• Resistance Rx = Vx/Ix along the x-axis of the anisotropic sample is
given by;
Four probe method – Anisotropic crystals and
surfaces
• In order to reveal information about the
anisotropy either the current/voltage probes
need to be exchanged or the 4P probe
geometry needs to be rotated
• The anisotropy ratio Rx/Ry is easily obtained,
which directly refers to the anisotropy of the
resistivities
• Electrical resistance ratio Rx/Ry versus the
resistivity anisotropy degree ρx/ρy for the
infinite 3D half plane and 2D sheet
depending on the adopted 4P probe
geometric configuration
Electrical studies – Four probe method
• Despite its long history of almost a hundred years, the 4P probe
transport technique is still a leading method in both fundamental and
application-driven research
• In Van der Pauw method, where the shape of the sample is not
important as long as the four probes are located on the sample
periphery or along one of its planes of symmetry
• van der Pauw theorem has been shown to be applicable to anisotropic
materials of arbitrary shape as well, it only allows one to measure the
geometric mean √𝜌 𝑥𝜌 𝑦
ZnO – Electrical studies
• Very low resistivity due to Gd doping
• Metal-semiconductor transition at around 180 K

Temperature dependent resistivity for Gd implanted and 650 oC annealed ZnO

ZnO – Electrical studies
• Resistivity data modelled using inhomogeneous
resistivity model*,
1
 1 1 

R  
 Ra Rm  Rs 

where,
A schematic of inhomogeneous resistivity model with normal metallic, ρ m,
Rm = Rm0 + Rm1 × Tn1; semiconducting, ρs, and disordered, ρa, resistivities (left) and the resistance
network used to model the data (right).
Rs = Rs0 × exp(Δ/(kBT)); and
Ra = Ra0 - Ra1 × Tn2

*Khalid et al. Phys. Rev. B 85, 134424 (2012).

ZnO – Electrical studies
• Rm associated with metallic islands 0.44

could possibly be related to

Experiment
0.42 Fit

superparamagnetic defect clusters 0.40

0.38

 (m .cm )
0.36

• a nearly temperature independent 0.34

Ra, consistent with the assumption 0.32

that the corresponding region is 0.30

disordered 0.28
0 50 100 150 200 250 300
T (K)

Temperature dependent resistivity for a 5% Gd implanted and

• Obtained an activation of 54 meV, 650 oC ZnO single.

which is close to the 60 meV found in

low energy H implanted ZnO [Khalid et
al. Phys. Rev. B 85, 134424 (2012)]
Magnetic studies – VSM & SQUID
Magnetic Moments and Magnetic Fields
• A loop of electric current generates a magnetic
dipole field
• Field lines run from the North pole to the South
pole
• Field lines indicate the direction of force that would
be experienced by a North magnetic monopole
• Density of flux (or field) lines determines forces on
magnetic poles
• Direction of flux indicates direction of force on a
North pole
B

A
Magnetic Materials
• Material with a net magnetic moment is
magnetized
• Magnetization is the magnetic moment per unit
volume within the material
• Number density of magnetic dipole moments
within material
• unpaired electron spins mainly
• the orbital motion of electrons within the
material to a lesser extent
Flux density within coil and magnetic field
• Increases in proportion to the electric current
• Increases in proportion to the number of turns
per unit length in the coil
• Generally, the orbital and spin magnetic
moments within atoms respond to an applied
magnetic field
• Flux lines are perturbed by specimen
• Magnetic materials tend to concentrate flux lines
• Magnetic properties of the material
B  0 H  M
Measuring magnetic moment of sample
• Pass sample through small “sensing”
coil
• Measure voltage generated across
coil
• Voltage proportional to moment on
specimen
• Use large coil to apply magnetic field
to sample
• Use a cryostat or furnace to vary
temperature of sample
Response of magnetic material to H
• Generally, M changes in magnitude as H is
varied.
• Magnitude of response is called the
“magnetic susceptibility” of the material
• Magnetic susceptibility is sometimes
written as
  MH
• And sometimes as the slope of M vs H
  dM dH
Response of magnetic material to H
• There is a variety of ways that M responds
to H
• Response depends on type of material
• Response depends on temperature
• Response can sometimes depend on the
previous history of magnetic field strengths
and directions applied to the material
Magnetic hysteresis
• M depends on previous state of magnetization
• Remnant magnetization Mr remains when
applied field is removed
• Need to apply a field (coercive field) in
opposite direction to reduce M to zero.
Magnetization vs. temperature
• Heating a magnetized material generally
decreases its magnetization.
• Remnant magnetization is reduced to zero
above Curie temperature Tc
• Heating a sample above its Curie temperature
is a way of demagnetizing it
• Thermal demagnetization
Magnetic Signal Levels
Vibrating Sample Magnetometer (VSM)
• Vibrating-sample magnetometry (VSM) is a scientific tool that
measures magnetic properties
• VSM involves vibration of a magnetic material within a uniform
magnetic field H, generating an electric current in properly placed
sensing coils.
• The resulting voltage developed in the sensing coils varies in
proportion to the magnetic moment of the specimen.
• An electromagnet or a superconducting magnet may generate a
magnetic field.
Vibrating Sample Magnetometer (VSM)
• In 1956 D. O. Smith at MIT first proposed the idea of vibrating-coil
magnetometer

• Paper title - Development of a Vibrating‐Coil Magnetometer [Review

of Scientific Instruments 27, 261 (1956)]

• The paper states “The vibrating‐coil magnetometer measures the

magnetization of a small sample of magnetic material placed in an
external magnetizing field by converting the dipole field of the sample
into an ac electrical signal”.
Vibrating Sample Magnetometer (VSM)
• A VSM operates on Faraday's law of induction,
which states that a changing magnetic field will
produce an electric field (ε),

Where, Δφ: change in magnetic flux

Δt: change in time

• This electric field can be measured and provides

information about the changing magnetic field.
 VSM – Measurement

VSM sample holder

Physical property measurement system (PPMS) VSM motor head

VSM – Measurement
• The VSM linear motor transport uses a uniquely
designed linear motor to vibrate the sample
• The sensitivity of the VSM detection coils is not
significantly affected by large magnetic fields, so the
PPMS VSM can perform sensitive measurements up
to the maximum field available from the PPMS
magnet
• VSM specification in PPMS from Quantum Design:
 Range of Temperature: 300 - 1000 K
 RMS Sensitivity: < 10-5 emu or 0.5%
 Noise Floor: < 10-5 emu rms (H = 0)
 Accuracy: < 1 x 10-5 emu/ tesla
 Temperature Precision: 0.5 K
 Temperature Accuracy: 2%
Superconducting QUantum Interference
Device (SQUID)
• SQUID is loop of superconductor that contains one or more
Josephson Junctions which exploit “Josephson effect”
• One of the discoveries associated with Josephson junctions was that
flux is quantized in units
• The great sensitivity of the SQUID devices is associated with
measuring changes in magnetic field associated with one flux
quantum.
• The device may be configured as a magnetometer to detect incredibly
small magnetic fields
Superconducting QUantum Interference
Device (SQUID)
• SQUID is loop of superconductor that contains one or more Josephson Junctions.
• Interface between two superconducting materials separated by a non-
superconducting barrier.
• A current may flow freely within the superconductors, but the barrier prevents the
current from flowing freely between them.
• However, the supercurrent may tunnel through the barrier, depending on the
quantum phase of the superconductors.
• The amount of supercurrent that may tunnel through the barrier is restricted by
the size and substance of the barrier.
• The maximum value the supercurrent may attain is called the critical current of the
Josephson junction, and is an important phenomenological parameter of a
junction).
SQUID – Josephson Junctions
• British physicist Brian David Josephson, who predicted in 1962 the
mathematical relationships for the current and voltage across the
superconductors coupled by a weak link
• Shared the Nobel Prize in Physics in 1973
SQUID – Josephson Junctions
• SQUID is loop of superconductor that contains one or more
Josephson Junctions.
• Interface between two superconducting materials separated
by a non-superconducting barrier.
• A current may flow freely within the superconductors, but the
barrier prevents the current from flowing freely between
them.
• However, the supercurrent may tunnel through the barrier,
depending on the quantum phase of the superconductors.
• The amount of supercurrent that may tunnel through the
barrier is restricted by the size and substance of the barrier.
• The maximum value the supercurrent may attain is called the
critical current of the Josephson junction, and is an important
phenomenological parameter of a junction).
SQUID – Josephson Junctions
• The great sensitivity of the SQUID devices is associated with
measuring changes in magnetic field associated with one flux
quantum.

• One of the discoveries associated with Josephson junctions was that

flux is quantized in units
 SQUID – Measurement

Magnetic property measurement system (MPMS)

Schematic of MPMS
SQUID – Magnetic moment from dipole fit
ZnO – Magnetic studies
• SQUID results - Ferromagnetic ordering at room temperature

Magnetisation curves for 5% Gd implanted and 650 oC annealed ZnO. Magnetisation curves for 5% Gd implanted and 650 oC annealed ZnO
Inset s show the M(H) raw-data for ZnO:Gd (upper-left panel) and
ZnO (bottom-right panel).
ZnO – Magnetic studies
6

• m' contributions are given as, 5

 2J  1  2J  1  1  x 
m'Gd  n' g B J  coth  x  coth   4

 2J  2J  2J  2 J 

m ' (m A )
3

where, x = gμBJB/(kBT) 2

n' D Peff  B B
2 2

m' D  1

3k BT
0
0 50 100 150 200 250 300 350
where, n'D: is the point defect T (K)

concentration per unit area Temperature dependent magnetization for a 5% Gd implanted

and 650 oC annealed ZnO single crystal at an applied magnetic
Peff: effective moment field of 1 Tesla (filled circles).

• F-centers point defects with a 0.0024% oxygen

vacancy
Optical studies – Photoluminesce and
UV-VISIBLE spectroscopy
Optical studies – Spectroscopy
• Interaction of Radiation with a sample

• The study of molecular or atomic structure of a substance by

observation of its interaction with electromagnetic radiation

• QUANTITATIVELY - For determining the amount of material in a

sample

• QUALITATIVELY – For identifying the chemical structure of a sample

Optical studies – Electromagnetic Spectrum
Optical studies – Radiation energy
• High energy sources produce breaking of bonds: X-Ray, γ Rays, …

• Medium energy sources excite electrons:UV / VISIBLE Spectroscopy

• Low energy sources produce vibrations in chemical bonds: Infrared

Energy

• Very low energy sources produce rotation of the chemical bonds:

Microwaves and Radio waves
Optical studies – Electromagnetic Spectrum

ENERGY 1.2 x105 1.2 x107 12000 310 150 0.12 0.0012
( kJ/mol)

Electronic excitation
e-

FREQUENCY
(Hz) 1020 1018 1016 1014 1012 108

Cosmic γ x Ultra Radio

visible
Infrared Microwave
rays rays rays violet waves
WAVELENGTH
(m)
10-12 10-11 10-9 10-6 10-3 10-1
Optical studies – Vibrational Energy Levels
Vibrational levels
Effects of the
S1
rotational levels
energy levels
depending on the
nature of the
energy received
absorption
Energy

Vibrational levels

rotational levels
S0
Ground state
UV-Vis IR mW
Optical studies – UV-Visible spectroscopy
• UV Radiation: Wavelength range 220 - 380nm
• VISIBLE Radiation: Wavelength range 380 - 780nm
• Substances can absorb varying amounts of UV and/or Visible radiation
at particular wavelengths – Coloured compounds absorb energy in both
UV and visible region of the electromagnetic spectrum.
• Substances can be liquids or solids and measurements are made with
instruments called SPECTROPHOTOMETERS or SPECTROMETERS.
• Modern instruments can be coupled to microscopes which allow solid
samples and very small samples of solids and liquids to be analyzed
both qualitatively and quantitatively.
Optical studies – UV-Visible spectroscopy
• If a particular wavelength of UV or Visible radiation can
be isolated from the source and passed through a
sample which can ABSORB some of the radiation then
the TRANSMITTED light intensity (Iz ) will less than the
INCIDENT light intensity (Io).
• The amount of light transmitted with respect to the
incident light is called TRANSMITTANCE (T) ie.,
Iz
T=
Io

• Sample can absorb all or none of the incident light and

therefore transmittance often quoted I as a percentage:
T (%) = z X 100
Io
Optical studies – UV-Visible spectroscopy
• Strengths of UV-Visible spectroscopy
 The technique is non‑destructive, allowing the sample to be
reused or proceed to further processing or analyses
 Measurements can be made quickly, allowing easy integration into
experimental protocol
 Instruments are easy to use, requiring little user training prior to
use.
 Data analysis generally requires minimal processing, again
meaning little user training is required.
 The instrument is generally inexpensive to acquire and operate,
making it accessible for many laboratories.
Optical studies – UV-Visible spectroscopy
• Limitations of UV-Visible spectroscopy
 Stray light
 Light scattering - light scattering from contaminants
 Interference from multiple absorbing species
 Geometrical considerations - Misaligned positioning of any one of
the instrument's components, especially the cuvette holding the
sample, may yield irreproducible and inaccurate results
Optical studies – UV-Visible spectroscopy
Optical studies – Photoluminesce spectroscopy
• Photoluminescence (PL) is a process in which
the substance absorbs photons (EM radiation)
and then re-radiates photons
• Photoluminescence implies both Fluorescence
and Phosphorescence
• Phosphorescence - ground state to triplet state
and back
• Fluorescence – ground state to singlet state and
back
• ~1,000 times more sensitive than UV-visible
spectroscopy
Optical studies – Photoluminesce spectroscopy
• Composition – Characteristics PL
frequencies
• Stress/Strain State – Changes in
Frequency of PL peaks
• Symmetry/ Orientation – Polarization
of PL peak
• Quality – Width of PL peak
• Amount – Intensity of PL peak
Optical studies – Photoluminesce spectroscopy
• Jablonski Energy Diagram: transitions & Time Scales, Energy Scale
Mechanical studies – Nanoindentation
Mechanical studies – Nanoindentation
• Nanoindentation – Mechanical probing of a material surface to nm-
scale depths, while simultaneously monitoring LOAD and DEPTH
• Optimizing material composition, structure, processing for particular
applications (bulk and thin films)
• Understanding whether thin films, lines, dots have different
mechanical properties than bulk counterparts
• Measuring deformation processes such as dislocation nucleation,
crack growth, etc.
Nanoindentation – Materials engineering
P

Johannes Brinell (1880s) 10 g

stress = s = P/A P = mg
strain = e = [Lf-Li]/Li H = P/[pD2/4]
A Units of stress, but
L NOT stress,
NOT a physical measure
sy n Indicates resistance to
plastic deformation D
E = s/e

Uniaxial tension/ Hardness testing

compression
Nanoindentation – Materials engineering

Indent to several depths to build stress-strain relation:

e = a/R
R s a P/pa2

Multiaxial, NOT uniaxial stress state

a Requires plastic deformation to see
indentation
Nanoindentation – Materials engineering

Microelectronic thin films (early 1980s)

Mechanical properties important: electromigration
Questions:
Is E a function of tf?
Is sy a function of tf?
Is n a function of tf?
10 nm – 1 mm tf
Use nanoindentation to measure thin film props
Consider sharp indenters to mitigate substrate effects
Nanoindentation – Materials science
• By probing materials near atomic and molecular dimensions, can we
learn about fundamental deformation mechanisms?
• Polymers: Entropic elasticity
• Biologicals: Ligand/receptor binding
• Progress due to rapid increases in microelectronics (data acquisition,
signal processing)
• Utility due to rapid progress in computational modeling (same
time/length scales)
Nanoindentation – Materials science

Show P-h response at loading/unloading.

Discuss hysteresis and what it means.
Introduce concepts of indirect measurement: Actually measuring voltages
Emphasize that this is a material signature, but gives no real property values
Nanoindentation – Materials science
dP/dh

Show variables in response:

P C = loading curvature
C dP/dh = unloading stiffness
Pmax, hmax
Wp We Wp = plastic work of indentation
Wt = total work of indentation

Show P-h response at loading/unloading.

Discuss hysteresis and what it means.
Introduce concepts of indirect measurement: Actually measuring voltages
Emphasize that this is a material signature, but gives no real property values
Nanoindentation – Materials science
35 mN

Load
2 mN
SiC (ceramic) 100 500 nm
16 nN
500

PE (polymer)
100 nm
Depth
Nanoindentation – Materials science
• Material assumptions
• Continuum: No structural length scales e.g.
grain size, film thickness
• Homogeneous: One phase
• Elastoplastic: Deforms via plastic yielding,
rather than fracture, phase transformation
Nanoindentation – Materials science
• Indenter considerations
• Ei >> Es: Ideally, deformation occurs only in sample material
• Primarily diamond (hardest natural material)

Spherical: Sharp:
* Elastic, THEN plastic * Immediately elastic AND plastic
* Difficult to machine diamond * Can facet diamond into pyramids, not cones

Vickers Berkovich
Nanoindentation – Instrumentation

NanoIndenter
MTS, TN

Triboindenter NanoTest
Hysitron, MN MicroMaterials, UK
Nanoindentation – working principle
Capacitance of Parallel Plates:
Electric field between two parallel plates: E = V/d

Voltage difference between two plates as +q moves from positive to negative plate:

Capacitance is the amount of charge Q stored per unit voltage V applied to plates:

Relevance to nanoindentation:
(1) As plates move closer, d decreases and V, C increase
(2) Temperature/noise insensitive displacement meter
Nanoindentation – working principle
Inductance of a solenoid

Inductance is
the change in
B(V) created
by a change
in I

For fixed A, a change in current I leads to:

Magnetic field of a solenoid:

Thus

Relevance to nanoindentation:
(1) Can be used to exact motion (change in I)
(2) Can be used to measure load (change in I or V)
Nanoindentation – working principle
1.

iii. Cm = Machine Compliance

Definition: Displacement of the instrument (load

train) in response to applied load

Importance: Need to subtract this response:

Ctotal = Csample + Cm 2.
Approach:
(1.) Nanoindent standard sample
Determine Cm empirically to get “correct” E, H
(2.) Compress machine with flat
Measure Cm directly
Nanoindentation – working principle

i. P(V)
Add mass to load train
Determine I, V to move mass (LOAD)
Calculate relationship: P = aV
Determine zero point: P = aV + b

ii. h(V)

Move indenter fixed, known distance

Measure corresponding C, V
Calculate relationship: h = aV
Determine zero point: h = aV + b
Nanoindentation – working principle

3-plate capacitor
P, h via same device
Nanoindentation – thin film
Ni coating on Pb-Sn solder: tf = 5 mm
• Results in thin films
• Substrate affects indentation coating coating
+ substrate
response
• Complicated relationship due to n
decreasing
• Empirical rule: hmax < 10% tf for constant
hardness
hardness
continuum analysis to hold
Nanoindentation – thin film
hf h
• Results in thin films
• Substrate affects indentation hs
response
• Complicated relationship due to n
8000

• Empirical rule: hmax < 10% tf for 7000 FILM

continuum analysis to hold 6000

Load [mN]
5000

4000 BULK
3000

2000

1000

0
0 0.1 0.2 0.3 0.4 0.5

Depth [nm]
Nanoindentation – thin film