Principles of Nanometrology

A.A. 2011-2012

About nanometrology
The standardization of methods for measurement, imaging and properties recording at nanoscale undergo continuous updating. The descriptions of methods and apparatuses represents a selection and are proposed on the basis of the Eighth Nanoforum Report: Nanometrology Published by the Nanoforum.org, European Nanotechnology Gateway, in July 2006.
(http://www.nano.org.uk/members/MembersReports/NANOMETROLOGY_Report.pdf)

Step by step
1.
2. 3. 4.

Size determination: PSD for particles (GSD, Grain Size Det., for polycrystalline materials)
Surface Specific Area, SSA Z potential, hydrodynamic radius and electrophoretic mobility Surface and 3D imaging, lattice properties

1. PSD, Particle Size Distribution

The particle-size distribution (PSD) of a powder, or granular material, or particles dispersed in fluid, is a list of values or a mathematical function that defines the relative amount, typically by mass, of particles present according to size. PSD is also known as grain size distribution

2. SSA, Specific Surface Area

The specific surface area, or the total surface area per gram of material, is one of the main properties characterizing nanomaterials, in which it is very larger than in bulk materials.

Measurement
The material is inserted in a closed container, under nitrogen. The gas adsorption to the surface causes a drop of the pressure of nitrogen proportional to the surface Area

Z- Potential
Zeta Potential analysis is a technique for determining the surface charge of nanoparticles in solution. Nanoparticles have a surface charge that attracts a thin layer of ions of opposite charge to the nanoparticle surface. This double layer of ions travels with the nanoparticle as it diffuses throughout the solution

 The electric potential at the boundary of the double layer is known as the Zeta potential of the particles and has values that typically range from +100 mV to -100 mV. Zeta Potential is an important tool for understanding the state of the nanoparticle surface and predicting the long term stability of the nanoparticle.

Electric Double Layer Surrounding nanoparticles

Measuring the Z potential.

A laser beam passes through a cell containing the nanoparticles suspension. When an electric field is applied to the cell, the charged particles moves. When interfering with the laser beam, they cause the laser intensity fluctuate: the recorded signal is proportional to the particle speed. Decrease in Z potential is followed by dramatical aggregation of nanoparticles, big aggregates does not move in the beam light. A scheme of the apparatus follows.

 Zeta potential is a measure of the magnitude of the electrostatic or charge repulsion or attraction between particles.
The Zetasizer Nano series uses second generation PALS (Phase Analysis Light Scattering), called M3PALS to measure the particle velocity.

 The measurement of zeta potential has important applications in a wide range of industries including; ceramics, pharmaceuticals, medicine, mineral processing, electronics and water treatment.

In water treatment, monitoring dosage using zeta potential measurements can reduce the cost of chemical additives by optimizing the dosage control.

1) laser; 2) attenuator; 3) cell; 4) compensation optics (Cancelling Dispersion; 5) computer

Hydrodynamic Radius

Electrophoretical mobility.
Perhaps the most widely used technique for measuring zeta potentials in electrophoresis. An electric field is applied across a sample, which induces charged particles to move. The direction and velocity (electrophoretic mobility) of the particles depends on the applied field. The velocity of a particle in an electric field is dependent on:

the strength of the electric field the dielectric constant of the liquid the viscosity of the liquid the zeta potential

4. Surface and 3D imaging, lattice properties

4b. SEM: Scanning Electron Microscopy

A scanning electron microscope (SEM) is a type of electron microscope that produces images of a sample by scanning it with a focused beam of electrons. The electrons interact with atoms in the sample, producing various signals that can be detected and that contain information about the sample's surface topography and composition.

 The electron beam is generally scanned in a raster scan pattern, and the beam's position is combined with the detected signal to produce an image. SEM can achieve resolution better than 1 nanometer. Specimens can be observed in high vacuum, in low vacuum, and (in environmental SEM) in wet conditions.

SEM images

http://www-archive.mse.iastate.edu/microscopy/path2.html

TEM: Transmission Electron Microscopy

Transmission electron microscopy (TEM) is a microscopy technique whereby a beam of electrons is transmitted through an ultra-thin specimen, interacting with the specimen as it passes through.

SEM vs TEM
SEM is based on scattered electrons while TEM is based on transmitted electrons. SEM focuses on the samples surface and its composition whereas TEM provides the details about internal composition. Therefore TEM can show many characteristics of the sample, such as morphology, crystallization,

 TEM has much higher resolution than SEM. SEM allows for large amount of sample to be analysed at a time whereas with TEM only small amount of sample can be analysed at a time.

 SEM is used for surfaces, powders, polished & etched microstructures, IC chips, chemical segregation whereas TEM is used for imaging of dislocations, tiny precipitates, grain boundaries and other defect structures in solids

In TEM, pictures are shown on fluorescent screens whereas in SEM, picture is shown on monitor.

4c. AFM: Atomic Force Microscopy

Basics: The tip of a probe (cantilever) is slowly scanned across the surface. A laser beam, focused on the cantilever, records on a photodetector the deflection of the cantilever, caused by the interaction of its atoms with those on the sample surface. Resolution: depth: 0.5nm-5nm; lateral resolution: 0.2-130 nm.

AFM: Scheme

AFM image of Co3O4 nanoparticles

AFM techniques and applications

Contact Mode (CM): The signal is the movement of the tip, or the adjustments needed to maintain the deflection constant. The stiffness of the lever must be lower than the interatomic forces at the sample surface (1 - 10 nN/nm). For topological recordings. Lateral Force Microscopy (LFM): The twisting of the cantilever is a function of the friction levels in different areas of the sample surface. Force Modulation (FM): The tip (or the sample) is oscillated at a high frequency and pushed into the repulsive regime. The slope of the force-distance curve is correlated to the sample's surface elasticity. Phase Imaging: The phase shift of the oscillating tip is related to specific properties of the sample, such as friction, adhesion, and viscoelasticity.

4d. NMR: Nuclear Magnetic Resonance

Basics: NMR studies a magnetic nucleus by aligning it with a very powerful external magnetic field and perturbing this alignment using an electromagnetic field. The relaxation spectra is a function of nuclear identity, 3D structure of macromolecules in solution or pore dimensions. Resolution: in the nm range.

4e. SAXS: Small Angle X Ray Scattering

Basics: X ray is incident on to a sample and scattered electrons from the sample are analyzed at very low angles. The lattice interplanar spacing of the crystal is a function of the wavelength and of the incidence angle of the x-ray.

Resolution: between 1 nm and >200 nm.

SAXS: Scheme

(http://pubs.usgs.gov/of/2001/of01-041/htmldocs/xrpd.htm)

SAXS: Scheme
(http://pubs.usgs.gov/of/2001/of01-041/htmldocs/xrpd.htm)

BRAGG law: 2d(sin) = o d = lattice interplanar spacing of the crystal = x-ray incidence angle (Bragg angle) = wavelength of the characteristic x-ray

Two-dimensional small-angle X-ray scattering image.

Nanostructure of two styrene-dienestyrene triblock copolymers. Left: a lamellaforming triblock showing a biaxial texture (four-spot pattern). Right: a cylinderforming triblock showing a singlecrystal texture (sixspot pattern).
Images: Sasha Myers, http://www.princeton.edu/cbe/news/archive/

4f. SANS: Small Angle Neutron Scattering

Basics: A neutron source generates a collimated beam; neutrons are scattered by the sample, placed in the beam. A position sensitive neutron detector detects scattered neutrons with 0.05 2 3. The scattered intensity is a function of position. Resolution: between 0.5 nm and 500 nm.

SANS: Scheme

(http://www.ncnr.nist.gov/instruments/usans/)